JPH0876448A - Binary system developer - Google Patents

Abstract

PURPOSE: To provide a developer which contains specific toner and carrier, has good chargeability without charge control agent, scatters less toner, and excels in the quality of image. CONSTITUTION: A binary system developer contains toner and carrier. A toner particle contains resin for fixing, magnetic powder dispersed in the resin, and stearic acid metallic salt. The resin for fixing is composed of a component which contains resin having an anion polar group. It contains the magnetic powders at a ratio of 0.1-5 weight parts for 100 weight parts of the resin of fixing and metal stearate at a ratio of 0.01-10 weight parts for 100 weight parts of the resin for fixing. A particle of carrier has a core particle and a covering layer. The core particle is composed of a magnetic material expressed by a formula MOFe2 O3 (M is a metal such as Cu, Zn). The covering layer is composed of a resin component which contains thermosetting resin and thermoplastic resin. The thermoplastic resin contains 0.1-20 millimol of the fourth class ammonium group for 100g of resin component.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a two-component developer, and more specifically, it has good transfer efficiency and can reproduce a desired density for a long time even if a charge control agent is not contained in the toner. The present invention relates to a long-life two-component developer capable of obtaining an image, which is preferably used in an electrophotographic image forming apparatus such as an electrostatic copying machine or a laser beam printer.

[0002]

2. Description of the Related Art In an electrophotographic image forming apparatus, a two-component developer is used as one of the developers for developing an electrostatic latent image on a photoconductor. This two-component developer contains a toner containing a coloring agent such as carbon black and a fixing resin, and a magnetic carrier containing iron powder, ferrite particles and the like.

During development, the toner and carrier are mixed to charge the toner to a predetermined polarity, and then the mixture is conveyed to the photoconductor in the form of a magnetic brush. The photoconductor is rubbed by this magnetic brush, and toner adheres to the electrostatic latent image on the surface of the photoconductor. A charge control agent is generally contained in the toner particles in order to make the amount of toner adhered constant and give a predetermined charge amount to the toner in order to provide a stable image. Negative charge control agents such as metal-containing complex dyes containing a metal such as chromium (eg, azo dyes) and oxycarboxylic acid metal complexes (eg, salicylic acid metal complexes) are used for negatively chargeable toners. No. 3-67268), and positively chargeable toners use oil-soluble dyes such as nigrosine and positive charge control agents such as amine-based control agents (JP-A-56-56).
106249).

The charge control agents that have been conventionally used are often compounds containing heavy metals such as chromium-containing complexes.
When using these compounds, compounds that have passed various toxicity tests and safety tests are selected from the viewpoint of environmental safety. However, even if there is no problem in safety as a compound or in the form of being contained in the toner,
It would be more desirable to avoid the use of charge control agents containing these heavy metals. Further, since the charge control agent has a higher unit price than the fixing resin and the colorant such as carbon black, which are the materials constituting the toner, it increases the unit price of the toner despite the content rate of about several percent.
Therefore, there is a demand for the development of a toner containing no charge control agent containing such a heavy metal.

Further, in the conventional toner, the toner component adheres to the particle surface of the carrier due to long-term use, so that the charged state of the particle surface of the carrier is similar to the charged state of the toner particle surface. come. As a result, there is also a drawback that toner scattering occurs and transfer efficiency decreases.

[0006]

DISCLOSURE OF THE INVENTION The present invention is to solve the above-mentioned conventional problems, and an object thereof is to:
It is an object of the present invention to provide a two-component developer in which the toner does not scatter and the image quality is excellent because the toner has good charging performance even though it does not contain any charge control agent. Another object of the present invention is to provide a two-component type developer which does not cause spent even after long-term use and, as a result, maintains good image quality and has stable transfer efficiency.

[0007]

The present invention is a two-component developer comprising a toner and a carrier; the toner comprises toner particles; the toner particles are a fixing resin, and in the resin. Magnetic powder and a metal stearate dispersed therein; the fixing resin is a composition containing a resin having an anionic polar group; the magnetic powder is based on 100 parts by weight of the fixing resin. The toner is contained in the toner particles in a proportion of 0.1 to 5 parts by weight; the metal stearate is contained in the toner particles in a proportion of 0.01 to 10 parts by weight with respect to 100 parts by weight of the fixing resin. Contained; the carrier particles have core particles and a coating layer covering the core particles; the core particles are made of a magnetic material represented by the following formula (A): MOFe ₂ O ₃ (A) Here, M is Cu, Zn, Fe, Ba, Ni, M , M
It is at least one metal selected from the group consisting of n, Al and Co; the coating layer is a resin composition containing a thermosetting resin and a thermoplastic resin; the thermoplastic resin is a quaternary It contains an ammonium group; and the content of the quaternary ammonium group is 0.1 to 20 mmol based on 100 g of the resin composition; thereby, the above object is achieved.

In a preferred embodiment, the extraction liquid when the toner is extracted with methanol is 280 to 350.
has substantially no absorption peak in the nm region, and 400
The absorbance in the region from to 700 nm is substantially zero.

In a preferred embodiment, the magnetic powder is 0.5 to 3 with respect to 100 parts by weight of the fixing resin.
It is contained in a ratio of parts by weight.

In a preferred embodiment, the metal stearate salt is at least one selected from the group consisting of zinc stearate and magnesium stearate.

In a preferred embodiment, the toner particles have a volume-based average particle diameter of 5 to 15 μm, and the toner particles have a volume-based average particle diameter of 0.05 to 1.0 μm.
m spacer particles are attached.

In a preferred embodiment, the core particles have a particle size of 50 to 150 μm.

In a preferred embodiment, the weight of the coating layer is 0.001 with respect to 100 parts by weight of the core particles.
To 2.5 parts by weight.

In a preferred embodiment, the thermosetting resin is a modified or unmodified silicone resin, thermosetting acrylic resin, thermosetting styrene-acrylic resin, phenol resin, urethane resin, thermosetting polyester resin. , An epoxy resin, and an amino resin.

