JPH0876510A - Two-component developer - Google Patents

Abstract

PURPOSE: To suppress the scattering of a toner and to improve an image by incorporating toner particles contg. a specified fixing resin, a specified amt. of magnetic powder and a releasing agent and a carrier having specified core particles and coating layers coating the core particles. CONSTITUTION: This two-component developer contains toner particles contg. a fixing resin, magnetic powder dispersed in the resin and a releasing agent and a carrier. The fixing resin consists of a monomer having an anionic polar group or a polymer compsn. obtd. from the monomer and a copolymer compsn. contg. a monomer having >=12C alkyl group in the side chain. The magnetic powder is contained in the toner particles by 0.1-5 pts.wt. per 100 pts.wt. of the fixing resin. The particles of the carrier have core particles and coating layers coating the core particles. The core particles have recesses in the surfaces and are made of a magnetic material represented by the formula MOFe2 O3 (where M is a metal such as Cu or Zn). The coating layers consist of a thermosetting resin and a resin compsn. contg. the thermosetting resin, fill the recesses in the core particles and coat 0.1-60% of the surface area of the core particles.

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]

SUMMARY OF THE INVENTION The present invention is a two-component developer containing a toner and a carrier; the toner contains toner particles; the toner particles are a fixing resin; The fixing resin contains dispersed magnetic powder and a releasing agent; and the fixing resin contains (1) a monomer having an anionic polar group and a monomer having an alkyl group having 12 or more carbon atoms in its side chain. Monomer containing a polymer composition and a polymer composition obtained from a monomer containing (2) a monomer having an anionic polar group and a monomer having an alkyl group having 12 or more carbon atoms in its side chain A composition containing at least one of (1) and (2) of a resin composition comprising a polymer composition obtained from the body; the magnetic powder is 0.1 parts by weight relative to 100 parts by weight of the fixing resin. To 5 parts by weight in the toner particles; particles of the carrier. Has a coating layer covering the core particles and the core particles; the core particles has a recess on the surface and 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
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 thermosetting resin and a thermoplastic resin, and at least the concave portion of the core particle. Coating layer covering 0.1 to 60% of the surface area of the core particles;
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 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 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 coating layer comprises a thermosetting resin and a thermoplastic resin in a weight ratio of 99.
5: 0.5 to 51:49, more preferably 99: 1 to 90:10 by weight.

In a preferred embodiment, the melting point or softening point of the thermoplastic resin is lower than the thermosetting temperature of the thermosetting resin, and more preferably the melting point or softening point of the thermoplastic resin is , Below 150 ° C.

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. , At least one selected from the group consisting of epoxy resins, and amino resins.

In a preferred embodiment, the thermoplastic resin is a group consisting of a thermoplastic acrylic resin, a thermoplastic styrene-acrylic resin, an olefin copolymer resin or wax, a low melting point polyamide resin, and a low melting point polyester resin. It is at least one selected from.

[0017]

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, in order to further enhance the function of the toner, a polymer obtained by using a monomer having an alkyl group having 12 or more carbon atoms in its side chain is contained as a constituent component of the fixing resin. This suppresses the generation of spent due to the release agent. 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 carrier particles have the coating layer that fills at least the concave portions of the core particles, so that the spent resistance is improved and the toner is stably charged.

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 surface of the toner particles. is there.

The carrier of the developer whose chargeability of the carrier becomes insufficient due to the 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 with the spent, the abscissa represents this (shown as the amount of spent), 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 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 the particles 2 are formed on the surface of the particles 1 of the carrier, toner scattering occurs and the 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 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 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 based on 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. The image density is low because the charge amount is insufficient. 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,
Therefore, the toner does not adhere sufficiently to the electrostatic latent image, resulting in a low image density.

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, a toner may contain a charge control agent, so that spent may occur.

