JPH0876422A - Binary system developer - Google Patents

Abstract

PURPOSE: To provide a developer that is provided with a good chargeability without containing any electrostatic charge control agent utterly, less in toner scattering and excellent in image quality by comprising a toner and a carrier specified each. CONSTITUTION: This developer comprises a toner and a carrier. Toner grain contains a kind of fixing resin and magnetic powder dispersed in this resin. This fixing resin consists of a kind of resin with an anionic polar group, and the magnetic powder is contained at the rate of 0.1 to 5 pt.wt. to 10 pt.wt. of the fixing resin. Volume reference mean grain size in this toner grain is 5 to 15μm, and a spacer grain of 0.05 to 1.0μm in this volume reference means grain size is stuck to the surface. Carrier grains have a core grain and a covered layer. This core grain is made up of a magnetic material to be shown in a formula of MOFe2 O3 , wherein M is a metal to be selected out of a group of Cu, Zn, Fe, Ba, Ni, Mg, Mn, Al and Co. In addition, the covered layer consists of a resin composition containing a resin with a cotionic polar group.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a two-component developer,
More specifically, it is a long-life two-component developer that has good transfer efficiency and can obtain a copy image of desired density over a long period of time, even though it does not contain a charge control agent in the toner. The present invention relates to a developer preferably used in an electrophotographic image forming apparatus such as a 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]

SUMMARY OF THE INVENTION The present invention is a two-component developer comprising a toner and a carrier; the toner comprises toner particles; the toner particles are in a fixing resin and in the resin. Containing dispersed magnetic powder; the fixing resin is a composition containing a resin having an anionic polar group; the magnetic powder is 0.1 to 5 parts by weight with respect to 100 parts by weight of the fixing resin. The carrier particles have a core material and a coating layer that covers the core particles; the core particles are magnetic materials represented by the following formula (A). Nari: MOFe ₂ O ₃ (A) where M is Cu, Zn, Fe, Ba, Ni, Mg, M
At least one metal selected from the group consisting of n, Al and Co, and the coating layer is made of a resin composition containing a resin having a cationic polar group; It

In a preferred embodiment, when the above toner is extracted with methanol, the extraction liquid is 280 to 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.

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 resin having a cationic polar group is a resin having a basic nitrogen-containing group.

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

[0012]

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. The first is to use a resin having an anionic polar group as the fixing resin in the toner particles, and the second is to contain the magnetic powder in a predetermined ratio in the toner particles.
And thirdly, the coating layer of the carrier particles contains a resin having a cationic polar group. Further, if necessary, spacer particles having a predetermined particle diameter are attached to the surfaces of the toner particles, so that the transfer efficiency from the photoconductor onto the transfer paper is enhanced.

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 charge control agent, because the charge control agent is present at a considerably high concentration on the surface of the toner particles. 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 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 with the spent, and the abscissa represents the weight (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 toner, the inventors mixed a carrier with a charge control agent, a fixing resin, carbon black as a colorant, and a wax. -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 2
Since 2 is formed on the particle surface of carrier particles 1, toner scattering occurs and transfer efficiency decreases.

Thus, the charge control agent, as described above,
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 the 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 described above, as the second requirement, the magnetic powder is contained in the toner particles in a predetermined ratio, that is, 0.1 to 5 parts by weight relative to 100 parts by weight of the fixing resin. This is adopted to compensate 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 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 a third requirement, the carrier is provided with a charging property by containing a resin having a cationic polar group in the coating layer of the carrier particles. As a result, even when this carrier is combined with a toner containing no charge control agent, the chargeability of the toner is significantly improved. As a result, the chargeability of the toner becomes 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 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 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 particles of the same magnetic powder 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.

Fine particles having a particle size of about 0.015 μm have been used as an external additive as a conventional fluidity improving agent for toner, and such particles form a sufficient gap between the photoreceptor and the toner particles. Therefore, it does not function as the spacer particles for the above purpose.

[0031]

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 generally used. 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.

Acrylic ester monomers are represented by the following general formula (I):

[0038]

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):

[0042]

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):

[0046]

[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):

[0050]

[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):

[0054]

[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 mono-olefinic monomer is represented by the following general formula (VI):

[0058]

[Chemical 6]

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

As such a monomer, 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 (internally added) in the toner particles, any of the magnetic powders conventionally used for a one-component magnetic toner 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.