[0015]

The two-component developer of the present invention does not contain any charge control agent such as an azo dye or a metal complex of oxycarboxylic acid. Therefore, as will be described later, the spent due to the charge control agent is not generated, so that high-quality image copying can be performed for a long time. Since the toner in the developer contains no charge control agent, such a charge control agent, that is, a dye-based compound, is not detected from the toner by any chemical or physical means. For example, these compounds are not detected by a chemical reaction in the toner used in the developer of the present invention. Alternatively, absorption peaks due to these compounds are not detected at all in the organic solvent extract of the toner used in the developer of the present invention. For example, when the toner used in the developer of the present invention is extracted with an organic solvent, for example, methanol, the extract liquid is 280-35.
It has substantially no absorption peak in the region of 0 nm, and 40
The absorbance in the region of 0 to 700 nm is substantially zero. Here, “having substantially no absorption peak” means that no absorption peak was detected in the extract obtained by extracting 0.1 g of toner with 50 ml of methanol, or even if it was detected, the absorbance at the peak position was 0. It means less than or equal to 05. Similarly, that the absorbance is substantially zero means that the absorbance of the extract obtained by extracting 0.1 g of the toner with 50 ml of methanol is not more than 0.05.

In the two-component developer of the present invention, the instability of the charge amount due to the fact that the toner does not contain the above charge control agent is compensated by the following matters. Firstly, the resin having an anionic polar group is used as the fixing resin in the toner particles, and secondly, the magnetic powder is contained in the toner particles in a predetermined ratio.
In the present invention, stearic acid metal salt is used in a predetermined ratio to further enhance the function of the toner. As a result, the fixability of the transferred image is improved, the smoothness of the surface of the obtained copy image is also increased, and a glossy copy image is obtained. Further, if necessary, by attaching spacer particles having a predetermined particle size to the surface of the toner particles,
The transfer efficiency from the photoconductor to the transfer paper is improved. In the present invention, in order to further enhance the function of the developer, a coating layer of carrier particles contains a thermosetting resin and a thermoplastic resin, and the thermoplastic resin contains a quaternary ammonium group in a predetermined ratio. Include.

The above will be described in detail below.

FIG. 1 shows the absorbance curve of the methanol extract of the toner used in the developer of the present invention at 200 to 700 nm. As shown in this curve, this extract does not have any peaks attributed to each charge control agent.
That is, it has substantially no absorption peak in the region of 280 to 350 nm, and the absorbance in the region of 400 to 700 nm is substantially zero. On the other hand, the absorbance curve of the methanol extract of the toner containing the azo-type chromium metal complex salt dye as the charge control agent is 400 to 700 nm, especially 5
The toner has a peak in the range of 50 to 570 nm (FIG. 2), and the absorption curve of the methanol extract of the toner containing the salicylic acid metal complex as the charge control agent is 28.
It has a peak in the region of 0 to 350 nm (FIG. 3).

The absorption due to the charge control agent is observed in the methanol extract of the toner containing the above charge control agent because the charge control agent is present at a considerably high concentration on the toner particle surface. is there.

The carrier of the developer whose chargeability of the carrier becomes insufficient due to generation of spent is extracted with methanol,
When the absorbance at 400 to 700 nm is examined, a peak due to the charge control agent is observed in that region. For example, a toner containing an azo chromium complex salt dye, the absorbance curve of which is shown in FIG. 2, is used for a long time,
FIG. 4 shows the absorbance curve of the methanol extract of the carrier when the spent was generated. In FIG. 4, a peak is recognized at the same position as that of the charge control agent in FIG. In the past, it was thought that the spent was caused by the resin for fixing the toner adhering to the particle surface of the carrier to form a resin film, but due to the above fact, one of the main causes of the spent generation is charging. It was found that the control agent was transferred from the toner particles to the surface of the carrier particles.

The inventors further conducted the following experiment in order to investigate the relationship between the charge control agent and the spent. First, a toner having toner particles containing an azo chromium complex salt dye at a ratio of 1.5 wt% as a charge control agent was mixed with a carrier to obtain a developer. FIG. 5 shows the relationship between the elapsed time when the operation of mixing and stirring the toner of the developer and the carrier is continued and the weight of the deposit adhered to the particle surface of the carrier by the spent. The weight of the deposits is shown in FIG. 5 as the percentage of spent relative to the total weight of the carrier having the deposits. Further, FIG. 6 shows the relationship between the elapsed time and the toner charge amount. Further, the same measurement was performed for the developer containing the toner having the toner particles not containing the charge control agent and the carrier. The results are also shown in FIGS. 5 and 6. In FIGS. 5 and 6, the black circle plots show the measured values of the toner containing the charge control agent, and the white circle plots show the measured values of the toner without the charge control agent.
From FIGS. 5 and 6, it can be seen that the toner containing the charge control agent has a larger amount of deposits on the particle surface of the carrier due to the spent and the degree of decrease in the charge amount is larger than that of the toner containing no charge control agent.

The weight of the toner component adhering to the surface of the particles of the carrier was measured by means of the spent, the abscissa represents this (shown as the spent amount), and the ordinate represents the amount of the charge control agent in the toner component. The graph taken is shown in FIG. The dotted line shows the amount of the charge control agent when it is assumed that the toner component attached by the spent is the same as the component forming the toner particles. From FIG. 7, it can be seen that a large amount of the charge control agent is deposited and adheres to the particle surface of the carrier in the initial stage of using the developer. In FIG. 7, the reason why the measured value approaches the calculated value indicated by the dotted line with the increase in the amount of spent is that this is an experimental result in a closed system without toner replenishment. If there is a replacement, the difference between the two will be further widened.

Further, in order to investigate the relationship between the components constituting the toner particles and the spent, the inventors mixed a charge control agent, a fixing resin, carbon black as a colorant, and wax with a carrier. -The weight of the deposits on the surface of the particles of the carrier produced by the passage of time with stirring was measured. FIG. 8 shows the result. In FIG.
The white circles show the results when the test was conducted using the charge control agent, the black circles the carbon black, the squares the fixing resin, and the triangles the wax. It can be seen from FIG. 8 that the charge control agent is most likely to cause the spent to adhere to the surface of the particles of the carrier.