When the transferred image is heat-fixed with a heat roll, a release agent is usually contained in the toner particles in order to prevent offset on the transfer paper. As this release agent, various waxes and olefin resins are used. These are heated and kneaded together with the fixing resin and the magnetic powder in the toner manufacturing process. However, the releasing agent has an SP value (solubility parameter value) different from that of the fixing resin which is usually used.
Are not compatible with each other and do not sufficiently disperse in the resin during the above heating and kneading. For this reason, in the obtained toner particles, the releasing agent is present in relatively large particles in a non-uniform manner, and the releasing agent particles are also present on the surface of the toner particles.
Therefore, when such toner particles are used, the release agent adheres to the surface of the carrier particles as a spent. On the other hand, in the present invention, since the fixing resin contains a polymer obtained by using a monomer having an alkyl group having 12 or more carbon atoms in the side chain as described above, the fixing agent and the The compatibility with the fixing resin used in the invention is improved, and the problem of the spent is eliminated.

In the present invention, in order to further improve the transfer efficiency of the toner image, spacer particles having a particle diameter 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.

Fine particles having a particle diameter of about 0.015 μm have been used as an external additive as a conventional fluidity improver for toner. 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.

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, the carrier particles are composed of core particles and a partial coating resin coating layer which fills at least the concave portions on the surface of the core particles. By partially exposing the surface of the core particles in this way, the resistance of the particles of the carrier can be adjusted. Can be charged. Further, since the concave portions of the core particles are filled, the particle surface of the carrier becomes smooth, and the spent of the toner hardly occurs. Therefore, when the toner used in the present invention is combined with the carrier used in the present invention, a developer having extremely few spents and having good developing characteristics due to stabilization of toner charge can be obtained.

[0037]

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 includes (1) a monomer having an anionic polar group and an alkyl group having 12 or more carbon atoms in its side chain. And (2) a polymer composition obtained from a monomer containing a monomer having an anionic polar group and an alkyl group having 12 or more carbon atoms in the side chain. It is a composition containing at least one of a resin composition comprising a polymer composition obtained from a monomer containing the monomer. In the present specification, the “side chain” of a monomer means a site capable of forming a side chain of a (co) polymer obtained by using the monomer.

The copolymer composition containing a monomer having an anionic polar group and a monomer having an alkyl group having 12 or more carbon atoms in the side chain has a monomer having an anionic polar group and a side chain. Obtained by copolymerization using a monomer having an alkyl group having 12 or more carbon atoms, and a monomer having an anionic polar group and a monomer having an alkyl group having 12 or more carbon atoms in the side chain. Or a copolymer of these monomers with other monomers.

Polymer composition obtained from a monomer containing a monomer having an anionic polar group and a polymer obtained from a monomer containing a monomer having an alkyl group having 12 or more carbon atoms in the side chain In the resin composition comprising the composition, a polymer composition obtained from a monomer containing a monomer having an anionic polar group is a homopolymer of a monomer having an anionic polar group or another monomer. A polymer composition obtained from a monomer containing a monomer having an alkyl group having 12 or more carbon atoms in the side chain may be a copolymer with a monomer, It may be a homopolymer of a monomer having a or a copolymer with another monomer. Any of the above copolymers may be a random copolymer, a block copolymer or a graft copolymer.

The fixing resin used in the present invention is preferably a copolymer containing the above-mentioned (1) a monomer having an anionic polar group and a monomer having an alkyl group having 12 or more carbon atoms in its side chain. A combined composition, more preferably a copolymer of a monomer having an anionic polar group, a monomer having an alkyl group having 12 or more carbon atoms in the side chain, and another monomer is there.

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.

Next, the monomer having an alkyl group having 12 or more carbon atoms in its side chain will be described. The alkyl group having 12 or more carbon atoms includes an acyclic linear hydrocarbon group, an acyclic branched hydrocarbon group and a cyclic hydrocarbon group.

