JP2003066717A - Image forming method and toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image forming method and toner, which decrease development streaks and void and outputs a highly accurate image. SOLUTION: The image forming method uses toner T and a developing device 4. The developing device 4 has toner carrier 4a that holds toner on its peripheral face, and a toner regulating member 3 that has two layers, i.e., a rubber material and a thin metal plate, which are not bonded together. The toner comprises at least a binding resin, wax, and a coloring agent. In the endothermic curve in the DSC measurement of the toner, at least one of the maximum value is in the range of 110 to 160 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming method used in electrophotography, an electrostatic recording method and the like, and a toner used in the image forming method.

[0002]

2. Description of the Related Art Conventionally, as an electrophotographic method, U.S. Pat. No. 2,297,691 and JP-B-42-23910 are known.
There are many known methods disclosed in Japanese Patent Publication No. 43-24748 and Japanese Patent Publication No. 43-24748. Generally, a photoconductive substance is used to form an electric latent image on a photoconductor by various means. Then, the latent image is developed with a developer (hereinafter, referred to as toner), and the toner image is transferred to a transfer material such as paper, if necessary, and then heating, pressure, heating / pressurizing, solvent vapor, etc. To obtain a copy, and the toner remaining on the photoreceptor without being transferred is cleaned by various methods, and the above steps are repeated.

In recent years, such a copying apparatus has begun to be used not only as a general purpose copying machine for copying original documents but also in the field of personal copying for individuals. Therefore, smaller size, more personality, more ecology, and higher reliability have been rigorously pursued, and the copying machine has been configured with elements having high customer satisfaction in various respects. As a result, the performance required of the toner has become higher, and if the performance improvement of the toner cannot be achieved, a better machine cannot be established.

In order to downsize the copying machine, there is a demand for a developer which can contribute to simplifying and downsizing the apparatus related to each process step. For example, when a two-component developer is used in the development process, it is difficult to downsize the device in consideration of the need for an ATR mechanism for controlling the mixing ratio of toner and carrier. On the other hand, when the one-component developer is used, it is advantageous in downsizing the apparatus.

Various methods have been studied as a developing method using a one-component developer. For example, JP-A-55
JP-A-18656 proposes a jumping developing method. An elastic blade composed of an elastic body such as a rubber member is brought into contact with the outer surface of the toner carrier, which is a rotating body,
The toner is rubbed with the rotation of the toner carrier while being in contact with the toner carrier under pressure by the action of the elastic force generated when the toner carrier is displaced by a predetermined amount. It has a function of uniformly controlling the layer thickness of the toner adsorbed and held on the outer peripheral surface of the body by the action of a magnetic force, and frictionally charging the toner.

In a developing device which uses such an elastic blade as a toner regulating member, the toner is forcibly rubbed between the toner carrier and the toner regulating member, so that the toner always has a high and stable tribo. In addition to obtaining a high-density and high-quality image, there is an advantage that the frictional charging mechanism for the toner can be simplified and the device can be downsized.

In order to further reduce the size of the copying machine and promote ecology by using this developing method, a cartridge that does not increase the size of the copying machine body such as a hopper for replenishing toner is used, but the cartridge is used. In recent years, a system for directly supplying toner from a toner container to a developing device has been widely used.

On the other hand, an elastic blade, particularly a toner regulating member using a rubber material, is permanently deformed when used for a certain period of time. Therefore, the toner regulating member needs to be replaced with a new one after being used for a predetermined period of time, which causes a problem of an increase in operating cost. Also,
Although it is possible to reuse the toner regulating member from the viewpoint of resource reuse, it is difficult to reuse the toner regulating member using a rubber material due to deterioration of the rubber material and the like. This is not desirable from an ecological point of view. Therefore, in order to extend the life of the toner regulating member, a two-layer toner regulating member in which a rubber member and a metal member are bonded together has been considered.

However, it is technically very difficult to bond the rubber member and the metal member, and if the material of the rubber member is limited or the adhesive is not smooth, the contact portion between the toner regulating member and the toner carrying member will be. Becomes uneven, it becomes difficult to form a uniform toner layer, and problems such as development streaks occur.

On the other hand, it is common practice to add wax to the toner in order to impart releasability to the toner. A toner containing two or more kinds of wax in order to exert the effect of adding wax is disclosed in Japanese Examined Patent Publication No. 52-330.
5, JP-A-58-21559, JP-A-6-216
2-100775, JP-A-4-124676, JP-A-4-299357, and JP-A-4-362.
It is disclosed in Japanese Patent Laid-Open No. 953, Japanese Patent Laid-Open No. 5-197192, and the like.

The wax contained in these toners is a component which deteriorates the toner having a main endothermic peak in a low temperature region or a high temperature region in the endothermic peak at the time of heating of the DSC curve measured by a differential scanning calorimeter, Many contain many less effective ingredients. Further, when waxes having different melting temperatures are used, if the temperatures are too far apart, it is difficult to sufficiently exhibit the function of the wax when the toner is melted. When such a toner and a two-layered toner regulating member are combined, the surface of the toner regulating member and the toner surface on the toner carrier are poor in matching property, so that the surface of the toner regulating member or the surface of the toner carrier is not scratched or scraped. In some cases, development streaks may be accelerated and development streaks due to toner fusion on the toner carrier, and further white spots may occur.

As described above, the image forming method and the image forming toner in consideration of the development streak in the personal copying apparatus are still insufficient and have many points to be improved.

[0013]

SUMMARY OF THE INVENTION The present invention has been made from the above point of view, and greatly improves the problems of the prior art as described above, suppresses development streaks, and enables high-definition image output. An object of the present invention is to provide an image forming method and a toner.

Another object of the present invention is to provide an image forming method and a toner for suppressing white spots due to development.

[0015]

Means for Solving the Problems The inventors of the present invention have reached the following invention in the course of earnestly studying to develop an image forming method and a toner which can solve the above-mentioned various problems and meet the object of the present invention. .

That is, the present invention is an image forming method including at least a developing step of developing an electrostatic charge image on an image bearing member by using a developing device, wherein the developing device comprises a toner and the toner on the outer periphery thereof. At least a toner carrying member carried on the surface and a toner regulating member having one end supported by the developing device main body and the other end abutting the surface of the toner carrying member to regulate the layer thickness of the toner on the toner carrier. The toner regulating member has two layers of a rubber material and a metal thin plate, and the rubber material and the metal thin plate are not bonded, and the toner contains at least a binder resin, a wax and a colorant. The image forming method is characterized in that the toner contains at least one maximum value in the temperature range of 110 to 160 ° C. in the endothermic curve in DSC measurement of the toner.

Further, the present invention is a toner used in the image forming method of the present invention, which contains at least a binder resin, a wax and a colorant, and has at least one maximum in the endothermic curve in the DSC measurement of the toner. Value 110
The toner has a temperature range of up to 160 ° C.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The present inventor considers the reason why the image forming method and toner of the present invention exert their original effects as follows.

When an elastic blade made of only an elastic resin is used as the toner regulating member instead of the toner regulating member having two layers of a rubber material and a thin metal plate, which is a feature of the present invention, a large number of images are formed. At the time of ejection, the elastic blade is slightly bent, which causes troubles in toner regulation and easily causes development streaks. Further, for example, when a blade made of a thin metal plate is used, the durability of the blade is improved, but the toner carrier is scratched or scratched, and development streaks frequently occur.