From the above facts, the charging failure due to the spent of the conventional two-component magnetic developer is explained as follows. First, as shown in the upper part of FIG. 9, in the initial stage of use of the developer, the carrier particles 1 are positively charged and the toner 2 is negatively charged, and the toner exists as the negative polarity toner 21. When this developer is used, the toner component containing the charge control agent as a main component in the toner particles adheres to the surface of the carrier particles 1. Since the deposit 201 formed by this spent is negatively charged, the toner having a positive charge with respect to the deposit 201, that is, the opposite polarity toner 22 is formed. This reverse polarity toner 22
Are formed on the surface of the particles 1 of the carrier, toner scattering occurs, and the transfer efficiency decreases.

As described above, the charge control agent is
Since it may contain a heavy metal, it is preferable not to contain it. Further, as described above, it is a main cause of spent, causing toner scattering, lowering of transfer efficiency, and the like. Therefore, the toner used in the developer of the present invention In, the charge control agent is not contained at all.

The instability of the charge amount due to the absence of the charge control agent, mainly the lack of the charge amount, is due to the use of the fixing resin having an anionic polar group in the toner as described above. Will be supplemented. Since the fixing resin itself is provided with a negative charge by the anionic polar group, the insufficient charge amount of the toner particles is compensated. Since this polar group exists by binding to the skeleton of the resin itself, it does not migrate to the particle surface of the carrier like a charge control agent and cause spent. However, conversely, the chargeability near the surface of the toner particles is
Since it is not so large, the coupling between the toner particles and the carrier particles by the Coulomb force in the magnetic brush during development is still insufficient. Therefore, when high-speed copying is performed, the bondability between the carrier particles and the particles is weak, and the toner scattering is not sufficiently suppressed. There is a drawback that the inside of the copying machine is contaminated by the scattering of the toner and so-called fog occurs in the image of the copy.

In the present invention, as a second requirement as described above, the magnetic powder is contained in the toner particles at a predetermined ratio, that is, 0.1 to 5 parts by weight relative to 100 parts by weight of the fixing resin. Incorporation is employed to make up for the shortage of the charge amount of the toner particles. Since the magnetic powder is contained in the toner particles, a magnetic attractive force is generated between the toner particles and the carrier particles. In this way, in addition to the Coulomb force between the toner particles and the particles of the carrier, a magnetic attraction force is generated, so that toner scattering is prevented. Generally, the smaller the amount of charge per toner particle,
Since the number of toner particles attached to a given electrostatic latent image is increased, the apparent development sensitivity is increased.

The content of the above magnetic powder in the toner particles is
As described above, the amount is 0.1 to 5 parts by weight per fixing resin. When the content of the magnetic powder is less than 0.1 part by weight, the charge amount of the toner is insufficient as described above, the particles are not sufficiently bonded to the carrier particles, and the toner is easily scattered. That is, there is a drawback that so-called fog occurs in the image of the copy. When the content of the magnetic powder exceeds 5 parts by weight, the binding force between the carrier particles and the toner particles becomes too large, so that the toner does not adhere sufficiently to the electrostatic latent image,
As a result, the image density becomes low.

To date, attempts have been made to incorporate (internally add) magnetic powder into toner particles for the purpose of improving the resolution of images. For example, JP-A-56-1062
No. 49 discloses toner particles containing 10% by weight of ferrite, and JP-A No. 59-162563 discloses toner particles containing 5 to 35% by weight of magnetic fine powder. . However, in either case, the image density of the obtained copy is low because the amount of the magnetic powder is excessive. Japanese Patent Application Laid-Open No. 3-67268 discloses a toner to which magnetic powder is externally added at a ratio of 0.05 to 2% by weight. However, since the magnetic powder is not internally added to the toner particles, it tends to be nonuniformly attached to the surface of the toner particles, and the magnetic attraction between the toner particles and the carrier particles is insufficient. In any of the above-mentioned conventional techniques, since the toner contains the charge control agent, problems such as spent may occur.

In the present invention, as described above, the toner particles further contain a metal stearate in a predetermined ratio, that is, 0.01 to 10 parts by weight based on 100 parts by weight of the fixing resin. As a result, the melt viscosity of the toner particles is reduced, and as a result, the penetration of the toner into the transfer paper is improved in the heat fixing by the heat roll, and the fixability of the image is improved. Furthermore, since the melting temperature of the metal stearate is lower than that of the fixing resin, the metal stearate seeps out on the surface of the toner particles during fixing, and when the transfer image is fixed, the surface of the image is smoothed. And a glossy copy image is obtained. Furthermore, by incorporating the stearic acid metal salt in the above-mentioned proportion in the toner particles, the resistance of the toner can be appropriately reduced, and a high-density copied image can be obtained.

In the present invention, in order to further improve the transfer efficiency of the toner image, spacer particles having a particle size of 0.05 to 1.0 μm are preferably attached to the surface of the toner particles. The spacer particles can act as a fluidity improver for the toner particles and form a gap between the photoreceptor and the toner particles when attached to the electrostatic latent image on the photoreceptor. Therefore, even if the charge amount of the toner becomes high due to copying for a long time, the toner can be easily transferred from the surface of the photoconductor, so that the transfer efficiency becomes high. When the spacer particles are the same magnetic powder particles as those internally added to the toner particles, the binding ability between the toner particles and the particles of the carrier becomes higher, and the toner scattering and fog can be further reduced.

As a conventional fluidity improving agent for toner, fine particles having a particle diameter of about 0.015 μm are used as an external additive. Such particles form a sufficient gap between the photoconductor and the toner particles. Therefore, it does not function as the spacer particles for the above purpose.

In the present invention, a specific magnetite or ferrite is used as the material for the core particles of the carrier. Since these compounds have little change in electric resistance due to environmental changes or changes with time, they can impart a stable charging property to the developer. Further, when a magnetic field is applied in the developing device, soft ears can be formed, so that the toner image formed on the photoconductor is less likely to be disturbed, and so-called white stripes do not occur in the image of the copy.