As the monomer having an alkyl group having 12 or more carbon atoms in the side chain, 1 carbon atom bonded by an ester bond is used.
Acrylic ester-based monomer such as acrylic acid or methacrylic acid ester having two or more alkyl groups, vinyl ester-based monomer having an alkyl group having 12 or more carbon atoms bonded by an ester bond, and an ether bond bonded A vinyl ether monomer having an alkyl group having 12 or more carbon atoms, an olefin monomer having 14 or more carbon atoms having a double bond at the 1-position, and at least one substituent consisting of an alkyl group having 12 or more carbon atoms Monovinyl aromatic monomer, having a double bond at the 1st and 3rd positions and having 12 carbon atoms
Examples thereof include diolefin-based monomers having at least one alkyl group, and these may be used alone or in combination of two or more.

The acrylic ester type monomer having an alkyl group having 12 or more carbon atoms in the side chain is represented by the following general formula (I)
Indicated by:

[0047]

Embedded image

Here, R ¹ is a hydrogen atom or a lower alkyl group, and R ² is an alkyl group having 12 or more carbon atoms.

Examples of such a monomer include lauryl acrylate, tridecyl acrylate, stearyl acrylate, docosyl acrylate, dicyclohexylmethyl acrylate, dicyclohexylpropyl acrylate, cyclododecyl acrylate, cycloundecanemethyl acrylate, methacryl Lauryl acid, tridecyl methacrylate,
Examples thereof include stearyl methacrylate, docosyl methacrylate, dicyclohexylmethyl methacrylate, dicyclohexylpropyl methacrylate, cyclododecyl methacrylate, cycloundecane methyl methacrylate and the like.

The vinyl ester monomer having an alkyl group having 12 or more carbon atoms in the side chain is represented by the following general formula (II):

[0051]

Embedded image

Here, R ³ is an alkyl group having 12 or more carbon atoms.

Examples of such a monomer include vinyl laurate, vinyl tridecanoate, vinyl stearate, vinyl docosanoate, vinyl triacontanate, vinyl pentylcyclohexanoate, vinyl dicyclohexyl acetate and the like.

The vinyl ether type monomer having an alkyl group having 12 or more carbon atoms in the side chain is represented by the following general formula (III)
Indicated by:

[0055]

[Chemical 3]

Here, R ⁴ is an alkyl group having 12 or more carbon atoms.

Examples of such a monomer include vinyl lauryl ether, vinyl stearyl ether, vinyl docosyl ether, vinyl cyclododecyl ether and the like.

The mono-olefinic monomer having a carbon number of 14 or more having a double bond at the 1-position is represented by the following general formula (IV):

[0059]

[Chemical 4]

Here, R ⁵ and R ⁶ are each independently a hydrogen atom or an alkyl group having 12 or more carbon atoms.

Examples of such a monomer include 1-tetradecene and 1-eicosene.

The monovinyl aromatic monomer having at least one substituent having an alkyl group having 12 or more carbon atoms is represented by the following general formula (V):

[0063]

[Chemical 5]

Here, R ⁷ is a hydrogen atom, a lower alkyl group, an alkyl group having 12 or more carbon atoms, or a halogen atom, and R ⁸ is an alkoxy group, an amino group, a nitro group, or an alkyl group having 12 or more carbon atoms. And Φ is a phenylene group. The phenylene group may further have another substituent, and in this case, the substituent includes a lower alkyl group, a halogen atom, an alkoxy group, an amino group, a nitro group, an alkyl group having 12 or more carbon atoms, and the like. it can. Further, the alkyl group having 12 or more carbon atoms has an ester bond,
They may be bonded via a (thio) ether bond or an amide bond.

Examples of such a monomer include m- or p
-Lauryl styrene, m-stearyl or p-stearyl styrene, α-methyl-3-stearyl styrene, m
-Or p-stearoxystyrene, 4-vinylbenzoic acid stearyl, 4-stearoylaminostyrene and the like can be mentioned.