(Compounding Agent in Toner Particles) The toner particles are
As described above, the fixing resin and the magnetic powder are contained as essential components, and if necessary, a compounding agent that 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 above pigment is used 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, such as a pulverizing and classifying method, a melt granulating method, a 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 pre-mixed with a mixer such as a Henschel mixer, then kneaded with 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. As the spacer particles, 0.05 to
Either organic or inorganic inert particles of 1.0 μm, preferably 0.07 to 0.5 μm can be used. Materials for such inert particles include silica, alumina,
Examples thereof include titanium oxide, magnesium carbonate, acrylic resin, styrene resin, magnetic materials 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 10% by weight or less based on the total weight of the toner, preferably 0.1-10.
%, More preferably 0.1 to 5% by weight. 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 a particle. 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 a magnetite (when M is Fe) or a 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 diameter of 30 to 200.
μm, 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 1
It is 0 ⁹ Ω · cm, preferably 10 ⁶ to 10 ⁸ Ω · 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 having a cationic polar group in the resin composition forming the coating layer of carrier particles may be a thermoplastic resin or a thermosetting resin. From the viewpoint of heat resistance and durability, a thermosetting resin or a mixture containing a thermosetting resin is suitable. The cationic polar group includes a basic nitrogen-containing group, and the basic nitrogen-containing group includes a primary, secondary, or tertiary amino group, quaternary ammonium group, amide group, imino group, imide group, Examples include a hydrazino group, a guanidino group, and an amidino group. Amino groups or quaternary ammonium groups are particularly preferred.

Examples of the thermoplastic resin having a cationic polar group include the thermoplastic acrylic resin having a cationic polar group, a thermoplastic styrene-acrylic resin, a polyester resin, a polyamide resin, and an olefin copolymer resin. As the thermosetting resin, modified or unmodified silicone resin having the above-mentioned cationic polar group, thermosetting acrylic resin, thermosetting styrene-acrylic resin, phenol resin, urethane resin, thermosetting polyester resin, epoxy There are resins and amino resins. Such a resin having a cationic polar group can be obtained by polymerizing a monomer containing a monomer having a cationic polar group. Alternatively, it can be obtained by binding a compound having a cationic polar group to a resin having no cationic polar group. Furthermore, a polymerization initiator having a cationic polar group is selected as a polymerization initiator when (co) polymerizing a monomer having a cationic polar group and / or another monomer to synthesize a resin. It is also possible to introduce a cationic polar group into the resulting resin.

As for the silicone-based or titanium-based resin which can be prepared from alkoxysilane or alkoxytitanium, a resin having a cationic polar group is acted upon by a silane coupling agent having a cationic polar group during or after the preparation of the resin. It is possible to obtain Examples of such silane coupling agents include N-β (aminoethyl) γ-aminopropyltrimethoxysilane and N-β
(Aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-
Phenyl-γ-aminopropyltrimethoxysilane and the like. These types of silane coupling agents are
Since it is possible to bind to the surface of the core particle through the hydroxyl group that is usually present on the surface of the core particle, the coating layer can be formed alone. As the polymerization initiator having a cationic polar group, there is an amidine type azobis compound.

The resin having a cationic polar group forming the coating layer may be used alone or in a mixture, or may be used as a mixture with a resin having no cationic polar group. The resin having a cationic polar group usually contains the cationic polar group in an amount of 0.1 to 2000 mmol, preferably 0.5 to 1500 mmol, per 100 g of the resin. When used in combination with a resin having no cationic polar group, the resin composition constituting the coating layer of carrier particles preferably contains the cationic polar group in the above proportion.

The resin composition constituting the coating layer of carrier particles contains at least one of the above-mentioned resins having a cationic polar group and, if necessary, a resin having no cationic polar group. As the mixture of the resin having a cationic polar group and the resin having no cationic polar group, a mixture of an alkylated melamine resin and a styrene-acrylic copolymer, a mixture of an alkylated melamine resin and an acrylic modified silicone resin and so on. Further, in the resin composition, if necessary, silica, alumina, carbon black, a fatty acid metal salt, a silane coupling agent,
Additives such as silicone oil are contained, and these have the function of adjusting the properties of the coating layer.

(Preparation of Carrier) The composition containing the resin having a cationic polar group is applied to the surface of core particles by a known method to form a coating layer. For example, the coating layer is formed by mixing the solution or dispersion liquid of the above resin composition with the core particles, coating the solution or dispersion liquid of the resin composition on the surface of the core particles, and drying.
When a thermosetting resin or a reactive resin oligomer is used, it can be cured by heating after coating a solution or dispersion of an uncured resin or oligomer. In forming the coating layer, any of commonly used dipping method, spraying method, fluidized bed method, moving bed method, 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 and xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, a ketone solvent 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 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.

[0088]

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

Example 1 <Preparation of Toner>

[0090]

[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 diameter of 0.015 μm were added to the toner particles in a ratio of 0.3 parts by weight to 100 parts by weight of the toner particles, and mixed with a Henschel mixer. Then, a toner is obtained.