In the present invention, in order to further enhance the function of the developer, the coating layer of carrier particles contains a thermosetting resin and a thermoplastic resin, and the thermoplastic resin is provided with a quaternary ammonium group. Is included in the ratio.
Thereby, at the time of thermosetting, the thermoplastic resin containing the quaternary ammonium group is repelled from the thermosetting resin,
Will not be buried in resin. Therefore, better chargeability is imparted to the carrier than the case where a general cationic polar group is contained. Therefore, even when this carrier is combined with a toner containing no charge control agent, the chargeability of the toner is stable. Further, since the conventional charge control agent is not contained, the generation of spent on the carrier particles is effectively prevented, so that the life of the developer can be extended. In general, the resin having a quaternary ammonium group may be a thermosetting resin or a thermoplastic resin, but the present invention relates to the thermoplastic resin contained in the resin composition. Contains a quaternary ammonium group. This makes it possible to impart stable charging properties to the toner without lowering the durability of the coating layer. Further, by containing a quaternary ammonium group in an amount of 0.1 to 20 mmol with respect to 100 g of the resin composition, the charging property is further stabilized.

[0035]

BEST MODE FOR CARRYING OUT THE INVENTION The preferable modes of the present invention will be described below. Hereinafter, in the present specification, "lower alkyl group"
Is an alkyl group having 1 to 5 carbon atoms.

(Fixing Resin) The fixing resin contained in the toner particles of the two-component developer of the present invention is a composition containing a resin having an anionic polar group. Such a resin is obtained by polymerizing a monomer containing a monomer having an anionic polar group, and the obtained resin may be a homopolymer or a copolymer.

The resin used as the fixing resin is preferably a copolymer of a monomer having an anionic polar group and another monomer. For example, it may be a random copolymer, a block copolymer or a graft copolymer of a monomer having an anionic group and another monomer.

Examples of the monomer having an anionic polar group include a monomer having a carboxylic acid group, a sulfonic acid group or a phosphonic acid group, and a monomer having a carboxylic acid group is particularly preferable. As the monomer having a carboxylic acid group, an ethylenically unsaturated carboxylic acid is used, which includes acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, etc., and carboxylic acid such as maleic anhydride. Monomers capable of forming groups or lower alkyl half esters of dicarboxylic acids such as maleic acid and fumaric acid can also be used. Examples of the monomer having a sulfonic acid group include styrenesulfonic acid, 2-acrylamido-
2-methyl propane sulfonic acid etc. are mentioned. Examples of the monomer having a phosphonic acid group include 2-acid phosphoxypropyl methacrylate, 2-acid phosphoxyethyl methacrylate, and 3-chloro-2-acid phosphoxypropyl methacrylate.

These anionic polar group-containing monomers are
It may be a free acid, an alkali metal such as sodium or potassium, an alkaline earth metal such as calcium or magnesium, or a salt such as zinc.

The above-mentioned monomer having an anionic polar group and the other monomer to be polymerized as required are selected so that the resulting polymer has the fixability and chargeability required for the toner. , A combination of one or more monomers having an ethylenically unsaturated bond is used. Examples of such monomers include acrylic ester monomers, monovinyl aromatic monomers, vinyl ester monomers, vinyl ether monomers, diolefin monomers, monoolefin monomers. and so on.

The acrylic ester-based monomer is represented by the following general formula (I):

[0042]

Embedded image

Here, R ¹ is a hydrogen atom or a lower alkyl group, and R ² is a hydrocarbon group having 11 or less carbon atoms or a hydroxyalkyl group having 11 or less carbon atoms.

Examples of such a monomer include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate,
Phenyl acrylate, methyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, β-
Examples thereof include ethyl hydroxyacrylate, γ-hydroxyacrylate propyl, δ-hydroxyacrylate and β-hydroxymethacrylate.

Monovinyl aromatic monomers are represented by the following general formula (II):

[0046]

Embedded image

Here, R ³ is a hydrogen atom, a lower alkyl group or a halogen atom, R ⁴ is a hydrogen atom, a lower alkyl group, a halogen atom, an alkoxy group, an amino group, a nitro group or the like, and Φ is a phenylene group. Is.

Examples of such a monomer include styrene and α
-Methylstyrene, vinyltoluene, α-chlorostyrene, o-, m-, or p-chlorostyrene, p-ethylstyrene and the like.

The vinyl ester monomer is represented by the following general formula (III):

[0050]

[Chemical 3]

Here, R ⁵ is a hydrogen atom or a lower alkyl group.

Examples of such a monomer include vinyl formate,
Examples include vinyl acetate and vinyl propionate.

The vinyl ether type monomer is represented by the following general formula (IV):

[0054]

[Chemical 4]

Here, R ⁶ is a monovalent hydrocarbon group having 11 or less carbon atoms.

Examples of such a monomer include vinyl methyl ether, vinyl ethyl ether, vinyl-n-butyl ether, vinyl phenyl ether and vinyl cyclohexyl ether.

The diolefin monomer is represented by the following general formula (V):

[0058]

[Chemical 5]

Here, R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, a lower alkyl group or a halogen atom.

As such a monomer, butadiene,
Examples include isoprene and chloroprene.

The monoolefin monomer is represented by the following general formula (VI):

[0062]

[Chemical 6]

Here, R ¹⁰ and R ¹¹ are each independently a hydrogen atom or a lower alkyl group.

Examples of such a monomer include ethylene, propylene, isobutylene, butene-1, pentene-1,
4-methylpentene-1 and the like.