The diolefin-based monomer having a double bond at the 1- and 3-positions and having at least one alkyl group having 12 or more carbon atoms is represented by the following general formula (VI):

[0067]

[Chemical 6]

Here, R ⁹ , R ¹⁰ and R ¹¹ are each independently a hydrogen atom, a lower alkyl group, an alkyl group having 12 or more carbon atoms, or a halogen atom.

Examples of such a monomer include 1,3-hexadecadiene, 1,3-docosadiene and 2-methyl-
1,3-docosadiene and the like can be mentioned.

The above-mentioned monomer having an anionic polar group and / or a monomer having an alkyl group having a carbon number of 12 or more in the side chain, and other monomers to be polymerized as the case requires, The combination is selected to have the fixability and chargeability required of the toner, and a combination of one or more monomers having an ethylenically unsaturated bond is used.
Examples of such monomers include acrylic ester-based monomers, monovinyl aromatic-based monomers, vinyl ester-based monomers, vinyl ether-based monomers, diolefin-based monomers,
There are mono-olefin type monomers.

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

[0072]

[Chemical 7]

Here, R ¹² is a hydrogen atom or a lower alkyl group, and R ¹³ 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 as other monomers are represented by the following general formula (VIII):

[0076]

Embedded image

Here, R ¹⁴ is a hydrogen atom, a lower alkyl group or a halogen atom, R ¹⁵ 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 as another monomer is represented by the following general formula (IX):

[0080]

[Chemical 9]

Here, R ¹⁶ 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 as another monomer is represented by the following general formula (X):

[0084]

[Chemical 10]

Here, R ¹⁷ 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-based monomer as another monomer is represented by the following general formula (XI):

[0088]

[Chemical 11]

Here, R ¹⁸ , R ¹⁹ and R ²⁰ are each independently a hydrogen atom, a lower alkyl group or a halogen atom.

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

Monoolefin-based monomers as other monomers are represented by the following general formula (XII):

[0092]

[Chemical 12]

Here, R ²¹ and R ²² are each independently a hydrogen atom or a lower alkyl group.

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

A monomer having an anionic polar group and / or having 1 carbon atom in the side chain, which is obtained by polymerizing the above-mentioned monomer.
Specific examples of the copolymer composition obtained from a monomer containing a monomer having two or more alkyl groups include (meth) acrylic acid-stearyl (meth) acrylate copolymer, styrene- (meth ) Stearyl acrylate- (meth) acrylic acid copolymer, (meth) acrylic acid ester- (meth) acrylic acid stearyl- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid ester- (meth)
Stearyl acrylate- (meth) acrylic acid copolymer,
Styrene-stearyl (meth) acrylate-maleic acid copolymer, maleic acid-stearyl (meth) acrylic acid copolymer, styrene-tridecyl (meth) acrylate-
Examples include (meth) acrylic acid copolymers and styrene- (meth) acrylic acid lauryl- (meth) acrylic acid copolymers. Furthermore, a polyester resin having an anionic polar group can be used. When the anionic polar group is present in the form of a free acid, such a composition has the anionic polar group in a ratio such that the acid value is 2 to 30, preferably 5 to 15. Is desirable. 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 composition, that is, the concentration of the anionic polar group, is lower than the above range, the chargeability of the toner is insufficient. Conversely, when it is higher than the above range, the toner has hygroscopicity. Not preferable. Further, the monomer having an alkyl group having 12 or more carbon atoms in the side chain is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, and more preferably 100 parts by weight of the total monomers. 1 to 5 parts by weight is preferably copolymerized. When the copolymerization amount of the monomer having an alkyl group having 12 or more carbon atoms in the side chain is less than the above range, the compatibility between the release agent and the fixing resin is deteriorated and the spent is liable to occur. If it is too large, the Tg of the fixing resin will be low, resulting in poor storage stability.