<Preparation of Carrier>

[0094]

[Table 2]

As magnetic core particles, spherical ferrite particles having an average particle size of 100 μm were used. 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 A coating agent having the composition shown in Table 2 was used to obtain a developer in the same procedure as in Example 1.

Example 3 Using the coating agent having the composition shown in Table 2, a developer was obtained in the same procedure as in Example 1.

Comparative Example 1 A developer was obtained in the same manner as in Example 1 except that the coating layer was not used and the coating layer of carrier particles was not formed.

[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) Transfer Efficiency The toner amount in the toner hopper before the start of copying and the toner amount in the toner hopper after copying a predetermined number of 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 a predetermined number of sheets was measured and used as the toner recovery amount. From these values,
The transfer efficiency of the toner was calculated by the following formula (i). Here, the original used for copying is a character original in which the area ratio of the black portion is 8%.

This evaluation was carried out in order to carry out each evaluation test under item (b).

[0103]

[Equation 1]

(B) Image Density (ID) Copying is performed using a character original having an area ratio of black portion of 8%,
Copying was continued until the transfer efficiency was less than 70%. 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.

(C) Fog Density (FD) Copying was performed using a character original having an area ratio of black portion of 8%.
Copying was continued until the transfer efficiency was less than 70%. 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.

(D) Resolution Copying is performed using a character original having an area ratio of the black portion of 8%.
At the time of copying 50,000 sheets (when the transfer efficiency is less than 70% by then), the specified chart original (1
Copying was performed using a document using a plurality of patterns in which a predetermined number of parallel straight lines were drawn per mm), and the copied image was visually judged. The evaluation results are shown in Table 3.

(E) Amount of electrification Copying is performed using a character original whose area ratio of the black portion is 8%.
Copying was continued until the transfer efficiency was less than 70%. 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.

(F) Toner Scattering Copying is performed using a character original having an area ratio of the black portion of 8%.
Copying was continued until the transfer efficiency was less than 70%. 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.

(G) Durability The toner transfer efficiency was calculated from the toner consumption amount after copying 10,000 sheets and the collected toner amount. The durability was defined as the number of sheets when the transfer efficiency became less than 70% for the first time.
The evaluation results are shown in Table 3.

(H) Amount of Adhered Substances on Particle Surface of Carrier by Spent A copy is made using a character original having an area ratio of black portion of 8%.
The developer was sampled at the time of copying 50,000 sheets (when the transfer efficiency was less than 70% by that time). Place the developer on a 400 mesh sieve,
The toner and the carrier were separated by sucking from below with a blower. 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.

[0111]

[Table 3]

[Discussion of Evaluation Results] The developers obtained in Examples 1 to 3 were stable in a state where the image density, fog density, resolution, and charge amount were very good. Furthermore, no toner scattering was observed. In particular, the developers of Examples 1 to 3 had an extremely small amount of spent and further improved durability as compared with the developer of Comparative Example 1 using the particles of the carrier having no coating layer.

[0113]

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 contained in this developer contain a fixing resin having an anionic polar group. The core particles of the carrier contained in this developer are composed of a magnetic material having a specific composition,
In addition, a resin having a cationic polar group is used for the coating layer that coats the core particles. Further, spacer particles having a predetermined particle diameter are attached to the surface of the toner particles as needed. The toner of the developer of the present invention has sufficient chargeability, and the toner particles and carrier particles are also sufficiently bonded. 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. 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 9/113 G03G 9/10 321 351 (72) Inventor Seijiro Ishimaru 1-chome Tamatsukuri, Chuo-ku, Osaka 2-28 Mita Engineering Co., Ltd. (72) Inventor Kazuya Nagao 1-chome Tamatsukuri, Chuo-ku, Osaka City 2-28 Mita Engineering Co., Ltd. (72) Inventor Tomohide Iida 1-chome Takumazo, Chuo-ku, Osaka No. 28 Mita Industrial Co., Ltd.

Claims (5)

[Claims] 1. A two-component developer containing a toner and a carrier, wherein the toner contains toner particles, and the toner particles contain a fixing resin and a magnetic powder dispersed in the resin. 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.
The carrier particles are contained in the toner particles in an amount of 1 to 5 parts by weight, and the carrier particles have core particles and a coating layer for coating the core particles, and the core particles are represented by the following formula (A). The magnetic material is: MOFe ₂ O ₃ (A) where M is Cu, Zn, Fe, Ba, Ni, Mg, M
A two-component developer, which is at least one metal selected from the group consisting of n, Al and Co, and in which the coating layer is a resin composition containing a resin having a cationic polar group. 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. The developer according to claim 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 resin having a cationic polar group is a resin having a basic nitrogen-containing group. 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.