In order to solve these problems, even if a toner regulating member having two layers of a rubber material and a thin metal plate is used, when combined with a toner having high elasticity, fine scratches tend to occur on the surface of the toner regulating member. It is in. On the other hand, when combined with a toner having low elasticity, the toner is fixed and fused due to the unevenness of the surface of the toner carrier, and white spots tend to occur.

In order to solve this problem, a toner regulating member having two layers of a rubber material and a thin metal plate is used, and wax existing in the toner present in the gap between the toner regulating member and the toner carrying member is added to the toner regulating member. By exhibiting lubricity, scratches and abrasion of the toner carrier are reduced, development streaks are suppressed, and the plastic effect derived from wax does not impair the elasticity of the toner more than necessary. It has become possible to prevent toner fusion to the carrier and suppress streaks and white spots on the image. Specifically, a toner regulating member having two layers of a rubber material and a thin metal plate is used, and the DSC
By using the toner having at least one maximum value in the temperature range of 110 ° C. to 160 ° C. in the endothermic curve in the measurement, it becomes possible to suppress the occurrence of development streaks and white spots.

In the image forming method and toner of the present invention, it is preferable to interpose a powder between the rubber material and the thin metal plate of the toner regulating member in order to more effectively suppress the occurrence of development streaks and white spots. .

Embodiments of the present invention will be specifically described below. <1> Image forming method of the present invention The image forming method of the present invention has at least a developing step of developing the electrostatic charge image on the image bearing member using a developing device.
In addition to the developing process, a charging process for charging the image carrier, an electrostatic charge image forming process for forming an electrostatic charge image on the charged image carrier, a transfer process for transferring the developed toner image to a transfer material, and a transfer process. It includes a step used in a general image forming method such as a fixing step of fixing a toner image on a material.

In the charging step and transfer step which can be used in the image forming method of the present invention, a method of using a corona discharger which is not in contact with the image carrier, a roller type, a belt type,
There are any type of contact type such as a combination of a belt and an electrode blade, and any type can be used.

The image carrier of the present invention includes an amorphous silicon photoconductor and an organic photoconductor, and the organic photoconductor is preferably used.

The organic photoreceptor may be a so-called single-layer type in which the photosensitive layer contains a charge generating substance and a substance having a charge transporting property in the same layer, and the function separation is composed of the charge transporting layer and the charge generating layer. Type photoconductor may be used. A function-separated type photoreceptor is preferable, and among them, a laminated type photoreceptor having a structure in which a charge generation layer and then a charge transport layer are laminated in this order on a conductive substrate is one of the preferable examples. The image forming method of the present invention is particularly effective when an organic photoreceptor in which the surface of the image bearing member is an organic compound such as resin is used. When the organic compound forms the surface layer of the photoconductor, the wax contained in the toner exerts releasability at the contact point on the surface of the photoconductor, so that the transferability and the cleaning property are deteriorated.
It is preferable because it suppresses the occurrence of fusion and filming.

In the image forming method of the present invention,
It is preferable to have a cleaning step in order to remove the toner remaining on the surface of the image carrier after the transfer step.

The cleaning method used in the cleaning process includes a blade cleaning method, a mag brush cleaning method, a fur brush cleaning method,
Roller cleaning methods, and combinations thereof may be mentioned. A blade cleaning method is particularly preferable.

In the blade cleaning method, a resin having elasticity such as urethane rubber or silicone rubber is used as a blade, or a resin having elasticity like a chip is held at the tip of a blade made of metal or the like in the moving direction of the photoreceptor. It is used by abutting or pressing in the forward direction or the reverse direction. Preferably, the blade is brought into pressure contact in the direction opposite to the moving direction of the photoconductor. At this time, the contact pressure of the blade with respect to the photoconductor is preferably 20 g / cm or more, more preferably 30 to 80 g / cm in terms of linear pressure.

Since the toner of the present invention used in the image forming method of the present invention can obtain appropriate friction and is excellent in releasability and lubricity, it exhibits not only good cleaning property by blade cleaning but also photosensitive property. Even if the blade is brought into contact with the body, it is not easily scratched or scraped. On the other hand, fusion and filming are less likely to occur. The toner of the present invention will be described later.

The image forming method of the present invention may include a fixing step. As a means used in the fixing step, a heating / pressurizing roll fixing device or a fixedly supported heating body and the heating body are pressed against each other. In addition, a fixing unit that heat-fixes the toner by a pressure member that brings the transfer material into close contact with the heating body via the film can be used. The transfer material used in the present invention may be an intermediate transfer belt or an intermediate transfer member such as the belt, in addition to commercially available paper and OHT.

Next, the image forming method of the present invention will be described with reference to the drawings. FIG. 1 shows an example of an image forming apparatus using the image forming method of the present invention. However, the present invention is not limited to this.

The image bearing member 1 is made of an organic photosensitive member, is uniformly charged by the charging roller 1, and then is irradiated with a laser beam L modulated by an image signal by a laser scanner (not shown) to obtain a desired electrostatic charge image. Is formed. The electrostatic charge image is reversely developed by the toner T contained in the developing device 4 and visualized and developed as a toner image. On the other hand, the transfer material P fed by the feeding means (not shown) is guided to the transfer portion by the pair of conveying rollers 5a and 5b and the transfer entrance guides 6a and 6b, and a voltage having a polarity opposite to that of the toner is applied, The toner image is transferred onto the transfer material P by the transfer roller 7 as a transfer unit that forms a nip with the image carrier. After that, the transfer material P is removed of the excessive transfer current by the charge elimination needle 8, is then conveyed by the conveyance guide (conveyance unit) 10, is guided to the fixing device 100, and the toner image on the transfer material P is thermally fixed. . After the transfer, the toner remaining on the surface of the image carrier is cleaned by the cleaner 9, and the same image forming process is repeated again.

The toner regulating member used in the image forming method of the present invention has two layers of a rubber material and a metal thin plate, and the rubber material and the metal thin plate are not bonded. To make the toner regulating member into two layers without adhering the rubber material and the thin metal plate,
The method of superimposing and the method of superimposing by interposing a powder therebetween can be mentioned.

Specifically, one example is shown in FIG. 2. After the rubber material 3a is adhered and fixed to the blade supporting sheet metal 3d, a desired amount of the powder 3b is applied dry or wet to form the metal thin plate 3c.
Is a fixed one. The rubber material includes
A commercially available rubber material can be used, and in particular, polyurethane, silicone rubber, liquid rubber and the like are preferably used.

As the thin metal plate, a general-purpose metal material made into a thin plate by rolling or the like is used, and a SUS thin plate is particularly preferably used.

The rubber material or the thin metal plate may have any shape,
The size can be adjusted.

As the powder to be interposed between the rubber material and the thin metal plate, it is possible to use powder of an organic material or an inorganic material having a spacer effect which does not bring the rubber material and the metal material into contact with each other, and a mixture thereof. . In particular, a fluororesin powder that has little chemical influence on the rubber material and the metal material is preferably used.

The developing device used in the image forming method of the present invention comprises a developing container having at least the toner regulating member and a toner carrier, and a toner container detachably attached to the developing container for accommodating toner. And preferably. By using the developing device, it can be expected to reduce the toner replenishing operation load and the operating cost even in a personal copying machine.