A suitable fixing resin is composed of the above-mentioned monomer having an anionic polar group and at least one kind of the acrylic monomer of the formula (I), and if necessary, the compound of the formula (I
Any monomer of I) to formula (VI) may be copolymerized as an optional component. Further, other monomers may be copolymerized if necessary. Each of the above monomers is used to prepare the above resin.
One kind or a combination of two or more kinds can be used.

As the fixing resin used in the present invention, a composition containing the above-mentioned copolymer composition or a mixture of the polymer compositions is used, and in this composition, the above-mentioned copolymer composition or the polymer composition is used. In addition to the mixture of the combined composition, a polymer having no anionic polar group and having no side chain having an alkyl group having 12 or more carbon atoms may be contained. In that case, the content ratio of the anionic polar group and the content ratio of the monomer component having an alkyl group having 12 or more carbon atoms in the entire composition are preferably in the above ranges.

(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 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.

(Release Agent) As a compounding agent contained in the toner particles, a release agent can be mentioned. Examples of the release agent used in the present invention include natural and synthetic waxes and a molecular weight of 2000 to 16000, preferably a molecular weight of 300.
An olefin resin of 0 to 6000 may be used.
As the olefin resin, polypropylene, polyethylene, propylene-ethylene copolymer and the like can be used, but polypropylene is particularly preferable. The release agent is contained in an amount of 0.01 to 6 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the fixing resin.
The release agent has a function of preventing offset during heat fixing. If the amount of the release agent is less than 0.01 part by weight, the offset resistance at the time of heat fixing may be insufficient, and if it exceeds 6 parts by weight, the spent tends to be generated.

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

Examples of the compounding agents include coloring agents.

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

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

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

The above-mentioned 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.

(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 premixed 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 improving agent 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 the silica particles is usually about 0.015 μm in the primary particle size, and is 0.1% per the total weight of the toner, that is, the total weight of the toner particles and the external additive.
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 the 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 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. In the present invention, sintered ferrite particles are particularly preferable. 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, 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 core particles are generally obtained by granulating a magnetic material having a fine particle size of submicron into substantially spherical particles by means of spray granulation and then sintering by means such as firing. Although it is obtained, it has recesses or wrinkles on the surface due to shrinkage during sintering.

The resin composition forming the coating layer of carrier particles comprises a thermosetting resin and a thermoplastic resin. The thermoplastic resin preferably has appropriate compatibility and dispersibility with the thermosetting resin. By having such appropriate compatibility and dispersibility, the resin composition can be uniformly applied to the surface of the core particles in the state of a solution or a dispersion at the time of preparation of carrier particles described later.
Furthermore, during thermosetting, the thermoplastic resin may be repelled from the thermosetting resin, filled in the recesses on the surface of the core particle, and a partial coating may be formed on the surface of the core particle. As a result, the core particles are partially exposed on the particle surface of the carrier, and the high resistance of the carrier is controlled, so that it is possible to maintain a high image density without excessively charging the toner.

In order to sufficiently achieve the above effects, the coating layer contains a thermosetting resin and a thermoplastic resin in a weight ratio of 99.5: 0.5 to 51:49, preferably a weight ratio of 99. More preferably, the composition comprises from 1 to 90:10. Further, the melting point or softening point of the thermoplastic resin is preferably lower than the thermosetting temperature of the thermosetting resin. The melting point or softening point of the thermoplastic resin is preferably lower than 150 ° C.

Examples of the thermosetting resin include modified or unmodified silicone resin, thermosetting acrylic resin, thermosetting styrene-acrylic resin, phenol resin, urethane resin, thermosetting polyester resin, epoxy resin, amino resin. Examples of the thermoplastic resin include a thermoplastic acrylic resin, a thermoplastic styrene-acrylic resin, an olefin copolymer resin or wax, a low melting point polyamide resin, and a low melting point polyester resin.

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 properties of the coating layer.