Specific examples of the resin having an anionic polar group, which is a (co) polymer obtained by polymerizing the above monomers, include styrene-acrylic acid copolymer, styrene-maleic acid copolymer, and ionomer. Resin etc. further,
A polyester resin having an anionic polar group can be used. Such a resin has an acid value of 2 to 3 when the anionic polar group is present in the form of a free acid.
It is desirable to have an anionic polar group in a ratio of 0, preferably 5 to 15. When part or all of the anionic polar group is neutralized, it is preferable to have the anionic polar group in such a proportion that it has the above-mentioned acid value when it exists in the form of a free acid. When the acid value of the resin, that is, the concentration of the anionic polar group, is lower than the above range, the chargeability of the toner is insufficient, and when it is higher than the above range, the toner has hygroscopicity, which is preferable. Absent. A suitable fixing resin contains the above-mentioned monomer having an anionic polar group and at least one kind of the acrylic monomer of the formula (I) as an essential component, and if necessary, the compound of the formula (II ), A copolymer containing the monomer of the formula (VI) as an optional component is used. Each of the above monomers is
One kind or a combination of two or more kinds may be used for preparing the above resin.

As the fixing resin used in the present invention, a resin composition containing the above resin is used.
In addition to the above resin, a polymer having no anionic polar group may be contained. In that case, the content ratio of the anionic polar group in the entire composition is preferably in the above range.

(Magnetic Powder) As the magnetic powder contained (added internally) in the toner particles, any of the magnetic powders conventionally used for one-component magnetic toners can be used. Examples of the material of the magnetic powder include ferrosoferric oxide (F
e ₃ O ₄ ), iron sesquioxide (γ-Fe ₂ O ₃ ), zinc iron oxide (ZnFe ₂ O ₄ ), iron oxide yttrim (Y ₃ Fe)
₅ O ₁₂ ), iron cadmium oxide (CdFe ₂ O ₄ ), gadolinium iron oxide (Gd ₃ Fe ₅ O ₁₂ ), iron oxide copper (CuFe ₂
O ₄ ), lead iron oxide (PbFe ₁₂ O ₁₉ ), iron nickel oxide (NiFe ₂ O ₄ ), iron neodymium oxide (NdFe)
O ₃ ), iron oxide barium (BaFe ₁₂ O ₁₉ ), iron oxide magnesium (MgFe ₂ O ₄ ), iron manganese oxide (MnF
e ₂ O ₄ ), lanthanum iron oxide (LaFeO ₃ ), iron (F
e), cobalt (Co), nickel (Ni), etc. may be used. A particularly preferred magnetic powder is finely particulate iron trioxide (magnetite). Suitable magnetite has a regular octahedron shape and a particle size of 0.05 to 1.0 μm. The magnetite particles may be surface-treated with a silane coupling agent, a titanium coupling agent, or the like. The particle size of the magnetic powder contained in the toner particles is generally 1.0 μm.
m or less, preferably 0.05 to 1.0 μm.

The content of the above magnetic powder in the toner particles is
0.1 to 5 parts by weight, preferably 0.5 to 4 parts by weight, more preferably 0.5 to 5 parts by weight, per 100 parts by weight of the fixing resin.
3 parts by weight. If the amount of the magnetic powder is too small, as described above, the toner may scatter during development, or the transfer efficiency may decrease.

(Metal stearate) Examples of the metal stearate contained (internally added) in the toner particles include zinc stearate, magnesium stearate, aluminum stearate, calcium stearate, chromium stearate, mercury stearate and stearin. Examples thereof include cerium acid, ferric stearate, sodium stearate, lead stearate, barium stearate and the like, and these may be used alone or as a mixture of two or more kinds.
Among the above metal stearates, at least one selected from the group consisting of zinc stearate and magnesium stearate is preferable, and zinc stearate alone is particularly preferable. Instead of the metal salt of stearic acid, stearic acid amide may be used.

The content of the metal stearate in the toner particles is 0.01 to 100 parts by weight of the fixing resin.
The amount is 10 parts by weight, preferably 0.05 to 5 parts by weight, and more preferably 0.1 to 3 parts by weight. By including the metal stearate in the toner particles in such a ratio, the following effects can be obtained: the penetration of the toner into the transfer paper is improved, and the fixability of the transferred image is improved; The smoothness of the obtained image surface is improved and a glossy copy image can be obtained; and the toner resistance can be appropriately reduced, and a high density copy image can be obtained.

(Compounding Agent in Toner Particles) The toner particles are
As described above, the fixing resin, the magnetic powder and the metal stearate are contained as essential components, and if necessary, a compounding agent which can be usually compounded in the toner can be contained.

Examples of the compounding agent include a colorant and a release agent.

As the colorant, for example, the following pigments can be used.

Black pigments Carbon black, acetylene black, lamp black, aniline black.

Body pigments Barite powder, barium carbonate, clay, silica, white carbon, talc, alumina white.

The pigment is contained in the toner particles in an amount of usually 2 to 20 parts by weight, preferably 5 to 15 parts by weight, based on 100 parts by weight of the fixing resin.

As the release agent, various waxes and low molecular weight olefin resins are used. As the olefin resin, polypropylene, polyethylene, propylene-ethylene copolymer and the like can be used, but polypropylene is particularly preferable.

(Preparation of Toner) The toner particles used in the two-component developer of the present invention can be prepared by a general method for producing toner particles, for example, pulverizing and classifying method, melt granulating method, spray granulating method and It can be produced by a polymerization method, and is usually produced by a pulverizing and classifying method.

For example, the components for forming the toner particles are premixed by a mixer such as a Henschel mixer, then kneaded by using a kneading device such as a twin-screw extruder, cooled, and then pulverized. The toner particles are classified to obtain toner particles. The toner particles preferably have a volume-based average particle diameter (median diameter by Coulter counter) of 5 to 15 μm, particularly 7 to 12 μm.

If necessary, a fluidity improver such as hydrophobic vapor phase silica particles may be attached to the surface of the toner particles as an external additive to improve the fluidity of the toner. The particle size of the fluidity improving agent such as silica particles is usually about 0.015 μm in the primary particle size, and the particle size per unit weight of the toner, that is, the total weight of the toner particles and the external additive is 0.1.
It is externally added in an amount of 1 to 2.0% by weight.