The toner regulating member has one end supported by the main body of the developing device and the other end abutting the surface of the toner carrier to regulate the layer thickness of the toner on the toner carrier.

FIG. 3 shows an example of the developing device used in the present invention. The toner container 4 is provided in the developing container 4g.
a, a toner feeding member 4b, an opening shutter portion 4d, a toner regulating member 3 and the like are incorporated, and a toner container 4f having an agitating member 4e is attached to the developing container to form a developing device. In FIG. 3, the opening shutter unit 4
d is stored.

When the image is produced using the developing device and the toner is consumed, the toner container 4f may be removed and a new toner container may be set. The toner in the toner container 4f passes through the opening 4c and the toner feeding member 4b,
The toner is supplied to the toner carrier 4a, and the image can be output.

The above-mentioned toner container can be used in any shape, but more preferably, the toner container can be incorporated into a developing device used in a personal copying machine, the container shape with a small dead space, the toner replenishing property, and the like. In consideration of this, a cylindrical toner supply container is preferably used.

<2> Toner of the Present Invention The toner used in the present invention contains at least a binder resin, a wax and a colorant, and has at least one local maximum value of 11 in the endothermic curve in DSC measurement of the toner.
It is necessary to have the temperature range of 0 to 160 ° C. FIG. 4 is a schematic diagram when there is one maximum value in the endothermic curve of the toner DSC chart, and FIG. 5 is a schematic diagram when there are two maximum values in the endothermic curve of the toner DSC chart.

In the present invention, the endothermic curve of the DSC chart is a differential thermal analysis measuring device (DSC measuring device), for example,
Using DSC-7 (Perkin Elmer), AST
Created according to MD3418-82.

The measurement sample is 5 to 20 mg, preferably 10
Precisely weigh mg. This was placed in an aluminum pan, and an empty aluminum pan was used as a reference, and the temperature rising rate was 10 ° C./min. Measure under normal humidity. During this temperature raising process, the temperature 110 to 16
The endothermic peak of the main peak in the range of 0 ° C is obtained. The peaks that can be identified at this time are counted and set to the maximum value.

In order for the toner of the present invention to have the maximum value in the temperature range of 110 to 160 ° C. in the endothermic curve of the DSC chart of the toner, the wax shown below may be used. The wax used in the toner of the present invention includes the following waxes, which may be used alone or in combination. Aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax and paraffin wax; oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax; block copolymers thereof; carnauba wax, sazol Examples of the wax include waxes and waxes having a fatty acid ester as a main component such as montanic acid ester wax; those obtained by partially or entirely deoxidizing fatty acid esters such as deoxidized carnauba wax. Further, saturated straight-chain fatty acids such as palmitic acid, stearic acid, montanic acid, or long-chain alkylcarboxylic acids having a longer-chain alkyl group; unsaturated fatty acids such as blancic acid, eleostearic acid, and valinaric acid; stearic alcohol , Aralkyl alcohol, behenyl alcohol,
Saturated alcohols such as carnaubayl alcohol, ceryl alcohol, melysyl alcohol, or long-chain alkyl alcohols having a longer-chain alkyl group; polyhydric alcohols such as sorbitol; linoleic acid amide, oleic acid amide, lauric acid amide Saturated fatty acid amides such as methylenebisstearic acid amide, ethylenebiscapric acid amide, ethylenebislauric acid amide, hexamethylenebisstearic acid amide, ethylenebisoleic acid amide, hexamethylenebisoleic acid amide, etc. Unsaturated fatty acid amides such as N, N'-dioleyl adipamide, N, N'-dioleyl sebacic acid amide; aroma such as m-xylenebisstearic acid amide, N, N'-distearylisophthalic acid amide Bisami Kinds: Fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate (generally called metal soap); Grafting vinyl monomers such as styrene and acrylic acid on aliphatic hydrocarbon wax Graft waxes; partially esterified products of fatty acids such as behenic acid monoglyceride and polyhydric alcohols; and hydroxyl group-containing methyl ester compounds obtained by hydrogenating vegetable oils and fats.

The wax preferably used is a low molecular weight alkylene polymer obtained by radically polymerizing alkylene under high pressure or using a Ziegler catalyst or other catalyst under low pressure; and is obtained by thermally decomposing a high molecular weight alkylene polymer. Alkylene polymer; Low molecular weight alkylene polymer that is by-produced during the polymerization of alkylene is separated and purified; From the distillation residue of the hydrocarbon polymer obtained by the Arge process from the synthesis gas consisting of carbon monoxide and hydrogen, or the distillation residue A polymethylene wax obtained by extracting and fractionating a specific component from a synthetic hydrocarbon obtained by hydrogenating An antioxidant may be added to these waxes. Furthermore, linear alcohols, linear fatty acids, linear acid amides, linear esters, or montan derivatives are mentioned. It is also preferable that impurities such as liquid fatty acid have been previously removed from these waxes.

The wax used in the present invention is at least one mixture selected from the group consisting of a) a mixture of polypropylene and polyethylene, b) a mixture of polypropylene and a polyethylene derivative, c) a mixture of polypropylene and a polypropylene derivative. Is preferably used. When such a mixture is contained in the toner, high releasability and slipperiness can be imparted to the toner, and scratches or abrasion on the surface of the toner regulating member can be more effectively suppressed.

Regarding the molecular weights of the above polypropylene and polyethylene, the number average molecular weight (Mn) is preferably 200 to 2000, more preferably 300 to 1200, and the weight average molecular weight (in consideration of the dispersibility of the wax in the toner). Mw) is preferably 400 to 3000, and further 80
0-2500 is preferable. The mixing ratio of these mixtures is 1: 9 in any of a) to c), considering that the releasing property and the slipping property of each wax in the toner are exhibited.
It is preferably ˜9: 1. As the polyethylene derivative or the polypropylene derivative, a compound having at least one functional group on the side chain or terminal of the polymer of polyethylene or polypropylene is used in consideration of the dispersibility of the wax in the toner.

As a method for incorporating the above wax into the toner of the present invention, the following methods can be mentioned. (1) Wax, binder resin, colorant and, if necessary, other additives are sufficiently mixed by a mixer such as a ball mill, and then melted, kneaded and kneaded by using a heat kneader such as a heating roll, a kneader or an extruder. The mixture is kneaded to mix the wax and the resin component with each other, cooled and solidified, and then pulverized. (2) When two or more types of wax are contained, the waxes are melt-mixed in advance with stirring at the wax melting temperature or higher, cooled and solidified, and then pulverized, and then the method (1) is performed. (3) The binder resin is dissolved in a solvent, the temperature of the resin solution is raised, wax is added and mixed with stirring, and the solvent is removed, dried, and then pulverized, and then the method (1) is performed.

Among the above methods, the method (2) or (3) is preferable in terms of dispersibility of the wax component in the toner particles,
Furthermore, the method (3) is excellent in manufacturing stability.

The amount of the wax used in the present invention is 0.1 to 20 parts by weight, preferably 0.1% by weight per 100 parts by weight of the binder resin, in consideration of suppression of development streaks and white spots. 5-1
0 mass part is preferable. When two or more waxes are used, the total number of these waxes is preferably within the above range. In this case, the mixing ratio of wax can be set arbitrarily.