(Preparation of Carrier) The composition containing the thermosetting resin and the thermoplastic resin is applied to the core particle surface by a known method to form a coating layer. For example,
The solution or dispersion of the resin composition is mixed with core particles, and the surface or core particles are coated with the solution or dispersion of the resin composition, dried if necessary, and coated by curing by heating or the like. A layer is formed. 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 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 size of the carrier thus obtained is 30 to 200 μm, preferably 50 to 150 μm. The carrier particle coating layer covers 0.1% to 60% of the surface area of the core particles. The weight of the coating layer of carrier particles is 0.00 based on 100 parts by weight of the core particles.
1 to 2.5 parts by weight, preferably 0.005 to 2.0 parts by weight. The volume resistivity of the 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 in the range of 30 to 70 emu / g, preferably 45 to 65 emu / g.

The particle surface structure of the carrier of the two-component developer of the present invention is shown in FIG. 10 (enlarged side view) and FIG. 11 (enlarged sectional view). In the figure, carrier particles 11 are composed of core particles 12 and a coating layer 13. The surface of the core particle 12 has a concave portion 14, a relatively flat flat portion 15, and a convex portion 16. In the particles of the carrier used in the present invention, the resin filling layer 17 is present in the concave portion 14, and the exposed surface of the particle of the carrier is present in the flat portion 15 and the convex portion 16, and the coating layer is the partial coating layer 19a. Exists as. On the other hand, in the conventional carrier particle 10 using only the thermosetting resin, as shown in FIG. 12 (enlarged cross-sectional view), the resin is not completely filled in the concave portion 14 and the flat portion 1 is formed.
5 and the convex portion 16 have the continuous coating layer 19b. In the particles 11 of the carrier used in the present invention shown in FIG. 11, the coating resin layer is broken at the exposed portions 18a and 18b due to the cohesive failure of the low melting point thermoplastic resin during thermosetting to form the partial coating layer 19a.

(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.

[0124]

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

Example 1 <Preparation of Toner>

[0126]

[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 as a fluidity improving agent and hydrophobic alumina having an average particle diameter of 0.3 μm as spacer particles were added to 100 parts by weight of the toner particles. 0.
3 parts by weight and 0.6 parts by weight were added, and the mixture was mixed for 2 minutes with a Henschel mixer and externally added to obtain a toner.

<Preparation of carrier>

[0130]

[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 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.

Comparative Example 1 A developer was obtained in the same manner as in Example 1 except that 24.5 parts by weight of acrylic modified silicone resin and 0.5 part by weight of styrene-acrylic resin were used as coating agents. .

[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 Copying is performed using a character original having an area ratio of the black portion of 8%.
The toner scattering state in the copying machine at the time of copying 50,000 sheets 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 amount of toner in the toner hopper before the start of copying and the amount of toner 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%.

[0140]

[Equation 1]

Table 3 shows the evaluation results.

(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.

[0143]

[Table 3]

[Discussion of Evaluation Results] The developer obtained in Example 1 was stable in a very good image density and excellent in transfer efficiency as compared with the developer of Comparative Example 1. In particular, in the developer of Example 1, the amount of the deposits of the carrier on the particle surface of the carrier was about 3/5, which was smaller than that of Comparative Example 1, and no toner scattering was observed.

[0145]

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. In the toner particles of the toner used in this developer, (1) a copolymer composition containing a monomer having an anionic polar group and a monomer having an alkyl group having 12 or more carbon atoms in its side chain, And (2) a polymer composition comprising a monomer containing a monomer having an anionic polar group and a polymer composition comprising a monomer containing a monomer having an alkyl group having 12 or more carbon atoms in a side chain A fixing resin made of a composition containing at least one of a resin composition made from a substance and a magnetic powder is contained in the toner particles in a predetermined ratio, and a release agent is further contained. 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 a thermosetting resin and a thermoplastic resin are used in the coating layer for coating the core particles, and the recesses of the core particles are used. And partially cover its surface. Therefore, it is possible to impart a good charge to the toner without excessively charging the toner and maintain a high image density. Furthermore, the particle surface of the carrier becomes smooth, and spent is less likely to occur. Since the toner of the developer of the present invention contains a release agent, it is excellent in offset resistance and does not generate the spent as in the case of using a conventional release agent. Further, since the carrier has the above-mentioned coating layer, the chargeability of the spent and the toner is suitably controlled. The toner of such a developer has sufficient chargeability, and the toner particles and the carrier particles are also sufficiently bonded. Spent does not occur during copying, toner does not scatter, 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.