Further, in the present invention, preferably, spacer particles having a particle size larger than that of the fluidity improver particles are externally added to the toner particles. As the spacer particles, 0.05 to 1.0 μm, preferably 0.07 to 0.
Either 5 μm organic or inorganic inert particles can be used. Examples of the material of such inert particles include silica, alumina, titanium oxide, magnesium carbonate, acrylic resin, styrene resin, magnetic material and the like. The spacer particles can function as a fluidity improver and also have a function of enhancing transfer efficiency as described above.
As the spacer particles, it is generally preferable to use the same magnetic powder as that contained in the toner particles, particularly fine particulate iron trioxide tetraoxide (magnetite) particles. The use of magnetic powder particles as the spacer particles effectively acts on the toner scattering as described above. The spacer particles are contained in an amount of 10% by weight or less, preferably 0.1 to 10% by weight, more preferably 0.1 to 5% by weight, based on the total weight of the toner. If it is excessive, the density of the copied image will be insufficient. When magnetic powder is used as the spacer particles, the total amount of the magnetic powder and the magnetic powder contained in the toner particles is preferably 10 parts by weight or less based on 100 parts by weight of the fixing resin. If it is excessive, the image density may be low.

In order to externally add the fluidity improver and the spacer particles to the toner particles, for example, the fluidity improver and the spacer particles are sufficiently mixed, and this mixture is added to the toner particles and sufficiently crushed. Is good. As a result, the spacer particles adhere to the surface of the toner particles. Here, the term "adhesion" refers to either the state of being carried in contact with the surface of a particle or the state of being fixed in a state of being partially driven from the surface of the particle to the inside. In this way, the toner used in the developer of the present invention is obtained.

(Carrier Particles) The carrier particles used in the developer of the present invention are particles having a double structure having core particles and a coating layer for coating the core particles. This core particle is made of a magnetic material represented by the following formula (A): MOFe ₂ O ₃ (A) where M is Cu, Zn, Fe, Ba, Ni, Mg, M
It is at least one metal selected from the group consisting of n, Al and Co.

The compound represented by the above formula (A) is magnetite (when M is Fe) or ferrite (M is F).
(for metals other than e), M is Cu, Zn, Mn,
Ferrites such as Ni and Mg are preferably used. These magnetites or ferrites have a small rate of change in electric resistance with the passage of time, and can form soft ears when a magnetic field is applied in the developing device. The core particles made of these magnetic materials have a particle size of 30 to 200 μm.
m, preferably 50 to 150 μm. These core particles are obtained by granulating the fine particles of the magnetic material into spherical particles by means such as spray granulation and then firing.
This core particle has a volume resistivity of 10 ⁵ to 10 ⁹ Ω.
-Cm, preferably 10 < ⁶ > -10 < ⁸ > [Omega] -cm. The saturation magnetization of the core particles is in the range of 30 to 70 emu / g, preferably 45 to 65 emu / g.

The resin composition constituting the coating layer of carrier particles contains a thermosetting resin and a thermoplastic resin. The thermosetting resin includes a modified or unmodified silicone resin, a thermosetting acrylic resin, a thermosetting styrene-acrylic resin, a phenol resin, a urethane resin, a thermosetting polyester resin, an epoxy resin, and an amino resin. It is at least one selected from the group. The thermoplastic resin preferably has a quaternary ammonium group, and examples of such a thermoplastic resin include acrylic resins having a quaternary ammonium group, styrene-acrylic resins, polyester resins, polyamide resins, and olefin-based resins. There are polymer resins and the like. Such a thermoplastic resin having a quaternary ammonium group can be obtained by polymerizing a monomer containing a monomer having a quaternary ammonium group. Alternatively, it can be obtained by binding a compound having a quaternary ammonium group to a thermoplastic resin having no quaternary ammonium group.

The thermoplastic resin having a quaternary ammonium group contains the quaternary ammonium group in an amount of 0.1 to 20 mmol with respect to 100 g of the resin composition. By having a specific group in such a specific range,
Further, the stability of charging property is improved.

In the present invention, the coating layer may contain a thermoplastic resin other than the thermoplastic resin having a quaternary ammonium group as long as the characteristics of the coating layer are not deteriorated. Examples of such a resin include various resins known as a coating layer such as an acrylic resin, a styrene-acrylic resin, a polyester resin, a polyamide resin, and an olefin-based copolymer resin. These may be used alone or in combination of two or more.

Further, in the resin composition, if necessary,
Silica, alumina, carbon black, fatty acid metal salt,
Additives such as a silane coupling agent and silicone oil are contained, and these have the function of adjusting the characteristics of the coating layer.

(Preparation of Carrier) The resin composition containing a thermosetting resin and a thermoplastic resin is applied to the surface of the core particles by a known method to form a coating layer. For example, by mixing a solution or dispersion of the above resin composition with core particles, coating the solution or dispersion of the resin composition on the surface of the core particles, drying if necessary, and curing by heating or the like. Form a coating layer. In forming the coating layer, a generally used dipping method,
Any of a spray method, a fluidized bed method, a moving bed method, a rolling bed method and the like can be used. As a solvent capable of dissolving or dispersing the resin composition, a general organic solvent, for example, an aromatic hydrocarbon solvent such as toluene or xylene, acetone,
Methyl ethyl ketone, methyl isobutyl ketone, ketone-based solvents such as cyclohexanone, tetrahydrofuran,
Cyclic ethers such as dioxane, alcohols such as ethanol, propanol and butanol, cellosolve solvents such as ethyl cellosolve and butyl cellosolve, ester solvents such as ethyl acetate and butyl acetate, amide solvents such as dimethylformamide and dimethylacetamide. , Can be appropriately used according to the properties such as solubility of the resin used.

The particle diameter of the thus obtained carrier is 30 to 200 μm, preferably 50 to 150 μm. The weight of the coating layer of carrier particles is 100%
The amount is 0.001 to 2.5 parts by weight, preferably 0.005 to 2.0 parts by weight. The volume resistivity of particles of the obtained carrier is 10 ⁵ to 10 ¹³ Ω · cm, preferably 10 ⁷ to 10 ¹² Ω · cm, and the saturation magnetization is 3
0 to 70 emu / g, preferably 45 to 65 emu / g
Is in the range.