The toner of the present invention contains no THF insoluble matter, and the THF soluble matter of the toner has at least a peak or a high molecular weight peak in the shoulder in the region of molecular weight of 1 × 10 ^{5 to} 3 × 10 ^{6 in} the GPC chromatogram. It is preferable that the ratio of the high molecular weight is 5 to 45% by mass.

By containing such a high molecular weight component, preferable viscoelasticity can be imparted to the toner. When the amount is out of the above range, scratches and abrasion on the toner regulating member are promoted, and development streaks are likely to occur, and toner fusion to the toner carrier tends to occur.

In the present invention, the molecular weight distribution of the wax or toner is measured by GPC (gel permeation chromatography) under the following conditions. <GPC measurement conditions for wax or toner> Device: GPC-150C (manufactured by Waters) Column: GMH-HT (manufactured by Tosoh Corporation) Dual temperature: 135 ° C Solvent: o-dichlorobenzene (addition of 0.1% ionol) ) Flow rate: 1.0 ml / min. Sample: A sample having a concentration of 0.15 mass% is measured under the condition of 0.4 ml injection or more, and a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample is used for calculating the molecular weight of the sample. Further, it is calculated by converting with a conversion formula derived from the Mark-Houwink viscosity formula.

In the present invention, the content of the high molecular weight component of the toner is calculated from the peak area in the GPC chromatogram.

In the toner of the present invention, it is preferable to use the charge control agent in the toner particles (internal addition) or in the mixture with the toner particles (external addition). The charge control agent makes it possible to control the charge amount adapted to other systems such as a developing system, and particularly in the present invention, this makes it possible to optimize the toner charge amount on the transfer material. Good transferability can be obtained.

When the toner of the present invention has a negative triboelectric chargeability,
As a charge control agent, an organic metal complex salt such as a metal salicylate, a metal alkylsalicylate, a metal dialkylsalicylate, or a metal naphthoate; a dye such as a monoazo dye; a monoazo dye derivative such as a metal complex of a monoazo dye is contained. Is desirable.

Examples of the monoazo dye derivative as the negative charge control agent include those represented by the general formula (I).

[0061]

[Chemical 1] (In the formula, M represents a coordination center metal, and Cr, C having a coordination number of 6
O, Ni, Mn, Fe, etc. are mentioned. Ar is an aryl group, and examples thereof include a phenyl group and a naphthyl group, which may have a substituent. As the substituent in this case,
Examples thereof include a nitro group, a halogen group, a carboxyl group, an anilide group, an alkyl group having 1 to 18 carbon atoms, and an alkoxy group. X, X ′, Y and Y ′ are —O—, —CO—, —NH
Or -NR- (R is an alkyl group having 1 to 4 carbon atoms). A ⁺ represents hydrogen, sodium ion, potassium ion, ammonium ion, and aliphatic ammonium ion. )

In particular, the more effective charge control agent usable in the present invention is a monoazo iron complex salt represented by the general formula (II).

[0063]

[Chemical 2] (Wherein, X ₁ and X ₂ are a hydrogen atom, a lower alkyl group, a lower alkoxy group, a nitro group or a halogen atom, X ₁
And X ₂ may be the same or different, and m and m ′
Represents an integer of 1 to 3, Y ₁ and Y ₃ are hydrogen atoms, C 1 to
18 alkyl groups, alkenyl groups, sulfonamide groups,
Represents a mesyl group, a sulfonic acid group, a carboxyester group, a hydroxy group, a C1-18 alkoxy group, an acetylamino group, a benzoylamino group or a halogen atom, and Y ₁
And Y ₃ may be different, n and n ′ represent an integer of 1 to 3, Y ₂ and Y ₄ represent a hydrogen atom or a nitro group, and A ⁺
Represents a cation ion, has an ammonium ion of 75 to 98 mol%, and additionally has a hydrogen ion, a sodium ion, a potassium ion, or a mixed ion thereof. )

When the toner of the present invention has a positive triboelectric charging property, a modified product of nigrosine and a fatty acid metal salt as a charge control agent; tributylbenzylammonium 1-
Hydroxy-4-naphthosulfonate, quaternary ammonium salts such as tetrabutylammonium tetrafluoroborate, and onium salts such as phosphonium salts which are analogs thereof, lake pigments thereof, triphenylmethane dyes and lake pigments thereof , Metal salts of higher fatty acids;
Dibutyltin oxide, dioctyltin oxide,
Diorgano tin oxide such as dicyclohexyl tin oxide; diorgano tin borate such as dibutyl tin borate; guanidine compound, imidazole compound and the like can be used. Examples of rake agents include phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanic acid, ferrocyanide and the like.

These can be used alone or in combination of two or more kinds. Among these, a triphenylmethane compound and a quaternary ammonium salt whose counter ion is not halogen are preferably used.

Further, a homopolymer of the monomer represented by the general formula (III),

[0067]

[Chemical 3] (R ₁ represents H and CH ₃ , and R ₂ and R ₃ represent a substituted or unsubstituted alkyl group (preferably C1 to C4).) The above-mentioned styrene, acrylic acid ester, methacrylic acid ester or the like A copolymer with a coalescing monomer can be used.

The charge control agent in these cases also functions as (all or part of) the binder resin.

It is possible to contain one or more of the above charge control agents. The content of the charge control agent is 0.1 to 5 parts by mass with respect to 100 parts by mass of the binder resin of the toner, in consideration of controlling the fluidity and the amount of charge of the toner to avoid generation of fog and low density. Part is preferable, and 0.2 to 3 parts by mass is particularly preferable.

As the binder resin of the toner of the present invention, it is preferable to use vinyl resin or polyester resin as the main component.

Examples of the vinyl-based monomer used for producing the vinyl-based resin include the following.
For example, 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-
Butyl styrene, pn-hexyl styrene, pn-
Octyl styrene, pn-nonyl styrene, pn-
Styrene such as decyl styrene and pn-dodecyl styrene and its derivatives; ethylene, propylene, butylene,
Ethylenically unsaturated monoolefins such as isobutylene; unsaturated polyenes such as butadiene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide, vinyl fluoride; vinyl acetate, vinyl propionate, vinyl benzoate, etc. Vinyl ester acid; methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylic acid n
-Butyl, isobutyl methacrylate, n-methacrylic acid
Α-methylene aliphatic monocarboxylic acid esters such as octyl, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate , N-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, etc. Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone ; N- vinyl pyrrole, N- vinyl carbazole, N- vinyl indole, N- vinylpyrrolidone, etc. N- vinyl compounds, vinyl naphthalenes;
Examples thereof include acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide; and the above-mentioned α, β-unsaturated acid esters and dibasic acid diesters.

Other vinyl-based monomers include unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenylsuccinic acid, fumaric acid, mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride. object,
Unsaturated dibasic acid anhydrides such as alkenyl succinic anhydride;
Maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, alkenyl succinic acid methyl half ester, fumar Acid methyl half ester,
Half ester of unsaturated dibasic acid such as methyl half ester of mesaconic acid; Unsaturated dibasic acid ester such as dimethyl maleic acid and dimethyl fumaric acid; α, β-unsaturated acid such as acrylic acid, methacrylic acid, crotonic acid and cinnamic acid Saturated acid; α, β-unsaturated acid anhydride such as crotonic acid anhydride and cinnamic acid anhydride, and an anhydride of the α, β-unsaturated acid and lower fatty acid;
Examples thereof include monomers having a carboxyl group such as alkenyl malonic acid, alkenyl glutaric acid, alkenyl adipic acid, acid anhydrides thereof and monoesters thereof.