FIG. 10 is an enlarged side view of particles of the carrier of the developer of the present invention.

FIG. 11 is an enlarged cross-sectional view of particles of the carrier of the developer of the present invention.

FIG. 12 is an enlarged cross-sectional view of particles of a carrier of a conventional developer.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Carrier particle 2 Toner 22 Reverse polarity toner 11 Carrier particle 12 Core particle 13 Covering layer 14 Recessed portion 15 Flat portion 16 Convex portion 17 Resin filling layer 18a Carrier particle surface convex portion exposed portion 18b Carrier particle surface flat portion exposed portion 19a Partial coating layer 19b Continuous coating layer

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location G03G 9/107 9/113 G03G 9/08 325 365 9/10 321 351 352 (72) Inventor Tamura Eiichi 1-22-28 Tamatsukuri, Chuo-ku, Osaka Mita Kogyo Co., Ltd. (72) Inventor Nobuaki Kono 1-2-2 Tamatsukuri, Chuo-ku, Osaka Mita Kogyo Co., Ltd. (72) Inventor Kazuhiko Fujii 1-2-2 Tamatsukuri, Chuo-ku, Osaka Mita Industrial Co., Ltd.

Claims (12)

[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, a magnetic powder dispersed in the resin, and a mold release. And a fixing composition, wherein the fixing resin contains (1) a monomer having an anionic polar group and a monomer having an alkyl group having 12 or more carbon atoms in a side chain, and (2) ) A polymer composition obtained from a monomer containing a monomer having an anionic polar group and a polymer composition obtained from a monomer containing a monomer having an alkyl group having 12 or more carbon atoms in a side chain And a magnetic composition containing at least one of (1) and (2) of the resin composition, wherein the magnetic powder is 0.
1 to 5 parts by weight is contained in the toner particles, the carrier particles have core particles and a coating layer that coats the core particles, and the core particles have concave portions on the surface, And a magnetic material represented by the following formula (A): 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 thermosetting resin and a thermoplastic resin, and at least the concave portion of the core particle 0.1% to 60% of the surface area of the core particles
A two-component developer which is a coating layer for coating the. 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 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. 5. The developer according to claim 1, wherein the coating layer is a composition containing a thermosetting resin and a thermoplastic resin in a weight ratio of 99.5: 0.5 to 51:49. 6. The developer according to claim 1, wherein the coating layer is a composition containing a thermosetting resin and a thermoplastic resin in a weight ratio of 99: 1 to 90:10. 7. The developer according to claim 1, wherein the melting point or softening point of the thermoplastic resin is lower than the thermosetting temperature of the thermosetting resin. 8. The developer according to claim 1, wherein the melting point or softening point of the thermoplastic resin is lower than 150 ° C. 9. The core particles have a particle size of 50 to 150.
The developer according to claim 1, which has a thickness of μm. 10. The weight of the coating layer is the core particle 1
The developer according to claim 1, which is 0.001 to 2.5 parts by weight with respect to 00 parts by weight. 11. 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. 12. The thermoplastic resin is at least selected from the group consisting of a thermoplastic acrylic resin, a thermoplastic styrene-acrylic resin, an olefin copolymer resin or wax, a low melting point polyamide resin, and a low melting point polyester resin. The developer according to claim 1, which is a kind.