(Preparation of Developer) A two-component developer is obtained by mixing the above toner and carrier. The mixing ratio of carrier and toner is generally 98: 2 to 90: 1.
A weight ratio of 0, particularly a weight ratio of 97: 3 to 94: 6 is preferred.

Using the two-component type developer of the present invention, copying can be carried out by a general electrostatographic copying method. For example, after uniformly charging the photoconductive layer on the photoreceptor, imagewise exposure is performed to form an electrostatic latent image, and then a magnetic brush of a two-component magnetic developer is brought into contact with the photoreceptor to form the electrostatic latent image. Can be easily developed. The toner image formed by the development is transferred onto a transfer paper to form a transfer image, and the transfer image is fused and pressure-bonded with a heat roll to fix the image.

[0093]

EXAMPLES The present invention will be described with reference to examples.

Example 1 <Preparation of Toner>

[0095]

[Table 1]

The above components were melt-kneaded by a twin-screw extruder, then the kneaded product was ground by a jet mill and classified by an air classifier to obtain toner particles having an average particle size of 10.0 μm.

Hydrophobic silica fine particles having an average particle size of 0.015 μm are added (externally added) to the toner particles in a ratio of 0.3 parts by weight to 100 parts by weight of the toner particles, and The toner was obtained by mixing for 2 minutes with a Henschel mixer.

<Preparation of Carrier>

[0099]

[Table 2]

Spherical ferrite particles having an average particle size of 100 μm were used as the magnetic core particles. This ferrite particle 10
The coating agent having the composition shown in Table 2 was added to 00 parts by weight, and mixed using a heating and stirring device. After the solvent was removed by drying from the obtained mixture, heat treatment was performed at 200 ° C. for 1 hour to obtain carrier particles having a coating layer.

<Preparation of Developer> The above toner and carrier were uniformly mixed to obtain a two-component developer having a toner concentration of 3.5% by weight.

Example 2 Example 1 was repeated except that the content of the quaternary ammonium group was changed as shown in Table 2.
A developer was obtained in the same manner as in.

Comparative Example 1 A developer was obtained in the same manner as in Example 1 except that the styrene-acrylic resin containing a quaternary ammonium group was not included.

Comparative Example 2 Example 1 was repeated except that the content of the quaternary ammonium group was changed as shown in Table 2.
A developer was obtained in the same manner as in.

[Evaluation of Developer] The developers of Examples and Comparative Examples were evaluated for the following items. What was used for the test was an electronic copying machine (trade name "DC-468" manufactured by Sanda Kogyo Co., Ltd.
5)) modified machine (a modified copying machine for easily sampling the evaluation sample).

(A) Image Density (ID) 50,000 copies were made using a character original having a black area ratio of 8%. The density of the black solid portion in the copied image was measured every 5,000 sheets using a reflection densitometer (model number "TC-6D" manufactured by Tokyo Denshoku Co., Ltd.), and the average value was taken as the image density (ID). .
Here, the document used for sampling every 5,000 sheets is a document in which the area ratio of the black portion including the black solid portion is 15%. The evaluation results are shown in Table 3.

(B) Fog Density (FD) 50,000 copies were made using a character original having a black area ratio of 8%. The density of the non-image area in the copied image was measured every 5,000 sheets using a reflection densitometer (model number "TC-6D" manufactured by Tokyo Denshoku Co., Ltd.). The difference between the measured value and the value of the reflection density obtained by measuring the paper (base paper) before copying with a reflection densitometer was calculated, and the maximum value was defined as the fog density (FD). Here, the document used for sampling every 5,000 sheets is a document in which the area ratio of the black portion including the black solid portion is 15%. The evaluation results are shown in Table 3.

(C) Charge Amount 50,000 copies were made using a character original having an area ratio of black area of 8%. The charge amount of 200 mg of the developer was measured every 5,000 sheets using a "blow-off powder charge amount measuring device" (manufactured by Toshiba Chemical Co.), and the average value of the charge amount per 1 g of toner was calculated. The evaluation results are shown in Table 3.

(D) Toner Scattering 50,000 copies were made using a character original having an area ratio of the black portion of 8%. At this time, the toner scattering state in the copying machine was visually observed and evaluated according to the following criteria. ◯: No toner scatter x: Toner scatter is shown in Table 3.

(E) Transfer Efficiency The toner amount in the toner hopper before the start of copying and the toner amount in the toner hopper after copying 50,000 sheets were measured, and the toner consumption amount was calculated from the difference. On the other hand, the amount of toner collected in the cleaning process during the copying of 50,000 sheets was measured and used as the toner recovery amount. From these values, the toner transfer efficiency was calculated by the following equation (i). Here, the original used for copying is a character original in which the area ratio of the black portion is 8%. The evaluation results are shown in Table 3.

[0111]

[Equation 1]

(F) Amount of Adhered Substances on Surface of Particles of Carrier Due to Spent: A character original having an area ratio of black portion of 8% was used for copying.
At the time of copying 50,000 sheets, the developer was sampled. The developer was placed on a 400-mesh sieve and sucked from below with a blower to separate the toner from the carrier.
5 g of the carrier remaining on the sieve was put into a beaker, and toluene was further added to the beaker to dissolve the toner component adhering to the particle surface of the carrier by means of the spent. After that, the toluene solution was discarded while the carrier was attracted from below the beaker with a magnet. This was repeated several times until the toluene became colorless, and then the toluene adhering to the carrier was evaporated in an oven, and the weight of the residue obtained was measured. The difference between the weight of the carrier initially put in the beaker and the weight after evaporation of toluene is the amount of the toner component (spent amount) attached to the particle surface of the carrier by the spent. The spent amount is represented by mg of the toner component attached to 1 g of the carrier. The evaluation results are shown in Table 3.

[0113]

[Table 3]

[Discussion of Evaluation Results] The developers obtained in the examples have a smaller amount of the deposits of the carrier on the particle surface of the carrier and a lower fog density than the developers obtained in the comparative examples. The charge amount was stable and the transfer efficiency was excellent. Toner scattering was also not observed.