Further, acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate, 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1- A monomer having a hydroxyl group such as hydroxy-1-methylhexyl) styrene is also included as the vinyl-based monomer.

The glass transition temperature of vinyl resin is 45 to 8
0 degreeC is preferable and 55-70 degreeC is more preferable. The number average molecular weight (Mn) of the vinyl resin is 2,500.
Is preferably 50,000 to 50,000, more preferably 3,000 to 2
10,000 is preferable. Weight average molecular weight (Mw) is 1
It is preferably 50,000 to 1,500,000, more preferably 25,000 to 1,250,000.

The glass transition temperature of the vinyl resin is determined by the same measuring method as for toner. Further, the number average molecular weight and the weight average molecular weight of the vinyl resin are determined by the same measuring method as that for the wax or the toner. The vinyl-based resin is prepared by using a general polymerization method such as a suspension polymerization method or a solution polymerization method, but each polymerization method can also be prepared by combining them. The composition of the polyester resin used in the present invention is as follows.

The polyester resin used in the present invention is
45 to 55 mol% of all components are alcohol components,
It is preferable that 55 to 45 mol% is an acid component.

As the alcohol component, ethylene glycol, propylene glycol, 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, and a bisphenol derivative represented by the general formula (IV);

[0078]

[Chemical 4] (In the formula, R is an ethylene or propylene group, and x, y
Are each an integer of 1 or more, and the average value of x + y is 2 to 10. ) Or a diol represented by the general formula (V);

[0079]

[Chemical 5]

Further, glycerin, pentaerythritol, sorbit, sorbitan, and also polyhydric alcohols such as oxyalkylene ether of novolak type phenol resin can be used as the alcohol component.

The acid component of the polyester resin preferably contains 50 mol% of a divalent carboxylic acid in the total acid component in order to control the molecular weight distribution of the toner. Examples of the divalent carboxylic acid include benzenedicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and phthalic anhydride or anhydrides thereof; alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid or azelaic acid or anhydrides thereof, Further, succinic acid substituted with an alkyl group having 6 to 18 carbon atoms or an anhydride thereof; unsaturated dicarboxylic acid such as fumaric acid, maleic acid, citraconic acid, itaconic acid or an anhydride thereof may be mentioned.

Examples of the trivalent or higher acid component include polycarboxylic acids such as trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their anhydrides.

In the present invention, the preferred alcohol component of the polyester resin is the bisphenol derivative represented by the general formula (IV), and the acid component is phthalic acid, terephthalic acid, isophthalic acid or its anhydride, succinic acid, Dicarboxylic acids such as n-dodecenylsuccinic acid or its anhydride, fumaric acid, maleic acid, maleic anhydride, etc. may be mentioned. Preferred examples of the crosslinking component include trimellitic anhydride, benzophenonetetracarboxylic acid, pentaerythritol, and oxyalkylene ether of novolac type phenol resin.

The glass transition temperature of the polyester resin is 40.
-90 degreeC is preferable and 45-85 degreeC is more preferable. The number average molecular weight (Mn) of the polyester resin is preferably 1,000 to 50,000, more preferably 1,5.
00 to 20,000, particularly preferably 2,500 to 1
10,000 is preferable. Weight average molecular weight (Mw) is 3,
000 to 3,000,000 is preferable, and further 1
20,000-2,500,000, especially 40,000-
2,000,000 is preferred. The glass transition temperature of the polyester resin is determined by the same measuring method as for the toner. Further, the number average molecular weight and the weight average molecular weight of the above polyester resin are determined by the same measuring method as for the wax or toner. The polyester resin is prepared using a general polymerization method such as a condensation polymerization method.

The above-mentioned molecular weight distribution is imparted to a vinyl resin or a polyester resin, and a toner is prepared by combining it with other toner constituent materials, so that THF-insoluble matter is not contained and the THF-soluble matter of the toner is measured in a GPC chromatogram. It is possible to obtain a toner having at least a high molecular weight peak or a shoulder high molecular weight peak in the molecular weight range of 1 × 10 ^{5 to} 3 × 10 ⁶ and having a high molecular weight ratio of 5 to 45% by mass.

In the present invention, in order to further optimize the viscoelasticity of the toner, polyurethane, epoxy resin,
If necessary, polyvinyl butyral, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, etc. may be mixed with the above-mentioned binder resin and used. These binder resins are used in an amount of 1-100 with respect to 100 parts by weight of the binder resin described above.
It is preferable to mix them in a ratio of parts by mass.

When the toner of the present invention is used as a magnetic toner, the magnetic substance may also serve as a colorant. The magnetic substance contained in the magnetic toner of the present invention includes magnetite,
Iron oxides such as maghemite and ferrite, and iron oxides containing other metal oxides; metals such as Fe, Co and Ni, or these metals and Al, Co, Cu, Pb, Mg,
Ni, Sn, Zn, Sb, Be, Bi, Cd, Ca, M
Examples thereof include alloys with metals such as n, Se, Ti, W and V, and mixtures thereof.

Conventionally, as a magnetic material, iron tetroxide (Fe) has been used.
₃ O ₄ ), ferric sesquioxide (γ-Fe ₂ O ₃ ), zinc iron oxide (Z
nFe ₂ O ₄ ), yttrium iron oxide (Y ₃ Fe ₅ O ₁₂ ),
Iron cadmium oxide (CdFe ₂ O ₄ ), iron gadolinium oxide (Gd ₃ Fe ₅ —O ₁₂ ), iron oxide copper (CuFe ₂ O ₄ ),
Lead iron oxide (PbFe ₁₂ —O ₁₉ ), iron nickel oxide (Ni
Fe ₂ O ₄ ), iron neodymium oxide (NdFe ₂ O ₃ ), barium iron oxide (BaFe ₁₂ O ₁₉ ), magnesium iron oxide (M
gFe ₂ O ₄ ), iron manganese oxide (MnFe ₂ O ₄ ), lanthanum iron oxide (LaFeO ₃ ), iron powder (Fe), cobalt powder (Co), nickel powder (Ni), etc. are known.
In the present invention, the above-mentioned magnetic substance may be used alone or
It is preferable to selectively use a combination of two or more species. The preferred magnetic material used in the present invention is a fine powder of iron trioxide or γ-iron sesquioxide.

These magnetic materials have an average particle size of 0.05 to 2
At about μm, the magnetic characteristics under application of 795.8 kA / m are coercive force of 20 to 150 kA / m and saturation magnetization of 50 to 200 Am.
² / kg (preferably 50 to 100 Am ² / kg) and a residual magnetization of ^{2 to 20} Am ² / kg are desirable.

The average particle size of the above magnetic substance was determined by scanning the sample with a scanning electron microscope (FE-SEM (S-80, manufactured by Hitachi, Ltd.).
0)) is taken in a magnified photograph at a magnification of 20,000 times, the long axis values of 100 to 200 particles are randomly measured, and the average value is calculated. The magnetic characteristics are measured using, for example, a DC magnetization BH characteristic automatic recording device BHH-50 manufactured by Riken Denshi Co., Ltd. The magnetic characteristic value is obtained from a hysteresis curve at the time when a magnetic field of ± 795.8 kA / m is created.

The above-mentioned magnetic substance is prepared, for example, from ferrous sulfate as a raw material by a wet synthesis method in which an oxidation reaction is carried out in an aqueous solution.
Using the synthesized magnetic material as a raw material, first, it is oxidized by passing air at 750 ° C. for 2 hours to obtain α-Fe ₂ O ₃ ,
Next, the temperature is set to 350 ° C., and then a gas obtained by mixing hydrogen gas and nitrogen gas is bubbled for 3 hours to obtain the layer.

The amount of the magnetic material used is 10 to 200 parts by mass, preferably 20 parts by mass, based on 100 parts by mass of the binder resin.
It is preferable to use up to 150 parts by mass.

In the toner of the present invention, carbon black, titanium white, or any other pigment and / or dye can be used as the colorant, regardless of whether it is a single component or a two component. For example, when the toner of the present invention is used as a magnetic color toner, the dye may be C.I. I. Direct Red 1, C.I. I. Direct Red 4, C.I. I. Acid Red 1, C.I. I. Basic Red 1, C.I. I.
Mordant Red 30, C.I. I. Direct Blue 1,
C. I. Direct Blue 2, C.I. I. Acid Blue 9, C.I. I. Acid Blue 15, C.I. I. Basic Blue 3, C.I. I. Basic Blue 5, C.I. I. Mordant Blue 7, C.I. I. Direct Green 6, C.I.
I. Basic Green 4, C.I. I. There are Basic Green 6 etc. Examples of pigments include yellow lead, cadmium yellow, mineral fast yellow, navel yellow, naphthol yellow S, Hansa yellow G, permanent yellow NCG, tartrazine lake, red lead yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, benzidine orange G. , Cadmium red, Permanent red 4R, Watching red calcium salt, Eosin lake, Brilliant carmine 3
B, manganese purple, fast violet B, methyl violet lake, navy blue, cobalt blue, alkali blue lake, Victoria blue lake, phthalocyanine blue, fast sky blue, indanthrene blue BC, chrome green, chromium oxide, pigment green B, malachite. Green Rake, Final Yellow Green G, etc.

The amount of the colorant used is preferably 0.1 to 60 parts by mass, more preferably 0.5 to 50 parts by mass, based on 100 parts by mass of the binder resin.

Further, the toner of the present invention has environmental stability,
To improve charging stability, development stability, fluidity and storage stability,
It is preferable to mix inorganic fine powders, especially hydrophobicized inorganic fine powders. Examples thereof include silica fine powder, titanium oxide fine powder, and hydrophobized products thereof. They are preferably used alone or in combination.

As the silica fine powder, both the so-called dry method or fumed silica produced by vapor phase oxidation of a silicon halogen compound and the so-called wet silica produced from water glass can be used. However, dry silica having less silanol groups on the surface and inside the silicic acid fine powder and having no production residue such as Na ₂ O and SO ₃ ²⁻ is preferable.

In wet silica, a composite powder of silica and another metal oxide may be obtained by using another metal halogen compound such as aluminum chloride or titanium chloride together with a silicon halogen compound in the manufacturing process. It is possible and they are also included.

Further, the inorganic fine powder is preferably hydrophobized. The hydrophobic treatment is performed by treating with an organic silicon compound or the like that reacts with or physically adsorbs on the inorganic fine powder.

As a preferable method of the hydrophobic treatment, silica fine powder will be described below as an example. Examples thereof include a method in which a fine powder of dry silica produced by vapor-phase oxidation of a silicon halide is treated with a silane coupling agent, or simultaneously with a silane coupling agent and an organosilicon compound such as silicone oil.

Examples of the silane coupling agent used for the hydrophobizing treatment include dimethyldichlorosilane, trimethylchlorosilane, allyldimethylchlorosilane, hexamethyldisilazane, allylphenyldichlorosilane, benzyldimethylchlorosilane and vinyltrichlorosilane. Examples thereof include ethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, divinylchlorosilane, and dimethylvinylchlorosilane.

The silica fine powder is treated with a silane coupling agent by a dry treatment in which the vaporized silane coupling agent is reacted with a silica fine powder made into a ground state by stirring or the like, or the silica fine powder is dispersed in a solvent. It is possible to use a generally known method such as a wet method in which the silane coupling agent thus obtained is subjected to a drop reaction.

Examples of the organosilicon compound include silicone oil. As a preferred silicone oil, one having a viscosity of about 30 to 1000 centistokes at 25 ° C. is used.

In the case of the negatively chargeable silica fine powder, for example, dimethyl silicone oil, alkyl modified silicone oil, α-methylstyrene modified silicone oil, chlorophenyl silicone oil, fluorine modified silicone oil and the like are preferable.

In the case of positively chargeable silica fine powder, it is preferably treated with a silicone oil having an organo group having at least one nitrogen atom in its side chain, or a nitrogen-containing silane coupling agent.

Examples of the method for treating silicone oil include a method in which silica fine powder treated with a silane coupling agent and silicone oil are directly mixed using a mixer such as a Henschel mixer. Alternatively, it may be prepared by dissolving or dispersing silicone oil in an appropriate solvent, mixing it with silica fine powder, and removing the solvent.

As a preferred method for hydrophobizing the silica fine powder, there may be mentioned a method prepared by treating with dimethyldichlorosilane, then with hexamethyldisilazane, and then with silicone oil.

As described above, it is particularly preferable to treat the silica fine powder with two or more kinds of silane coupling agents and subsequently to treat with silicone oil, since the degree of hydrophobicity can be effectively increased.

The above inorganic fine powder preferably has a specific surface area of 30 m ² / g or more (particularly 50 to 400 m ² / g) measured by the BET method by nitrogen adsorption, regardless of the presence or absence of the hydrophobic treatment. To be In addition, the above-mentioned specific surface area is manufactured by Yuasa Ionics Co., Ltd., and is a fully automatic gas adsorption measuring device:
BE using an autosorb 1 and nitrogen as an adsorption gas
Calculated by the T multipoint method. The sample is pretreated by degassing at 50 ° C. for 10 hours.

External additives other than the inorganic fine powder such as the silica fine powder or the titanium oxide fine powder may be added to the toner of the present invention, if necessary. As an external additive,
For example, lubricants such as Teflon (registered trademark), zinc stearate, and polyvinylidene fluoride are preferable, and polyvinylidene fluoride is particularly preferable. Alternatively, abrasives such as cerium oxide, silicon carbide, and strontium titanate are preferable, and strontium titanate is particularly preferable. Alternatively, titanium oxide,
A fluidity-imparting agent such as aluminum oxide, and particularly a hydrophobicity-imparting agent is preferable. A small amount of anti-caking agent, or a conductivity-imparting agent such as carbon black, zinc oxide, antimony oxide, tin oxide, or white and black fine particles having opposite polarities can be used as a developing property improver.

The external additive mixed with the toner is 0.1 to 5 parts by mass (preferably, 100 parts by mass of the toner).
0.1 to 3 parts by mass) is preferably used.

When the toner of the present invention is a non-magnetic toner which also uses a carrier, for example, a non-coated carrier such as iron powder, ferrite powder, magnetite powder, glass beads, styrene-acrylic resin, silicone resin,
A carrier coated with a fluorine-modified acrylic resin or a granulated carrier can be used.