[0115]

As described above, according to the present invention, there is provided a two-component developer containing no charge control agent, which is a main cause of spent during copying. The toner particles of the toner contained in this developer contain a fixing resin having an anionic polar group, and the toner particles contain a magnetic powder and a metal stearate in a predetermined ratio. Further, spacer particles having a predetermined particle diameter are attached to the surface of the toner particles as needed. The core particles of the carrier contained in the developer are composed of a magnetic material having a specific composition, and the coating layer for coating the core particles is a resin composition containing a thermosetting resin and a thermoplastic resin, As the thermoplastic resin, a resin having a predetermined amount of quaternary ammonium group is used. The toner of the developer of the present invention has sufficient chargeability, and the toner particles and carrier particles are also sufficiently bonded. Further, the chargeability is further stabilized by using the carrier having the specific coating layer as described above. Therefore, a spent is not generated during copying, toner is not scattered, transfer efficiency is sufficient, and a copy image having a required density can be stably obtained for a long time. Since the toner particles contain the stearic acid metal salt in a predetermined ratio, the fixability of the transferred image and the smoothness of the surface of the obtained copied image are excellent. Such a two-component developer is preferably used in electronic image forming apparatuses such as electrostatic copying machines and laser beam printers.

[Brief description of drawings]

FIG. 1 is a graph showing the absorbance of a methanol extract of a toner used in a developer of the present invention at wavelengths of 200 to 700 nm.

FIG. 2 is a wavelength of 200 to 700 n of a methanol extract of a toner containing an azo chromium complex salt dye as a charge control agent.
It is a graph which shows the light absorbency in m.

FIG. 3 Wavelength 200 to 700 nm of a methanol extract of a toner containing a salicylic acid metal complex as a charge control agent.
It is a graph which shows the light absorbency in.

FIG. 4 is a schematic diagram of a carrier containing a toner containing an azo chromium complex salt dye as a charge control agent used in a two-component magnetic developer. 200-700 nm
It is a graph when the light absorbency in is measured.

FIG. 5 shows the mixing / stirring time when the operation of mixing / stirring the toner containing the charge control agent and the magnetic carrier or the mixing / stirring of the toner not containing the charge control agent and the magnetic carrier is continued. It is a graph which shows the relationship with a spent rate.

FIG. 6 shows the mixing / stirring time when the operation of mixing / stirring the toner containing the charge control agent and the magnetic carrier or the mixing / stirring of the toner not containing the charge control agent and the magnetic carrier is continued. It is a graph which shows the relationship with a charge amount.

FIG. 7 is a graph showing the relationship between the amount of the adhering substance of the carrier to which the toner component is attached due to the spent and the amount of the charge control agent in the toner that causes the spent.

FIG. 8 is a graph showing the relationship between the amount of spent and the mixing / stirring time when the operation of mixing / stirring each of the components in the toner and the magnetic carrier is continued.

FIG. 9 is an explanatory diagram illustrating occurrence of charging failure due to spent in a conventional two-component magnetic developer.

[Explanation of symbols]

 1 Carrier Particles 2 Toner 22 Reverse Toner

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G03G 9/107 9/113 G03G 9/08 365 9/10 321 351 352 (72) Inventor Tomohide Iida 1-22 Tamatsukuri, Chuo-ku, Osaka Mita Kogyo Co., Ltd. (72) Inventor Yoshiteru Hatase 1-2-2 Tamatsukuri, Chuo-ku Mita Kogyo Co., Ltd. (72) Inventor, Eiichi Tamura Osaka 1-22-Tamazo, Chuo-ku, Yokohama-shi Mita Engineering Co., Ltd.

Claims (8)

[Claims] 1. A two-component developer containing a toner and a carrier, wherein the toner contains toner particles, the toner particles being a fixing resin, and magnetic powder and stearin dispersed in the resin. An acid metal salt is contained, the fixing resin is a composition containing a resin having an anionic polar group, and the magnetic powder is contained in an amount of 0.
It is contained in the toner particles in a proportion of 1 to 5 parts by weight, and the metal stearate is contained in the toner particles in a proportion of 0.01 to 10 parts by weight with respect to 100 parts by weight of the fixing resin. The carrier particles have core particles and a coating layer that covers the core particles, and the core particles are made of a magnetic material represented by the following formula (A): MOFe ₂ O ₃ (A) where M is Cu, Zn, Fe, Ba, Ni, Mg, M
The coating layer is at least one metal selected from the group consisting of n, Al and Co, the coating layer is a resin composition containing a thermosetting resin and a thermoplastic resin, and the thermoplastic resin is a quaternary The resin composition 10 containing an ammonium group and having a content of the quaternary ammonium group is
A two-component developer whose amount is 0.1 to 20 mmol with respect to 0 g. 2. The extract obtained by extracting the toner with methanol has substantially no absorption peak in the region of 280 to 350 nm, and the absorbance in the region of 400 to 700 nm is substantially zero. Item 2. The developer according to Item 1. 3. The fixing resin 100 comprises the magnetic powder.
The developer according to claim 1, which is contained in a ratio of 0.5 to 3 parts by weight with respect to parts by weight. 4. The developer according to claim 1, wherein the metal stearate is at least one selected from the group consisting of zinc stearate and magnesium stearate. 5. The volume-based average particle diameter of the toner particles is 5
2. The developer according to claim 1, wherein spacer particles having a volume-based average particle diameter of 0.05 to 1.0 μm are attached to the surface of the toner particles. 6. The core particles have a particle size of 50 to 150.
The developer according to claim 1, which has a thickness of μm. 7. The core particle 10 has a weight of the coating layer.
0.001 to 2.5 parts by weight with respect to 0 parts by weight,
The developer according to claim 1. 8. The thermosetting resin is a modified or unmodified silicone resin, thermosetting acrylic resin, thermosetting styrene-acrylic resin, phenol resin, urethane resin, thermosetting polyester resin, epoxy resin, and The developer according to claim 1, which is at least one selected from the group consisting of amino resins.