The carrier is used in an amount of 10 to 1000 parts by mass (preferably 3 parts) with respect to 10 parts by mass of the toner.
It is preferable to use 0 to 500 parts by mass). The particle size of the carrier is 4 to 100 μm (preferably 10 to 80 μm).
m, more preferably 20 to 60 μm) is preferably used in matching with the toner of the present invention.

The toner of the present invention is prepared by thoroughly mixing the above-mentioned toner constituent materials with a mixing device, melting, kneading and kneading with a kneading device, cooling and solidifying, crushing with a crushing device, and classification. It can be produced by performing strict classification with a device and a sieve device.

Examples of the mixing device, kneading device, crushing device, classifying device, and sieving device used in the above production include the following.

(1) Example of mixing device for toner production ・ Henschel mixer (Mitsui Mining) ・ Super mixer (made by Kawata) ・ Ribo cone (manufactured by Okawara Works) ・ Nauta mixer (made by Hosokawa Micron) ・ Spiral pin mixer (Made by Taiheiyo Kiko) ・ Ledige mixer (Matsubo) ・ Turbulizer (made by Hosokawa Micron) ・ Cyclomix (made by Hosokawa Micron)

(2) Example of kneading device for toner production ・ KRC Kneader (Kurimoto Iron Works) ・ Bus Co Kneader (BuuS) ・ TEM extruder (made by Toshiba Machine) ・ TEX twin-screw kneader (Made in Japan) ・ PCM kneader (made by Ikegai Iron Works) ・ Three roll mill (manufactured by Inoue Seisakusho) ・ Mixing roll mill (manufactured by Inoue Seisakusho) ・ Kneader (manufactured by Inoue Seisakusho) ・ Kneedex (Mitsui Mining) ・ MS type pressure kneader (Moriyama Seisakusho) ・ Nider Ruder (Moriyama Seisakusho) ・ Banbury mixer (Kobe Works)

(3) Example of pulverizer for toner production ・ Counter jet mill (made by Hosokawa Micron) ・ Micron jet (made by Hosokawa Micron) ・ IDS type mill (manufactured by Nippon Pneumatic Mfg. Co., Ltd.) ・ PJM jet crusher (made by Nippon Pneumatic Mfg. Co., Ltd.) ・ Cross jet mill (Kurimoto Iron Works) ・ Ulmax (manufactured by Nisso Engineering) ・ SK Jet O Mill (manufactured by Seishin Enterprise) ・ Kryptron (Kawasaki Heavy Industries) ・ Turbo mill (made by Turbo Industry) ・ Innomizer (made by Hosokawa Micron)

(4) Toner manufacturing classifier-Clasir (manufactured by Seishin Company) -Micron Classifier (manufactured by Seishin Company) -Spedic Classifier (manufactured by Seishin Company) -Turbo Classifier (manufactured by Nisshin Engineering) -Micron Separator (Hosokawa Micron) ・ Turboplex (ATP) (Hosokawa Micron) ・ TSP Separator (Hosokawa Micron) ・ Elbow Jet (Nippon Mining) ・ Dispersion Separator (Nippon Pneumatic) ・ YM Micro Cut (Yasukawa Shoji) Made)

(5) Example of sieve device for toner production ・ Ultrasonic (manufactured by Koei Sangyo) ・ Resonator Sieve (manufactured by Tokuju Kosakusho) ・ Vibrasonic system (made by Dalton) ・ Soniclean (made by Shinto Kogyo) ・ Gyro shifter (made by Deoksugung) ・ Circular vibrating screen (made by Tokuju Kosakusho) ・ Turbo screener (manufactured by Turbo Industry) ・ Mitaro Shifter (Makino Sangyo)

Weight average particle diameter (D4) of the toner of the present invention
Takes into consideration toner replenishment performance, streak suppression during replenishment, etc.
It is preferably 5.5 to 13.5 μm. The particle size of the toner can be measured by various methods. In the present invention, Coulter Multisizer (manufactured by Coulter Co.) is used, and the electrolyte is 1% NaC using primary sodium chloride.
l Prepare an aqueous solution. As the electrolytic solution, for example, ISO
TON R-II (manufactured by Coulter Scientific Japan) can be used. As a measuring method, a surfactant as a dispersant in 100 to 150 ml of the electrolytic aqueous solution,
Preferably the alkylbenzene sulfonate is 0.1 to
Add 5 ml and 0.002-0.020 g of measurement sample
Add. The electrolytic solution in which the sample is suspended is about 1 ~
Dispersion treatment is performed for 3 minutes, and the sample solution is added to the cell of the measuring device with a pipette or the like. It should be noted that the volume distribution and the number distribution are calculated by measuring the volume and the number of the toner having a particle size of 2 μm or more using a 100 μm aperture as the aperture.

The weight average particle diameter according to the present invention is determined from the weight standard average particle diameter (D4: the median value of each channel is a representative value for each channel) determined from the volume distribution.

[0122]

EXAMPLES The present invention will be specifically described below based on Examples. However, this does not limit the embodiment of the present invention in any way. The number of parts in the examples is part by mass.

[0123]

Example 1 Binder resin (B-1 shown in Table 1) 100 parts Magnetic material 100 parts Wax (W-1 shown in Table 2) 5 parts Charge control agent 2 parts (General formula (II) The above mixture is melt-kneaded with a twin-screw extruder (PCM kneader manufactured by Ikegai Iron Works) heated to 130 ° C, and the cooled kneaded product is hammer milled (Ikegai Iron Works). ), And the coarsely pulverized material is finely pulverized with a jet mill (IDS type mill made by Nippon Pneumatic), and the obtained fine pulverization is classified with a fixed wall type air classifier (Hosokawa Micron Turboplex) for classification. Produced powder. Further, the obtained classified powder is subjected to strict classification of ultrafine powder and coarse powder at the same time with a multi-division classifier utilizing the Coanda effect (Elbow Jet classifier manufactured by Nittetsu Mining Co., Ltd.) to obtain a weight-average particle size. (D4) 7.5 μm negatively chargeable toner was obtained.

100 parts of the above toner, 1.2 parts of oil-treated silica and 0.4 part of strontium titanate were added,
The toner shown in Table 3 was obtained by mixing with a mixing device (Henschel mixer manufactured by Mitsui Mining Co., Ltd.).

[0125]

[Table 1]

[0126]

[Table 2]

[0127]

[Table 3] Next, this adjusted toner was evaluated by the following method.

As the electrophotographic apparatus, Canon laser beam printer LBP1710 was used. The toner regulating member of the developing device used in the above printer was composed of two layers of urethane rubber and SUS thin plate, and was replaced with the laminated toner regulating member. While replenishing the toner, a printout test was conducted continuously on 20,000 sheets under a low temperature and low humidity environment (15 ° C., 10 RH%) and a high temperature and high humidity environment (32.5 ° C., 80 RH%). An evaluation was made. The evaluation results are shown in Table 4.

The replenishing operation is performed by taking out the developing device from the main body, disassembling the developing container portion, replenishing the toner from the toner filling port, reassembling the developing container portion, and mounting the developing device again on the main body. I went there.

(1) Development streak The appearance of streaks in the toner coat layer on the toner carrier and the effect on the printout image were visually observed and evaluated.
The evaluation criteria are as follows. ◯: Not generated Δ: Development streaks appearing in the toner coat layer are less than 5, and there is no influence on the image. X: 10 or more development lines appearing in the toner coat layer,
Image defects occur.

(2) White Area The appearance of white areas in the toner coat layer on the toner carrier and the effect on the printout image were visually observed and evaluated.
The evaluation criteria are as follows. ◯: Not generated Δ: There are less than 5 white spots in the toner coat layer, and there is no effect on the image. X: 10 or more white spots appearing in the toner coat layer, causing image defects.

(3) Toner replenishment property When toner was replenished to the developing device, comprehensive evaluation was made on the ease of replenishment to the device, the attachment / detachment of the toner container, the mounting of the toner container, and the like. The evaluation criteria are as follows. ○: Easy to replenish Δ: Replenishment operation is complicated and difficult to replenish.

[0133]

[Embodiment 2] Instead of the toner regulating member used in Embodiment 1, two kinds of urethane rubber and SUS thin plate as shown in FIG. 2 are used.
A toner regulating member composed of layers and having a fluorine-based resin powder present in the gap between them is used in the developing device portion, and
LBP17 which enables use of a developing device having a toner container detachably arranged in the developing container as shown in FIG.
Evaluation was performed in the same manner as in Example 1 except that 10 modified machines were used,
The results shown in Table 4 were obtained. The toner was replenished by replacing the toner container in which the toner was consumed with a new toner container without removing the developing device.

[0134]

Examples 3 to 6 Binder resins B-1 to B- shown in Table 1
4, toners 2 to 6 shown in Table 3 were prepared in the same manner as in Example 1 except that the waxes W-2 to W-6 shown in Table 2 were used and the kind and addition amount of external additives were changed. Obtained.

Toners 2 to 6 were evaluated in the same manner as in Example 2 and the results shown in Table 4 were obtained.

[0136]

Comparative Examples 1 to 3 The binder resin B-2 shown in Table 1 and the waxes W-7 to W-9 shown in Table 2 were used, and the types and addition amounts of the magnetic substance and the external additive were changed. The toners 7 to 9 shown in Table 3 were obtained in the same manner as in Example 1 except for the above.

The electrophotographic apparatus used in Example 1 was evaluated in the same manner as in Example 1, and the results shown in Table 4 were obtained.

[0138]

[Table 4]

[0139]

According to the present invention, it is possible to provide an image forming method and a toner for obtaining a high-quality image without developing stripes and white spots.

[Brief description of drawings]

FIG. 1 is a schematic explanatory diagram of an image forming apparatus using an image forming method of the present invention.

FIG. 2 is a schematic explanatory view of a toner regulating member used in the image forming method of the present invention.

FIG. 3 is a schematic explanatory diagram of a developing device used in the image forming method of the present invention.

FIG. 4 is a schematic diagram in the case where there is one maximum value in the endothermic curve of the DSC chart of the toner.

FIG. 5 is a schematic diagram in the case where there are two maximum values in the endothermic curve of the DSC chart of the toner.

[Explanation of symbols]

1 charging roller 2 photoconductor 3 Toner regulating member 3a Rubber material 3b powder 3c Metal thin plate 3d blade support sheet metal 4 Developing device 4a toner carrier 4b toner feeding member 4c opening 4d opening shutter section 4e Stirrer 4f Cylindrical container (toner container) 4g developing container 5a, 5b Transport rollers 6a, 6b Transcription entrance guide 7 Transfer roller 8 Static elimination needle 9 cleaner 9a cleaning blade 10 Transport guide (transport unit) 100 fixing device 100a fixing film 100b film support 100c heater support 100c heater 100e pressure roller 11 Charging bias power supply 12 Development bias power supply 13 Transfer bias power supply T toner L laser light P transfer material

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Makoto Unno             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation F-term (reference) 2H005 AA01 AA06 CA04 CA13 CA14                       EA03 EA06                 2H077 AA03 AA35 AB03 AB12 AB15                       AC04 AD06 AD13 AD17 AD23                       AD35 EA03 EA12 EA13 FA00

Claims (10)

[Claims] 1. An image forming method comprising at least a developing step of developing an electrostatic charge image on an image bearing member using a developing device, wherein the developing device carries toner and a toner on an outer peripheral surface thereof. At least one of a toner carrier and a toner regulating member whose one end is supported by the developing device main body and whose other end is in contact with the surface of the toner carrier to regulate the layer thickness of the toner on the toner carrier, The toner regulating member has two layers of a rubber material and a metal thin plate, the rubber material and the metal thin plate are not adhered, and the toner contains at least a binder resin, a wax and a colorant. , At least one of the maximum values in the endothermic curve in the DSC measurement of the toner is 110 to 160.
An image forming method having a temperature range of ° C. 2. The image forming method according to claim 1, wherein powder is interposed between the rubber material and the thin metal plate. 3. The developing device comprises a developing container having at least a toner regulating member and a toner carrier, and a toner container detachably attached to the developing container for accommodating toner. The image forming method according to claim 1 or 2, which is characterized in that. 4. The toner does not contain a THF insoluble matter,
In the GPC chromatogram, the THF-soluble content of the toner has at least a peak or a high molecular weight peak of the shoulder in the region of a molecular weight of 1 × 10 ^{5 to} 3 × 10 ⁶ , and the ratio of the high molecular weight is 5 to 45% by mass. The image forming method according to any one of claims 1 to 3, characterized in that. 5. The wax is at least one mixture selected from the group consisting of a) a mixture of polypropylene and polyethylene, b) a mixture of polypropylene and a polyethylene derivative, c) a mixture of polypropylene and a polypropylene derivative. The image forming method according to any one of claims 1 to 4, further comprising: 6. A developing step of developing an electrostatic charge image on an image carrier using a developing device, wherein the developing device comprises a toner and a toner carrier carrying the toner on an outer peripheral surface thereof. At least one end is supported by the developing device main body, the other end side is in contact with the surface of the toner carrier, and at least a toner regulating member that regulates the layer thickness of the toner on the toner carrier, the toner regulating member, A toner for use in an image forming method, comprising two layers of a rubber material and a metal thin plate, wherein the rubber material and the metal thin plate are not adhered to each other, and comprising at least a binder resin, a wax and a colorant. A toner which is contained and has at least one maximum value in a temperature range of 110 to 160 ° C. in an endothermic curve in DSC measurement of the toner. 7. The toner according to claim 6, wherein powder is interposed between the rubber material and the metal thin plate. 8. The developing device includes a developing container having at least a toner regulating member and a toner carrier, and a toner container detachably attached to the developing container for accommodating toner. The toner according to claim 6 or 7, which is characterized in that. 9. A toner THF containing no THF insoluble matter.
Soluble fraction has a molecular weight of 1 x 1 in GPC chromatogram
It has at least a high molecular weight peak or a shoulder in the region of 0 ^{5 to} 3 × 10 ⁶ , and the ratio of the high molecular weight is 5 to 5.
The toner according to claim 6, which is 45% by mass. 10. The wax is at least one mixture selected from the group consisting of a) a mixture of polypropylene and polyethylene, b) a mixture of polypropylene and a polyethylene derivative, c) a mixture of polypropylene and a polypropylene derivative. The toner according to any one of claims 6 to 9, further comprising: