JP2013238734A - Carrier for electrophotography and two-component developer including the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a carrier for electrophotography that has good transfer efficiency, can charge toner stably for a long period, and prevents the occurrence of carrier depletion and white streaks of images; and a two-component developer including the carrier for electrophotography.SOLUTION: A carrier for electrophotography consists of a carrier core material made of ferrite; and a resin layer that covers the carrier core material, and contains magnetic fine particles that are not conductive under 1000 V applied voltage and have a resistance value of 10to 10Ω cm, and thermosetting organic fine particles having a triazine ring.

Description

  The present invention relates to an electrophotographic carrier and a two-component developer containing the same.

  In recent years, with the remarkable development of OA equipment, image forming apparatuses such as copying machines, printers, and facsimile machines using an electrophotographic system have become widespread.

In an image forming apparatus using an electrophotographic method, a charging process in which the surface of a rotationally driven photoreceptor is uniformly charged by a charging device; the surface of the photoreceptor is irradiated with laser light by an exposure device. An exposure step for forming an electrostatic latent image on the surface; a development step for developing the electrostatic latent image on the surface of the photoconductor with toner using a developing device to form a toner image on the surface of the photoconductor; An image is formed through a transfer step of transferring onto a transfer material (recording medium) by a transfer device; and a fixing step of fixing the toner image onto the transfer material by heating of the fixing device.
Then, the transfer residual toner remaining on the surface of the photoconductor after the image forming operation is removed by a cleaning device in a cleaning process and collected in a predetermined recovery unit, and the residual charge on the surface of the photoconductor after the cleaning becomes the next image formation. In order to prepare for this, the charge is removed by the charge removal device in the charge removal step.

The developer for developing the electrostatic latent image on the surface of the photoreceptor includes a one-component developer containing only toner, and a two-component developer containing toner and an electrophotographic carrier (hereinafter also referred to as “carrier”); There is.
In the two-component developer, the functions of stirring, transporting and charging the toner are given by the carrier, and the toner itself does not need to have the function of the carrier, and the function can be separated between the toner and the carrier. The controllability is improved as compared with the one-component developer contained in, and a high-quality image is easily obtained. For this reason, research on the toner and carrier constituting the two-component developer and the combined use has been actively conducted.

The carrier has two basic functions: a function of stably charging the toner to a desired charge amount, and a function of transporting the toner to the photoreceptor. The carrier is stirred in the developing tank, conveyed onto the magnet roller, forms a magnetic spike, passes through the regulating blade, returns to the developing tank again, and is repeatedly used. Accordingly, the carrier is required to have a stable basic function, particularly a function of stably charging the toner as it is continuously used.
Further, depending on the electrical characteristics (resistance) of the carrier, the influence on the image quality, such as inducing the carrier rise and whiteout of the image, is great.

In order to maintain the basic functions of the carrier, for example, the surface of the carrier core material is made of a resin coating layer (hereinafter referred to as “resin layer” with a styrene-acrylic copolymer resin or polyurethane resin having a high surface tension or a fluororesin having a low surface tension. Is also proposed.
However, a resin having a high surface tension has good adhesion to the carrier core material, but there is a problem that the toner tends to be spent (consumed). A resin with low surface tension is effective for toner spent, but has poor adhesion to the carrier core material. When the carrier is stirred in the developing tank, the resin layer is peeled off to stabilize the charge. There is a problem that it cannot be planned.

Japanese Patent Laid-Open No. 1-284862 (Patent Document 1) proposes a carrier in which a carrier core material is coated with a silicone resin containing an aminosilane coupling agent in order to obtain a desired chargeability.
On the other hand, in recent years, full-color electrophotography has progressed, and accordingly, improvement of toner, for example, external additives that are externally added to the toner surface has been actively performed. The external additive imparts fluidity to the toner and functions as a charge amount control aid.
In full color, when the particle size of the external additive is increased for the purpose of increasing the transfer efficiency of the toner, the contact opportunity between the toner and the carrier is hindered, and it becomes difficult to stably charge the toner. Further, the color toner has higher insulation than the monochrome toner due to its material, and it is difficult to stabilize the charging.
Therefore, the carrier of Patent Document 1 has a problem that the toner cannot be sufficiently charged when the particle diameter of the external additive is increased in order to improve the transfer efficiency of the toner.

  In view of this, Japanese Patent Application Laid-Open No. 2007-121911 (Patent Document 2) proposes a carrier in which a carrier core material (core particle) is coated with a resin containing nonmagnetic fine particles in order to stably charge the toner. . According to the carrier of Patent Document 2, even if the resin layer is worn by stirring with the toner, the non-magnetic fine particles serve as a spacer and the distance between the toner and the carrier core is kept constant. An increase in van der Waals force can be suppressed, and adhesion of toner to the carrier can be suppressed to maintain the charge imparting ability to the toner.

  Japanese Patent Application Laid-Open No. 2009-93135 (Patent Document 3) includes conductive fine particles coated with a noble metal such as gold, platinum and palladium in a resin layer, and a chain having an average number of connected particles of 4 or more by the noble metal. A carrier in which a structure is formed is disclosed. According to the carrier of Patent Document 3, the ability to impart charge to the toner can be improved by forming a chain structure in the resin layer and providing a conductive path.

  JP-A-10-333363 (Patent Document 4) discloses a carrier in which carbon fine particles having an average particle diameter of 1 to 20 μm or carbon fine particles plated with a conductive material are contained in a resin layer. . According to the carrier of Patent Document 4, the adhesion of toner to the carrier can be suppressed, and the rise of charging can be accelerated.

  Furthermore, JP-A-61-296363 (Patent Document 5) discloses a carrier in which specific metal oxide fine particles are contained in a resin layer. According to the carrier of Patent Document 5, the toner physically attached to the photoreceptor can be peeled off, and a good image can be formed.

  In addition, in JP-A-2001-22131 (Patent Document 6) and JP-A-2002-162792 (Patent Document 7), magnetite surface-treated with a tertiary amine compound, a silane coupling agent, silicone oil or the like is used. A carrier contained in a resin layer is disclosed.

JP-A-1-284862 JP 2007-121911 A JP 2009-93135 A JP 10-333363 A JP 61-296363 A JP 2001-22131 A JP 2002-162792 A

However, in the resin-coated carriers of Patent Documents 2 to 4, the conductivity of the carrier can be ensured, but if the electrical resistance is too low, the carrier rises easily. On the other hand, when the resistance is increased, a problem such as white spots in the image occurs. Furthermore, the ability to impart charge to the toner over a long period is insufficient, and the toner cannot be stably charged.
Further, Patent Document 5 does not describe a toner to which an external additive is externally added, and transfer efficiency becomes insufficient depending on a toner combined with a resin-coated carrier. Furthermore, since the resistance value as a carrier is lowered simply by including metal oxide fine particles, carrier adhesion is induced, and the above-described problems occur in practice.
Furthermore, in the resin-coated carriers of Patent Documents 6 and 7, the surface-treated magnetite increases the amount of charge in the initial charging stage in actual use, but the amount of charge decreases as the number of printed sheets increases, resulting in the effect of surface treatment. There is a problem that is virtually eliminated. This is presumably because the magnetite particles themselves act as charge leak points because the resistance of the magnetite particles themselves is low.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have performed a predetermined high resistance treatment such as surface oxidation, and do not break down (conduct) under an applied voltage of 1000 V and 10 It was found that charge leakage can be suppressed by adding magnetite fine particles having a resistance value of ⁷ to 10 ⁹ Ω · cm to the resin layer. However, in order to control the charge amount, a silane coupling having an amino group When an agent is used, there is a problem that the charge amount decreases as the number of printed sheets increases, and the difference in charge amount from the initial value widens.

  Accordingly, the present invention provides an electrophotographic carrier that has good transfer efficiency, can stably charge toner for a long period of time, and has no carrier rise or image blanking, and a two-component developer including the same. This is the issue.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have performed a predetermined high resistance treatment such as surface oxidation, and do not break down (conduct) under an applied voltage of 1000 V and 10 By adding magnetic fine particles having a resistance value of ⁷ to 10 ⁹ Ω · cm and thermosetting organic fine particles having a triazine ring (thermosetting fine particles) to the resin layer (coat layer), charge leakage can be suppressed, The present inventors have found that the above problems can be solved, and have completed the present invention.

Thus, according to the present invention, the carrier core material made of ferrite, and the magnetic fine particles covering the carrier core material and not conducting at 1000 V applied voltage and having a resistance value of 10 ⁷ to 10 ⁹ Ω · cm, An electrophotographic carrier comprising a resin layer containing thermosetting organic fine particles having a triazine ring is provided.

  In addition, according to the present invention, there is provided a two-component developer comprising the above-described electrophotographic carrier and a toner.

According to the present invention, it is possible to provide a carrier that is excellent without carrier rising and white spots and that can stably charge a toner for a long period of time and a two-component developer including the carrier.
That is, by forming an image using the two-component developer of the present invention, a high-quality image is reproduced with high definition, good color reproducibility, high image density, and few image defects such as fog. It can be formed stably.

In the carrier of the present invention, the magnetic fine particles have a volume average particle diameter of 0.08 to 0.8 μm, so that the magnetic fine particles are contained at a ratio of 0.05 to 55 parts by weight with respect to 1000 parts by weight of the carrier core material. Thus, the magnetic fine particles are subjected to surface oxidation treatment, whereby the above-described effect is further exhibited.
Further, the carrier of the present invention has a volume average particle diameter of 0.1 to 1 μm, so that the thermosetting organic fine particles are 0.05 to 50 to 100 parts by weight of the resin of the resin layer. When the resin layer is contained in the proportion by weight, the resin layer further includes conductive fine particles, and thus the above-described effect is further exhibited.

It is a figure which shows the relationship between the applied voltage and resistance value of the magnetic fine particle which carried out the surface oxidation process, and the untreated magnetic fine particle. It is a schematic diagram of the measuring jig used for the resistance value measurement of magnetic fine particles.

The carrier of the present invention includes a carrier core material made of ferrite, a magnetic fine particle and a triazine ring that cover the carrier core material, do not conduct under an applied voltage of 1000 V, and have a resistance value of 10 ⁷ to 10 ⁹ Ω · cm. And a thermosetting organic fine particle having a resin layer.
In this specification, unless otherwise specified, “average particle size” means “volume average particle size”.

  In the carrier of the present invention, the resin layer covering the carrier core material contains magnetic fine particles having specific physical properties and thermosetting organic fine particles (thermosetting fine particles) containing a triazine structure, thereby stabilizing the toner for a long period of time. Can be charged. Therefore, by forming an image using such a two-component developer containing a carrier, the image can be reproduced with high definition, color reproducibility is good, the image density is high, and image defects such as fog are high. A quality image can be formed stably.

  As in the prior art, in the case where the resin layer covering the carrier core material contains a conductive agent such as carbon black instead of magnetic fine particles, this is a case where a color toner having a high insulating property and a two-component developer are used. In the initial stage, the conductive agent can easily flow the electric charge between the toner and the carrier to sufficiently charge the toner. However, when the number of printed sheets increases, that is, when the toner on the carrier surface is replaced, the charge is depleted, that is, the carrier rises, and the toner cannot be sufficiently charged. This phenomenon becomes more prominent when the average particle diameter of the external additive externally added to the toner is increased in order to improve the transfer efficiency, and the contact between the toner and the carrier is inhibited.

On the other hand, the carrier of the present invention has optimum conductivity (conductivity), and the surface of the resin layer is scraped little by little to suppress adhesion of toner or the like to the surface, so that charging can be stabilized.
By incorporating magnetic fine particles and thermosetting organic fine particles having a triazine structure in the resin layer, it is considered that electric charge is supplied to the toner from the inside of the resin layer via the magnetic fine particles. Even if the average particle diameter of the external additive is large, the toner can be stably charged over a long period of time.
Further, since the magnetic fine particles have a resistance value of 10 ⁷ to 10 ⁹ Ω · cm, that is, appropriate conductivity, white spots (pinholes) in an image are improved when a two-component developer is used.
Further, normally, when conductive fine metal particles are added, conduction increases as the electrolysis strength increases, and carrier adhesion increases due to induction charging of carriers, but magnetic fine particles do not conduct even under high voltage (1000 V applied voltage). Therefore, carrier adhesion can be suppressed.

  The following description will be divided into items of (1) carrier, (2) two-component developer, (3) toner, and (4) image forming method. The magnetic fine particles and the thermosetting organic fine particles, which are the characteristics of the present invention, will be described in detail in the items (1) and (1-3) and (1-4) of the carrier.

(1) Carrier The carrier according to the present invention includes a carrier core material, a resin layer that covers (forms) the surface thereof, includes magnetic fine particles having specific electrical characteristics, and thermosetting organic fine particles having a triazine ring. (Also referred to as “coat layer”).

(1-1) Carrier core material (also referred to as “core particle”)
The carrier core material is not particularly limited as long as it is commonly used in the technical field, and examples thereof include magnetic metals such as iron, copper, nickel, and cobalt, and magnetic metal oxides such as ferrite and magnetite. With these carrier core materials, a carrier suitable for a developer used in the magnetic brush development method can be obtained.
Among these, particles containing a ferrite component are preferable. Since ferrite has a high saturation magnetization and a low density coat carrier, the use of the developer in the developer makes it difficult for the coat carrier to adhere to the photoreceptor, and a soft magnetic brush is formed, resulting in high dot reproduction. An image is obtained.

  Examples of ferrites include zinc ferrite, nickel ferrite, copper ferrite, barium ferrite, strontium ferrite, nickel-zinc ferrite, manganese-magnesium ferrite, copper-magnesium ferrite, manganese-zinc ferrite, manganese- Examples thereof include copper-zinc ferrite and manganese-magnesium-strontium ferrite.

Ferrite can be produced by a known method. For example, ferrite raw materials such as Fe ₂ O ₃ and Mg (OH) ₂ are mixed, and this mixed powder is heated in a heating furnace and calcined. After cooling the obtained calcined product, it is pulverized by a vibration mill so as to become particles of about 1 μm, and a dispersant and water are added to the pulverized powder to prepare a slurry. The slurry is wet pulverized with a wet ball mill, and the resulting suspension is granulated and dried with a spray dryer to obtain ferrite particles.

The average particle diameter of the carrier core material is preferably 25 to 100 μm, and more preferably 25 to 90 μm.
If the average particle diameter of the carrier core material is in the above range, the toner can be stably conveyed to the electrostatic latent image formed on the photoreceptor, and a high-definition image can be formed over a long period of time. it can.
When the average particle size of the carrier core material is less than 25 μm, it may be difficult to control carrier adhesion. On the other hand, when the average particle diameter of the carrier core material exceeds 100 μm, a high-definition image may not be formed.

(1-2) Resin The resin forming the resin layer is not particularly limited as long as it is a resin that is commonly used in the technical field, and examples thereof include acrylic resins, acrylic-modified resins, and silicone resins.
In the present invention, one of the above resins can be used alone or in combination of two or more.

Examples of the acrylic resin include polyacrylate, polymethyl methacrylate, polyethyl methacrylate, poly-n-butyl methacrylate, polyglycidyl methacrylate, polyfluorinated acrylate, styrene-methacrylate copolymer, styrene-butyl methacrylate copolymer, and styrene. -Ethyl acrylate copolymer.
Commercially available acrylic resins include, for example, product names manufactured by Mitsubishi Rayon Co., Ltd .: Dainar SE-5437, product names manufactured by Sekisui Chemical Co., Ltd .: product names manufactured by S-LEC PSE-0020, products manufactured by Sanyo Chemical Industries, Ltd .: HAIMER ST95, Mitsui Chemicals product name: FM601, etc.

The silicone resin suppresses toner spent and can improve the adhesion between the carrier core material and the resin layer, and is preferably a cross-linked silicone resin.
As shown below, the cross-linked silicone resin is a known silicone resin in which hydroxyl groups bonded to Si atoms or a hydroxyl group and an OX group are crosslinked and cured by a heat dehydration reaction, a room temperature curing reaction, or the like.

(In the formula, plural Rs are the same or different and represent a monovalent organic group, and the group OX represents an acetoxy group, an aminoxy group, an alkoxy group, an oxime group, etc.)

  As the crosslinkable silicone resin, either a heat curable silicone resin or a room temperature curable silicone resin can be used. In order to crosslink the thermosetting silicone resin, the resin is heated to about 200 to 250 ° C. Moreover, although heating is not required to cure the room temperature curable silicone resin, it may be heated at 150 to 280 ° C. in order to shorten the curing time.

  Among the cross-linked silicone resins, those in which the monovalent organic group represented by R is a methyl group are preferable. This cross-linked silicone resin has a fine cross-linked structure, and when this is used to form a resin layer of a carrier core material, a good carrier such as water repellency and moisture resistance can be obtained. However, if the cross-linked structure becomes too dense, the resin layer tends to become brittle, so selection of the molecular weight of the cross-linked silicone resin is important.

The weight ratio of silicon to carbon (Si / C) in the cross-linked silicone resin is preferably 0.3 to 2.2.
If Si / C is less than 0.3, the hardness of the resin layer may be reduced, and the carrier life may be reduced. On the other hand, if Si / C exceeds 2.2, the charge imparting property of the carrier to the toner is easily affected by the temperature change, and the resin layer may become brittle.

  Examples of commercially available cross-linked silicone resins include product names manufactured by Toray Dow Corning Co., Ltd .: SR2400, SR2410, SR2411, SR2510, SR2405, 840RESIN, 804RESIN, products manufactured by Shin-Etsu Chemical Co., Ltd .: KR350, KR271, KR272. , KR274, KR216, KR280, KR282, KR261, KR260, KR255, KR266, KR251, KR155, KR152, KR214, KR220, X-4040-171, KR201, KR5202, and KR3093.

The resin is preferably a silicone resin, particularly a cross-linked silicone resin, and may contain other resins as long as the preferred characteristics are not impaired.
Examples of other resins include epoxy resins, urethane resins, phenol resins, acrylic resins, styrene resins, polyamides, polyesters, acetal resins, polycarbonates, vinyl chloride resins, vinyl acetate resins, cellulose resins, polyolefins, and copolymers thereof. Resin, compounded resin, etc. are mentioned, Acrylic resin is preferable at a point with high charging ability among these. For example, a bifunctional silicone oil may be included in order to further improve the moisture resistance, releasability, and the like of a resin layer formed of a silicone resin (particularly a cross-linked silicone resin).

(1-3) Magnetic Fine Particles In the carrier of the present invention, 1000 V is applied as a magnetic fine particle to the resin layer covering the carrier core material together with the thermosetting organic fine particles having a triazine ring described in detail in the next item (1-4). It includes magnetic fine particles that do not conduct under voltage and have a resistance value of 10 ⁷ to 10 ⁹ Ω · cm.
Thereby, the charge imparting ability of the carrier to the toner can be further improved, the toner can be stably charged over a long period of time, and the mechanical strength of the resin layer and the adhesion of the resin layer to the carrier core material can be improved. Can be improved.
Therefore, by forming an image using the two-component developer containing the carrier of the present invention, the image can be reproduced with high definition, color reproducibility is good, image density is high, and image defects such as fog are high. A quality image can be formed stably.

The volume resistance value of the magnetic fine particles under an electric field of 1000 V / cm can be measured with a measuring jig as shown in FIG.
FIG. 2 is a schematic diagram of a measuring jig used for measuring the resistance value of the magnetic fine particles.
The measuring jig 1 includes a magnet 2, an aluminum electrode 3, and a base (acrylic resin plate) 4. The distance between the electrodes 3 is 1 mm, and parallel plate electrodes having a size of 10 mm × 40 mm are formed. 200 mg of magnetic fine particles are inserted between the electrodes, and then the magnet 2 (surface magnetic flux density 1500 gauss, magnet area 10 mm × 30 mm of the facing portion) is arranged so that the N pole and the S pole face each other. Hold in between. The bridge resistance value is calculated by measuring the current value when 1000 V is applied to the electrode 3 at a DC voltage of 1 V step, and this value is set as the volume resistance value of the magnetic fine particles.

As the magnetic fine particles, magnetic fine particles of the same material as the carrier core material are used.
The magnetic fine particles of the present invention have specific physical properties as described above. When magnetic fine particles having no such physical properties are used, the magnetic fine particles of the present invention are subjected to high resistance treatment such as surface oxidation treatment. Magnetic fine particles can be obtained.
Examples of the surface oxidation treatment include fluid oxidation in an oxidizing atmosphere such as 250 to 500 ° C. in the air. Specific processing will be described in the embodiment.

The magnetic fine particles preferably have an average particle diameter of 0.05 to 0.8 μm, and more preferably 0.08 to 0.5 μm.
If the average particle diameter of the magnetic fine particles is in the above range, when the resin layer is formed on the surface of the carrier core material, it is possible to stably prevent the magnetic fine particles from being unevenly distributed in the resin layer and between the carriers. Since the magnetic fine particles do not form irregularities on the surface of the resin layer, a uniform resin layer can be formed. The reason for this is not clear, but it is presumed that small metal oxide fine particles are held uniformly by the mutual magnetic force.
When the magnetic fine particles used as a raw material do not have an appropriate average particle size, it may be subjected to a pulverization treatment or a classification treatment using a known apparatus such as a sand mill in advance before the high resistance treatment. . Specific processing will be described in the embodiment.

The blending amount of the magnetic fine particles is not particularly limited, but is preferably 0.05 to 65 parts by weight, and more preferably 0.5 to 40 parts by weight with respect to 1000 parts by weight of the carrier core material.
When the blending amount of the magnetic fine particles is in the above range, the excellent effect of the present invention is exhibited.
That is, the blending amount of the magnetic fine particles in the resin layer is preferably 1 to 183 parts by weight and more preferably 10 to 133 parts by weight with respect to 100 parts by weight of the resin.
If the blending amount of the magnetic fine particles is less than 1 part by weight, the effect of the magnetic fine particles may not be sufficiently obtained. On the other hand, if the amount of the magnetic fine particles exceeds 183 parts by weight, the resin layer may not be formed uniformly.

(1-4) Thermosetting organic fine particles (also referred to as “organic fine particles”)
The carrier of the present invention is characterized in that the resin layer covering the carrier core material contains thermosetting organic fine particles having a triazine ring together with the magnetic fine particles described in detail in (1-3) above.
Thereby, the chargeability can be controlled more stably, and charge leakage can be suppressed by using the magnetic fine particles together.
The organic fine particles may be selected from those that do not dissolve in the solvent of the resin liquid for forming the resin layer described later. As a result, the organic fine particles can be dissolved and finely dispersed in the resin layer to avoid the expiration of the charge control function of the organic fine particles. The organic fine particles are not particularly limited as long as they are organic fine particles containing a triazine ring. Examples thereof include resin fine particles, benzoguanamine resin fine particles, acetoguanamine resin fine particles, and benzoguanamine / melamine resin fine particles. Among these, melamine resin fine particles and benzoguanamine / melamine resin fine particles are particularly preferable. Moreover, it is preferable that the average particle diameter is 0.1-1 micrometer.

Although the compounding quantity of organic fine particles is not specifically limited, It is preferable that it is 0.05-50 weight part with respect to 100 weight part of resin, and it is more preferable that it is 0.1-30 weight part.
If the amount of the organic fine particles is less than 0.1 parts by weight, the effect may not be obtained. On the other hand, when the compounding amount of the organic fine particles exceeds 50 parts by weight, the resin layer may not be made uniform.

(1-5) Conductive fine particles The resin layer preferably further contains conductive fine particles.
When the resin layer contains conductive fine particles, the ability of the carrier to impart charge to the toner can be more stably improved, that is, the carrier can be prevented from being charged up.

The conductive fine particles are not particularly limited as long as they are conductive fine particles commonly used in the technical field, and examples thereof include conductive carbon black, oxides such as conductive titanium oxide and tin oxide.
Carbon black can exhibit conductivity with a small addition amount and is suitable for black toner. On the other hand, conductive titanium oxide doped with antimony is suitable for the color toner because there is a concern about the detachment of carbon black from the resin layer.

Although the compounding quantity of electroconductive fine particles is not specifically limited, It is preferable that it is 0.1-30 weight part with respect to 100 weight part of resin, and it is more preferable that it is 1-20 weight part.
If the blending amount of the conductive fine particles is less than 0.1 parts by weight, the effect may not be obtained. On the other hand, if the blending amount of the conductive fine particles exceeds 30 parts by weight, the resin layer may not be made uniform.

(1-6) Coupling Agent The resin layer may further contain a coupling agent such as a silane coupling agent for the purpose of adjusting the toner charge amount.
Among the silane coupling agents, a silane coupling agent having an electron donating functional group is preferable, and examples thereof include an amino group-containing silane coupling agent represented by the following formula.
(Y) nSi (R) m
(In the formula, R is the same or different and each represents an alkyl group, an alkoxy group or a chlorine atom, Y represents the same or different hydrocarbon group containing an amino group, and m and n each represent an integer of 1 to 3. M + n = 4)

In the above formula, the alkyl group represented by R is, for example, a straight chain or branched chain having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, and tert-butyl group. Examples thereof include a chain alkyl group, and among these, a methyl group and an ethyl group are preferable.
Examples of the alkoxy group include linear or branched alkoxy groups having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, and a tert-butoxy group. Among these, a methoxy group and an ethoxy group are preferable.
Examples of the hydrocarbon group containing an amino group represented by Y, for _{example, - (CH 2) a-} X ( wherein, X is an amino group, an aminocarbonyl amino group, an aminoalkyl group, phenylamino group or dialkylamino A represents an integer of 1 to 4, and -Ph-X (wherein X is the same as above, -Ph- represents a phenylene group).

Specific examples of the amino group-containing silane coupling agent include the following.
H ₂ N (H ₂ C) ₃ Si (OCH ₃ ) ₃
H ₂ N (H ₂ C) ₃ Si (OC ₂ H ₅ ) ₃
H ₂ N (H ₂ C) ₃ Si (CH ₃ ) (OCH ₃ ) ₂
H ₂ N (H ₂ C) ₂ HN (H ₂ C) ₃ Si (CH ₃ ) (OCH ₃ ) ₂
H ₂ NOCHN (H ₂ C) ₃ Si (OC ₂ H ₅ ) ₃
H ₂ N (H ₂ C) ₂ HN (H ₂ C) ₃ Si (OCH ₃ ) ₃
H ₂ N—Ph—Si (OCH ₃ ) ₃ (wherein —Ph— represents a p-phenylene group)
Ph-HN (H ₂ C) ₃ Si (OCH ₃ ) ₃ (wherein Ph- represents a phenyl group)
(H ₉ C ₄ ) ₂ N (H ₂ C) ₃ Si (OCH ₃ ) ₃

In the present invention, one of the above coupling agents may be used alone or in combination of two.
Although the compounding quantity of a coupling agent is not specifically limited, It is preferable that it is 0.01-10 weight part with respect to 100 weight part of resin, and it is more preferable that it is 0.05-10 weight part.
When the blending amount of the coupling agent is within the above range, the toner is sufficiently charged and the mechanical strength of the resin layer is not significantly reduced.

(1-7) Production of Carrier The carrier of the present invention is obtained by applying a resin solution in which the constituent material of the resin layer is dissolved or dispersed in the solvent to the surface of the carrier core material, and then volatilizing and removing the solvent. It can be produced by forming a coating layer and further heat-curing or simply curing the coating layer during or after drying.

  The solvent is not particularly limited as long as it can dissolve the resin to be used. For example, aromatic hydrocarbons such as toluene and xylene, ketones such as acetone and methyl ethyl ketone, ethers such as tetrahydrofuran and dioxane, and higher alcohols. Organic solvents such as A solvent can be used individually by 1 type or in combination of 2 types.

  As a method of applying the resin liquid to the surface of the carrier core material, a known method can be adopted. For example, a dipping method in which the carrier core material is immersed in the resin liquid, a spray method in which the resin liquid is sprayed on the carrier core material, a fluidized bed method in which the resin liquid is sprayed in a state where the carrier core material is suspended by flowing air, and a kneader coater. Among them, a kneader coater method in which a carrier core material and a resin liquid are mixed and a solvent is removed may be used. Among these, the dipping method is preferable in that film formation is easy.

A drying accelerator may be used for drying the coating layer.
Known drying accelerators can be used, and examples thereof include lead such as naphthylic acid and octylic acid, metal soap such as iron, cobalt, manganese and zinc salts, and organic amines such as ethanolamine. A drying accelerator can be used individually by 1 type or in combination of 2 types. The addition amount is about 0.1 to 5 parts by weight with respect to 100 parts by weight of the solvent.

  The coating layer may be cured by appropriately setting the heating temperature in accordance with the type of resin or solvent, for example, heating at about 150 to 280 ° C. When a normal temperature curable silicone resin is used as the resin, heating is not required, but for the purpose of improving the mechanical strength of the resin layer to be formed and shortening the curing time, about 150 to 280 ° C. You may heat to.

The total solid content concentration of the resin liquid is not particularly limited, but the film thickness of the cured resin layer is usually 5 μm or less, preferably about 0.1 to 3 μm, taking into consideration the workability of application to the carrier core material. It may be adjusted as follows.
The carrier thus obtained preferably has a high electrical resistance and a spherical shape, but the effect of the present invention is not lost even if it is conductive or non-spherical.

(2) Two-component developer The two-component developer of the present invention includes the carrier of the present invention and a toner. The toner will be described in the next section (3).

The two-component developer of the present invention can be produced by mixing the carrier of the present invention and a toner.
The mixing ratio of the carrier and the toner is not particularly limited, but considering that it is used in a high-speed image forming apparatus (40 sheets / min or more for A4 size images), the average particle diameter Dk of the carrier / the average particle diameter Dt of the toner is In a state of 5 or more, the ratio (St / Sk × 100) of the total projected area St (total projected area of all toner particles) of the toner to the total surface area Sk (total of the surface areas of all carrier particles) of the carrier is 30 to 70. It is preferable to mix so that it may become%. As a result, the chargeability of the toner can be stably maintained in a sufficiently good state, and it can be used as a suitable two-component developer that can stably form a high-quality image for a long period of time even in a high-speed image forming apparatus.

The “surface area of the resin-coated carrier” can be measured as follows.
For example, the average particle diameter of the carrier is measured by a particle size distribution measuring apparatus (manufactured by Nikkiso Co., Ltd., model: Microtrac MT3000), and based on this, the specific gravity of the carrier is set to 4.7, and calculation is performed from the weight of the carrier to be mixed.
The “projection area of toner” can be measured as follows.
For example, the average particle diameter of the toner is measured by a particle size distribution measuring device (manufactured by Beckman Coulter, Inc., model: Coulter Counter Multisizer II), and based on this, the toner weight is 1.0 The number of toners is calculated, and the total toner area is calculated by toner number × toner area (calculated assuming a circle).
From the above result, St / Sk × 100 is calculated.

For example, when Dk = 90 μm and Dt = 6.5 μm, in order to make St / Sk × 100 30 to 70%, 2.2 to 5.3 weight of toner with respect to 100 parts by weight of carrier in the two-component developer What is necessary is just to be about a part.
When high-speed development is performed with such a two-component developer, the toner consumption amount and the toner supply amount supplied to the developing tank of the developing device according to the toner consumption are maximized, and the balance between supply and demand is not lost. .
When the amount of the carrier in the two-component developer is large, the charge amount tends to be lower, and not only the desired development characteristics cannot be obtained, but the toner consumption amount is larger than the toner supply amount, which is sufficient for the toner. May not be able to provide a sufficient charge, which may lead to degradation of image quality. On the other hand, when the amount of the carrier is small, the charge amount tends to be high, and it becomes difficult for the toner to be separated from the resin-coated carrier by an electric field, resulting in deterioration of image quality.

(3) Toner The toner is not particularly limited as long as it is a toner commonly used in the technical field, and includes a binder resin and a colorant as essential components, and known additions such as a release agent and a charge control agent as necessary. It consists of toner base particles containing an agent, and an external additive may be added as necessary.

(3-1) Binder Resin The binder resin is not particularly limited as long as it is a resin for toner that is commonly used in the technical field. For example, polyester resin, polystyrene, styrene-acrylate copolymer resin, and the like. Styrene resins, acrylic resins such as polymethyl methacrylate, polyolefin resins such as polyethylene, polyurethane, and epoxy resins. Moreover, you may use resin obtained by mixing a raw material monomer mixture with a mold release agent and performing a polymerization reaction.
In the present invention, one of the above binder resins can be used alone or in combination of two or more.

Among the above binder resins, polyester resins (hereinafter referred to as “polyester resins”) can be suitably used.
The polyester resin usually includes at least one selected from a divalent alcohol component and a trihydric or higher polyhydric alcohol component, and at least one selected from a divalent carboxylic acid and a trivalent or higher polyvalent carboxylic acid. It can be obtained by a polycondensation reaction, esterification or transesterification by a known method.
The conditions in the condensation polymerization reaction may be set as appropriate depending on the reactivity of the monomer component, and the reaction may be terminated when the polymer has suitable physical properties. For example, the reaction temperature is about 170 to 250 ° C., and the reaction pressure is about 5 mmHg to normal pressure.

  Examples of the divalent alcohol component include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis (4-hydroxy). Phenyl) propane, polyoxypropylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2-bis ( Alkylene oxide adducts of bisphenol A such as 4-hydroxyphenyl) propane and polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane; ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene Glycol, 1,3-propylene glycol, 1,4-butanediol, neo Diols such as n-glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol Bisphenol A; propylene adduct of bisphenol A; ethylene adduct of bisphenol A; hydrogenated bisphenol A and the like.

Examples of the trihydric or higher polyhydric alcohol component include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, sucrose (sucrose), 1 , 2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3, 5-trihydroxymethylbenzene and the like can be mentioned.
In the present invention, one of the above divalent alcohol component and trihydric or higher polyhydric alcohol component can be used alone or in combination of two or more.

  Examples of divalent carboxylic acids include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, malon Examples include acids, n-dodecenyl succinic acid, n-dodecyl succinic acid, n-octyl succinic acid, isooctenyl succinic acid, isooctyl succinic acid, and acid anhydrides or lower alkyl esters thereof.

Examples of the trivalent or higher polyvalent carboxylic acid include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, and 1,2,4-naphthalene. Tricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, Examples thereof include tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, empole trimer acid, and acid anhydrides or lower alkyl esters thereof.
In the present invention, one of the above divalent carboxylic acids and trivalent or higher polyvalent carboxylic acids can be used alone or in combination of two or more.

The polyester resin preferably has a weight average molecular weight of 3000 to 50000.
If the weight average molecular weight of the polyester resin is less than 3000, the peelability at the fixing high temperature side may be deteriorated. On the other hand, if the weight average molecular weight exceeds 50,000, the low-temperature fixability may be deteriorated.

The polyester resin preferably has an acid value of 5 to 30 mg KOH / g.
If the acid value of the polyester resin is less than 5 mgKOH / g, the charging characteristics of the resin will be lowered, and the charge control agent will be difficult to disperse in the polyester resin, which will adversely affect the charge build-up property and the charging stability during continuous use. There is. On the other hand, when the acid value of the polyester resin exceeds 30 mgKOH / g, the hygroscopicity becomes high and the chargeability may become unstable.

(3-2) Colorant As the colorant, various types of organic and inorganic pigments and dyes commonly used in the technical field can be used. For example, black (black), white, yellow (Yellow), orange, red (magenta), purple, blue (cyan) and green colorants.

Examples of the black colorant include inorganic pigments such as carbon black and composite oxide black; and organic pigments such as aniline black.
Carbon black is classified into channel black, roller black, disk black, gas furnace black, oil furnace black, thermal black, acetylene black, etc. according to its manufacturing method, etc., and from these, the design characteristics of the toner to be obtained Depending on the case, an appropriate carbon black may be appropriately selected.

  Examples of the white colorant include inorganic pigments such as calcium carbonate, barium sulfate, zinc oxide (zinc white), lithopone, titanium oxide, antimony white, and zinc sulfide.

  Examples of yellow colorants include inorganic pigments such as yellow lead, cadmium yellow, yellow iron oxide, composite oxide yellow, bismuth yellow, chrome yellow, nickel titanium yellow, and ocher; C classified by color index Pigment Yellow 1, CI Pigment Yellow 5, CI Pigment Yellow 12, CI Pigment Yellow 15, and CI Pigment Yellow 17, CI Pigment Yellow 74, C.I. Organic pigments such as CI Pigment Yellow 93, CI Pigment Yellow 180 and CI Pigment Yellow 185; Nitro dyes such as CI Acid Yellow 1; CI Solvent Yellow 2 and CI Solvent Yellow 6, CI Solvent Yellow 14, CI Solvent Yellow 15, C.I. ., Such as oil-soluble dyes such as Solvent Yellow 19 and C.I. Solvent Yellow 21 and the like.

  Examples of orange colorants include inorganic pigments such as red chrome yellow and molybdenum orange; permanent orange GTR, pyrazolone orange, vulcan orange, indanthrene brilliant orange RK, benzidine orange G and indanthrene brilliant orange GK, classified by color index C. I. Pigment orange 31 and C.I. I. And organic pigments such as CI Pigment Orange 43.

  Examples of red (magenta) colorants include inorganic pigments such as Bengala, cadmium red, red lead, mercury sulfide, and molybdenum red; CI Pigment Red 49 and CI Pigment Red classified by color index. 57, CI Pigment Red 81, CI Pigment Red 122, CI Solvent Red 19, CI Solvent Red 49, CI Solvent Red 52, CI Basic Red 10 and And organic pigments such as CI Disperse Red 15.

  Examples of purple colorants include inorganic pigments such as manganese purple; organic pigments such as fast violet B and methyl violet lake.

  Examples of the blue (cyan) colorant include, for example, inorganic pigments such as bitumen and cobalt blue; CI pigment blue 15, CI pigment blue 16, and CI solvent classified by color index. Blue 55, CI Solvent Blue 70, CI Direct Blue 25, CI Direct Blue 86 and KET. And organic pigments such as BLUE111.

  Examples of the green colorant include inorganic pigments such as chrome green and chromium oxide; final yellow green G and C.I classified by pigment green B, micalite green lake, and color index. I. And organic pigments such as CI Pigment Green 7.

A pigment is preferable as a colorant because the pigment is excellent in light resistance and color developability as compared with a dye, and a toner excellent in light resistance and color developability can be obtained.
In the present invention, one of the above colorants may be used alone or in combination of two, and these combinations may be different colors or the same color.
Two or more colorants may be used as composite particles. The composite particles can be produced, for example, by adding an appropriate amount of water, lower alcohol or the like to two or more colorants, granulating with a general granulator such as a high speed mill, and drying.
Further, in order to uniformly disperse the colorant in the binder resin, a master batch may be used.
The composite particles and the master batch are mixed into the toner composition during dry mixing.

In the master batch, for example, the binder resin and the colorant are dry-mixed with a mixer, the obtained powder mixture is kneaded with a kneader, and the obtained kneaded product is pulverized to, for example, a particle size of about 2 mm to 3 mm. Can be manufactured. As the binder resin, the same kind as that of the toner binder resin or a resin having good compatibility with the toner binder resin is used.
The blending ratio of the binder resin and the colorant is not particularly limited, but the colorant is about 30 to 100 parts by weight with respect to 100 parts by weight of the binder resin.

For dry mixing of the masterbatch, a known apparatus commonly used in the technical field can be used. For example, Henschel mixer (trade name, manufactured by Mitsui Mining Co., Ltd. (currently Nihon Coke Industries)), super mixer (trade name) Henschel type mixing equipment such as Mechano Mill (trade name, manufactured by Okada Seiko Co., Ltd.), Ong Mill (trade name, manufactured by Hosokawa Micron Co., Ltd.), Hybridization System (trade name, manufactured by Nara Machinery Co., Ltd.) ) And Cosmo system (trade name, manufactured by Kawasaki Heavy Industries, Ltd.).
What is necessary is just to set the conditions of mixing suitably with the mixer, masterbatch raw material, etc. to be used.

For the melt-kneading of the masterbatch, using a known apparatus commonly used in the technical field, a single-screw, twin-screw or multi-screw extruder (extruder), kneader, two or three roll mills, lab blast mill, etc. The following general kneaders may be mentioned. Specifically, TEM-100B (model, manufactured by Toshiba Machine Co., Ltd.), PCM-65 / 87, PCM-30 (all of these models, manufactured by Ikekai Co., Ltd.) and other single-screw or twin-screw extruders, kneedex ( Examples thereof include open roll type kneaders such as trade name, Mitsui Mining Co., Ltd. (currently Nihon Coke Industries Co., Ltd.). One of these kneaders can be used alone or in combination of two or more.
The kneading temperature depends on conditions such as the softening temperature of the binder resin, but is usually about 50 to 150 ° C, preferably about 50 to 120 ° C.
Other melt kneading conditions may be appropriately set depending on the kneader to be used, the master batch raw material, and the like.

The blending amount of the colorant is not particularly limited, but is preferably 5 to 20 parts by weight, and more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the binder resin.
When using a masterbatch, the amount of the masterbatch used may be adjusted so that the blending amount of the colorant is within the above range.
When the blending amount of the colorant is within the above range, an image having a high image density and image quality can be formed without impairing various physical properties of the toner.

(3-3) Release agent (also referred to as “wax”)
As the release agent, release agents commonly used in the art can be used, for example, petroleum wax such as paraffin wax and microcrystalline wax and derivatives thereof; Fischer-Tropsch wax, polyolefin wax (polyethylene wax, Hydrocarbon waxes such as polypropylene wax), low molecular weight polypropylin wax and polyolefin polymer wax (such as low molecular weight polyethylene wax) and derivatives thereof; carnauba wax, rice wax and candelilla wax and derivatives thereof, wood wax Plant waxes such as beeswax, animal waxes such as beeswax and spermaceti; oils and fats synthetic waxes such as fatty acid amides and phenol fatty acid esters; long chain carboxylic acids and derivatives thereof Body; long-chain alcohols and derivatives thereof; silicone polymer; such as higher fatty acids. Derivatives include oxides, block copolymers of vinyl monomers and waxes, graft modified products of vinyl monomers and waxes, and the like.
In this invention, 1 type of said mold release agent can be used individually or in combination of 2 or more types.

The release agent is preferably a hydrocarbon release agent. Moreover, it is preferable that the melting | fusing point is 70 degrees C or less, and the minimum is about 60 degreeC.
Although the compounding quantity of a mold release agent is not specifically limited, It is preferable that it is 0.2-20 weight part with respect to 100 weight part of binder resin, and it is more preferable that it is 0.5-10 weight part.
When the amount of the release agent is within the above range, an image having a high image density and image quality can be formed without impairing various physical properties of the toner.

(3-4) Charge control agent (also referred to as “charge control agent” or “charge control agent”)
As the charge control agent, charge control agents for positive charge control and negative charge control that are commonly used in the art can be used.

Examples of charge control agents for positive charge control include nigrosine dyes, basic dyes, quaternary ammonium salts, quaternary phosphonium salts, aminopyrines, pyrimidine compounds, polynuclear polyamino compounds, aminosilanes, nigrosine dyes and derivatives thereof, triphenylmethane Derivatives, guanidine salts, amidine salts and the like can be mentioned.
Examples of charge control agents for controlling negative charges include oil-soluble dyes such as oil black and spiron black, metal-containing azo compounds, azo complex dyes, naphthenic acid metal salts, metal complexes and metal salts of salicylic acid and its derivatives ( Examples of the metal include chromium, zinc, zirconium, etc.), boron compounds, fatty acid soaps, long-chain alkyl carboxylates, and resin acid soaps.
Among these, boron compounds are particularly preferable because they do not contain heavy metals.

In the present invention, one of the above charge control agents may be used alone or in combination of two or more.
The blending amount of the charge control agent is not particularly limited, but is preferably 0.1 to 3 parts by weight, particularly preferably 0.2 to 2 parts by weight with respect to 100 parts by weight of the binder resin.
If the blending amount of the charge control agent is within the above range, an image having a high image density and image quality can be formed without impairing various physical properties of the toner.

(3-5) Toner Manufacturing Method (Toner Manufacturing Method)
The toner is a known method such as a general toner production method, for example, a dry method such as a pulverization method, a suspension polymerization method, an emulsion aggregation method, a dispersion polymerization method, a dissolution suspension method, and a melt emulsion method. Can be produced. Among these, the pulverization method is particularly preferable in that the number of steps is small and the amount of capital investment is small as compared with the wet method.
In the preparation of toner by a pulverization method, a toner material containing at least a binder resin, a colorant and a release agent, and optionally a charge control agent is mixed and melt-kneaded to obtain a kneaded product, and then the kneaded product is cooled, solidified and pulverized. Thereafter, particle size adjustment such as classification is performed as necessary to obtain toner particles.
A known apparatus can be used for each step of mixing, melt-kneading, pulverization, and classification.

(3-6) External additive As the external additive, an external additive commonly used in the technical field can be used, and examples thereof include silica, titanium oxide, silicon carbide, aluminum oxide, and barium titanate. Those that have been surface treated (hydrophobized) with a silicone resin, a silane coupling agent or the like are preferred.
In the present invention, one of the above external additives may be used alone or in combination of two or more.

In the present invention, it is preferable to use a plurality of external additives having different average particle diameters in combination. From the viewpoint of improving transfer efficiency, at least one of the plurality of external additives has an average particle diameter of 0.1 μm or more, and the average particle diameter of the plurality of external additives is 0.2 μm or less. preferable.
For example, when two types of external additives having different average particle diameters are used, the smaller one has an average particle diameter of 0.007 to 0.5 μm, and the larger one has an average particle diameter of 0.5 to 0.2 μm. The ratio of the smaller average particle diameter to the larger average particle diameter is preferably 1: 5 to 1:20.

The addition amount of the external additive is not particularly limited, but is preferably 0.1 to 3.0 parts by weight, particularly preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the toner base particles.
When the amount of the external additive is within the above range, an image having a high image density and image quality can be formed without impairing various physical properties of the toner.

(4) Image Forming Method The image forming method using the two-component developer of the present invention comprises a step of forming a latent image on the image carrier and a latent image formed on the image carrier using the two-component developer. Including a step of developing and forming a toner image, and is excellent in image reproducibility including color reproducibility, and can form a high-definition and high-image density image stably and for a long time.

The present invention will be specifically described below with reference to production examples, examples and comparative examples, but the present invention is not limited to these production examples and examples.
In Production Examples, Examples and Comparative Examples, each physical property value was measured by the following method.

[Average particle diameter of carrier core material, magnetic fine particles and conductive particles: μm]
About 10 to 15 mg of a measurement sample is added to 10 mL of a 5% aqueous solution of an ether type nonionic surfactant (polyoxylauryl ether, HLB = 13.6, manufactured by Kao Corporation, product name: Emulgen 109P), and ultrasonic waves are added. Dispersion treatment is performed at a frequency of 20 kHz for 1 minute using a disperser (manufactured by SMT Co., Ltd., model: UH-50). About 1 mL of the obtained dispersion is measured with a particle size distribution measuring device (manufactured by Nikkiso Co., Ltd., model: Microtrac MT3000), and the volume average particle size is obtained from the result.

[Average particle diameter of toner base particles: μm]
To 50 ml of electrolytic solution (Beckman Coulter, trade name: ISOTON-II), 20 mg of toner base particles and 1 ml of sodium alkyl ether sulfate are added, and an ultrasonic disperser (manufactured by SMT Co., Ltd., model: UH-50). For 3 minutes at a frequency of 20 kHz. About 1 mL of the obtained dispersion was filled into a dedicated cell of a particle size distribution analyzer (Beckman Coulter, Model: Coulter Counter Multisizer 3) and stirred for 1 minute to confirm that the scattered light intensity was stable. The volume particle size distribution is measured under the conditions of an aperture diameter of 100 μm and the number of measured particles of 500000 counts, and the volume average particle size is obtained from the result.

[Melting point of wax: ° C]
Using a differential scanning calorimeter (manufactured by PerkinElmer Japan Co., Ltd., model: Diamond DSC), 0.01 g of a sample is heated from a temperature of 20 ° C. to 200 ° C. at a heating rate of 10 ° C./min, and then from 200 ° C. to 20 ° C. The DSC curve is measured by repeating the rapid cooling operation twice. The endothermic peak temperature corresponding to the melting of the DSC curve measured in the second operation is defined as the melting point of the wax.

[Surface oxidation treatment of magnetic fine particles]
Magnetite fine particles (average particle size 0.5 μm) as magnetic fine particles are stirred for 1 hour using a sand mill (manufactured by Asada Tekko, model: NM-L), and then a rotary kiln (manufactured by Advantech, model: KT-1500P) is used. Then, fluid oxidation was performed in air at 350 to 400 ° C. for 20 minutes.

Using a bridge-type resistor, the resistance (Ω · cm) to an applied voltage of 0 to 1000 V was measured for the surface-oxidized magnetite fine particles (average particle size 0.5 μm) and untreated magnetite fine particles.
For the untreated product, the measurement was stopped at 250 V for breakdown.
The obtained results are shown in FIG.
According to FIG. 1, it can be seen that the surface oxidation-treated magnetite fine particles maintain a resistance value with respect to the electric field strength.

[Manufacture of resin-coated carriers]
(Resin coated carrier 1)
Coating resin: 150 parts by weight of a 20% toluene solution of silicone resin (manufactured by Shin-Etsu Chemical Co., Ltd., product name: KR350) (30 parts by weight of resin),
Magnetic fine particles: Magnetite fine particles (average particle size 0.8 μm, resistance 10) that have been surface oxidized and classified in advance. Ω · cm, does not conduct even under 1000 V applied voltage) 12 parts by weight Organic fine particles (thermosetting organic fine particles): 5 parts by weight of melamine resin fine particles (average particle size 0.3 μm) Conductive fine particles: conductive carbon black toluene dispersion ( Solid concentration 15%, manufactured by Cabot Corporation, product name: VULCAN XC72) 8 parts by weight Coupling agent: silane coupling agent (100% solution, manufactured by Toray Dow Corning Co., Ltd., product name: SH6020) 3 parts by weight Solvent: 200 parts by weight of toluene

The mixture containing the above components was stirred for 5 minutes at a rotational speed of 500 rpm using a general-purpose stirrer (manufactured by Shinto Kagaku Co., Ltd., model: Three-One Motor BLh1200) to prepare a coating resin solution. 1000 parts by weight of a carrier core material (Mn—Mg ferrite) having an average particle diameter of 35 μm was added to and mixed with the obtained coating resin solution, and further mixed for 5 minutes at a rotation speed of 500 rpm using the above stirrer. The obtained mixture was depressurized (about 6.0 × 10 ⁴ Pa) and heated (about 100 ° C.) to remove the toluene solvent, thereby forming a coating layer on the surface of the carrier core material.
The obtained carrier core material having the coating layer is heated at 200 ° C. for 1 hour using a safety oven (manufactured by ESPEC Corporation, model: SPH (H) 102) to cure the coating layer to form a resin layer. And about 2000 g of resin-coated carrier (1) (12 parts by weight of magnetic fine particles with respect to 1000 parts by weight of carrier core material) was obtained through a 100-mesh sieve.
Table 1 shows each component of the resin-coated carrier 1 and the blending amount thereof.

(Resin coated carriers 2-17)
Resin-coated carriers 2 to 17 were obtained in the same manner as the resin-coated carrier 1 except that the components of the resin-coated carrier shown in Table 1 and their blending amounts were used.
Only in the case of the resin-coated carrier 2, an acrylic resin (styrene-methyl methacrylate copolymer, copolymerization ratio 20:80, molecular weight 85) is used instead of a 20% toluene solution of a silicone resin (indicated as (I) in Table 1). , 000, indicated in Table 1 as (b)) 20% toluene solution.

Further, instead of magnetite fine particles (average particle diameter 0.8 μm, expressed as (A) in Table 1) as magnetic fine particles, magnetic fine particles having different average particle diameters as shown below ((i) to (o) in Table 1). ) And untreated magnetite fine particles (average particle diameter of 0.8 μm, indicated as (ka) in Table 1) that have not been surface-oxidized in advance.
Magnetic fine particles (I): Magnetite fine particles
Average particle size 2.0μm, resistance 10 ⁷ Ω · cm
Magnetic fine particles (um): Barium ferrite fine particles
Average particle size 0.1 μm, resistance 10 ⁸ Ω · cm
Magnetic fine particles (E): Strontium ferrite fine particles
Average particle size 2.2μm, resistance 10 ⁹ Ω · cm
Magnetic fine particles (o): Magnetite fine particles
Average particle size 0.08μm, resistance 10 ⁸ Ω · cm
The magnetic fine particles (A) to (O) do not conduct even under a 1000 V applied voltage.

Furthermore, instead of melamine resin fine particles (average particle size of 0.1 μm, expressed as (A) in Table 1) as organic fine particles, organic fine particles having different average particle sizes as shown below ((B) to ( E) is used.
Organic fine particles (B): Melamine resin fine particles
Average particle size 1.0μm
Organic fine particles (C): benzoguanamine / melamine resin fine particles
Average particle size 0.1μm
Organic fine particles (D): Melamine resin fine particles
Average particle size 1.5μm
Organic fine particles (E): benzoguanamine / melamine resin fine particles
Average particle size 0.05μm
Table 1 shows the components of the resin-coated carriers 2 to 17 and their blending amounts.

[Production of toner]
(Toner 1)
Binder resin: Polyester resin (acid value 21 mg KOH / g, aromatic alcohol component: PO-BPA and EP-BPA, acid component: fumaric acid and merit anhydride) 87.5 parts by weight Colorant: C.I. I. Pigment Blue 15: 1 5 parts by weight Mold release agent: nonpolar paraffin wax, melting point 78 ° C., weight average molecular weight: Mw 832
6 parts by weight Charge control agent: negatively charged salicylic acid compound (manufactured by Orient Chemical Co., Ltd., product name: Bontron E-84) 1.5 parts by weight

The above components are premixed using a Henschel mixer (Mitsui Mining Co., Ltd.) and then melt-kneaded using a twin-screw extruder (manufactured by Ikegai Co., Ltd., model: PCM-30) to obtain a melt-kneaded product. It was.
After the obtained melt-kneaded product is cooled by a cooling belt, it is coarsely pulverized using a cutting mill, then finely pulverized using a jet type pulverizer, and further classified using an air classifier. 2000 g of toner particles having a diameter of 6.5 μm were obtained.

  Next, 97.8% by weight of toner particles were subjected to a hydrophobic treatment with 1.2% by weight of silica fine particles (average particle size 100 nm) hydrophobized with i-butyltrimethoxysilane and hexamethyldisilazane (HMDS). Toner 1 (cyan) was added by adding 1.0% by weight of silica fine particles (average particle size 12 nm) and mixing using a Henschel mixer (Mitsui Mining Co., Ltd. (currently Nippon Coke Industries, Ltd.)). 1000 g of toner was obtained.

(Toner 2)
As a colorant, C.I. I. 1000 g of toner 2 (black toner) was obtained in the same manner as in the production of toner 1 except that carbon black was used instead of Pigment Blue 15: 1.

(Toner 3)
Toner 3 (cyan toner) is the same as toner 1 except that a boron compound (manufactured by Nippon Carlit Co., Ltd., product name: LR-147) is used as the charge control agent in place of the negatively charged salicylic acid compound. ) 1000 g was obtained.

(Toner 4)
1000 g of toner 4 (cyan toner) was obtained in the same manner as in the production of toner 1 except that silica fine particles hydrophobized with i-butyltrimethoxysilane (average particle size 100 nm) were not used.

[Production and Evaluation of Two-Component Developer]
Example 1
The toner 1 and the resin-coated carrier 1 are combined so that the mixing ratio is 60 (toner / carrier = 1/20), and the mixture is stirred and mixed for 20 minutes with a V-type mixer (manufactured by Tokuju Kogyo Co., Ltd., model: V-5). As a result, 1500 g of the two-component developer of Example 1 was obtained.
The chargeability, carrier adhesion, image quality, and coating state of the resin layer in the obtained two-component developer were evaluated.

(Examples 2-14 and Comparative Examples 1-3)
The two-component developers of Examples 2 to 12 and Comparative Examples 1 to 3 were obtained and evaluated in the same manner as in Example 1 except that the toner shown in Table 2 and the resin-coated carrier were combined in the mixing ratio.

[Evaluation]
(1) Charging property (1-1) Charging rise characteristic In the combination of a resin-coated carrier of two-component developer and toner, 0.95 g of the former and 0.05 g of the latter are put in a glass bottle having a capacity of 5 ml. The mixture was stirred for 60 minutes at 180 rpm using a rotary roll mill. The obtained two-component developer was collected, and the charge amount (μC / g) was measured using a suction type charge amount measuring device (manufactured by Trek Co., Ltd., model: Model 210HS). Further, the charge amount (μC / g) was measured in the same manner for the two-component developer obtained in the same manner except that the stirring time was changed to 60 minutes.
From the absolute value of the difference in charge amount between the obtained stirring time of 1 minute and 60 minutes, the charge rising characteristics were evaluated according to the following criteria.
○: Good (charge amount difference is 10 μC / g or less)
Δ: Acceptable (Charge amount difference exceeds 10 μC / g and 15 μC / g or less)
X: Defect (charge amount difference exceeds 15 μC / g)

(1-2) Charging life characteristics A two-component developer is set in a commercially available copying machine (manufactured by Sharp Corporation, model: MX-6000N) having a two-component developing device remodeled for measurement. The image density of the image area, the whiteness of the non-image area, and the charge amount of the two-component developer were measured after 50,000 sheets of 10% images were actually taken under the temperature of 50 ° RH.

(1-2-1) Image Density Image density was measured using a spectrocolorimetric densitometer (manufactured by Nippon Flat Plate Equipment Co., Ltd., model: X-Rite 938), and evaluated according to the following criteria.
○: Good (image density is 1.4 or more)
X: Defect (image density is less than 1.4)

(1-2-2) Whiteness Using a spectroscopic color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., model: SZ90 type), tristimulus values X, Y and Z were measured, and the obtained Z value was used. The whiteness was evaluated according to the following criteria.
○: Good (Z value is 0.5 or less)
Δ: Acceptable (Z value exceeds 0.5 and is 0.7 or less)
X: Defect (Z value exceeds 0.7)

(1-2-3) Charge Amount Charge amount (μC / g) was measured by using a suction-type charge amount measuring device (manufactured by Trek Co., Ltd., Model: Model 210HS), and 50,000 sheets of initial and 10% images were actually taken. The amount of charge was measured and the amount of charge was evaluated according to the following criteria from the absolute value of the difference between them.
○: Good (charge difference is 5 μC / g or less)
Δ: Acceptable (Charge amount difference exceeds 5 μC / g and 10 μC / g or less)
X: Defect (charge amount difference exceeds 10 μC / g)

(2) Carrier adhesion A two-component developer was set in the copying machine, and the number of carriers adhered in a fixed area (297 mm × 24 mm) in the non-image area on the image carrier was counted. At this time, a DC bias voltage of 200 V, an AC bias voltage of 1100 V, and a frequency of 9 kHz were applied to the developer carrier, and the surface of the image carrier was not charged. Carrier adhesion was evaluated from the obtained carrier adhesion number according to the following criteria.
○: Good (number of carriers attached is less than 15)
Δ: Possible (Number of carriers attached is 15 or more and 20 or less)
X: Defect (number of carriers attached exceeds 20)

(3) Image quality (clear image quality)
Set the two-component developer in the above copying machine, print a test chart of a specific image (an image where the high density area and the halftone image overlap), and remove white spots at the boundary between the halftone and the high density printing section. Sensory evaluation was performed. The evaluation was performed based on the judgment of five people and was performed according to the following criteria.
○ (Good): All 5 people are OK. △ (Yes): Out of 5 people, 3 or more people are OK. × (Bad): 2 out of 5 people are OK.

(4) Covering state of resin layer The resin-coated carrier immediately after production shown in Table 1 was observed with an electron microscope (magnification 1000), and the state of the resin layer was observed. The exposed part of the carrier core material was observed, and the coating state in which particles that were hardened with the coating resin and the additive were seen was judged as poor (x). Moreover, although the part which the carrier core exposed is seen, when there is no previous particulate solidified substance ((triangle | delta)), all the resin-coated carriers with which core exposure is not seen so much were made into (good).
Also, (1-2) the resin-coated carrier was taken out of the two-component developer after the charge life characteristics test and observed at (magnification 1000) to observe the state of the resin layer.
The state of the resin layer was evaluated according to the following criteria from the state of the resin-coated carrier after the test compared with the time of manufacture.
○ (Good): Little change in the resin layer × (Bad): The resin layer is clearly worn and there are many exposed portions of the carrier core material

(5) Comprehensive evaluation Based on the evaluation results of (1) to (4) above, comprehensive evaluation was performed according to the following criteria.
◎: For all evaluation items ○
○: There is Δ even in one evaluation item ×: There is × in one evaluation item Table 2 shows each component of the two-component developer, a mixing ratio thereof, and an evaluation result.

According to the results in Table 2, the toner containing the carrier of the present invention (Examples 1 to 14) is either a color toner or a black toner, and the chargeability, carrier adhesion, image quality, and coating state of the resin layer are the same. It turns out that it is favorable.
On the other hand, a toner containing a carrier containing untreated magnetite fine particles not surface-oxidized in the resin layer as a magnetic fine particle (Comparative Example 1) and a toner containing a carrier containing no magnetic fine particle (Comparative Example 2) are charged. In addition, it is found that the charge rising property of the life characteristic of charging is inferior, the former is inferior in carrier adhesion, and the latter is inferior in image quality.
Further, it can be seen that the toner containing the carrier not containing the organic fine particles (Comparative Example 3) has good carrier adhesion and coating state, but is inferior in chargeability and image quality.

1 Measuring jig 2 Magnet 3 Electrode 4 Base

Claims (8)

A carrier core material made of ferrite, a thermosetting organic material that covers the carrier core material, does not conduct under an applied voltage of 1000 V, and has a resistance value of 10 ⁷ to 10 ⁹ Ω · cm and a triazine ring An electrophotographic carrier comprising a resin layer containing fine particles.   The electrophotographic carrier according to claim 1, wherein the magnetic fine particles have a volume average particle diameter of 0.08 to 0.8 μm.   The electrophotographic carrier according to claim 1 or 2, wherein the magnetic fine particles are contained in a proportion of 0.05 to 55 parts by weight with respect to 1000 parts by weight of the carrier core material.   The electrophotographic carrier according to claim 1, wherein the magnetic fine particles are subjected to a surface oxidation treatment.   The electrophotographic carrier according to claim 1, wherein the thermosetting organic fine particles have a volume average particle diameter of 0.1 to 1 μm.   The electrophotographic carrier according to any one of claims 1 to 5, wherein the thermosetting organic fine particles are contained at a ratio of 0.05 to 50 parts by weight with respect to 100 parts by weight of the resin of the resin layer.   The electrophotographic carrier according to claim 1, wherein the resin layer further contains conductive fine particles.   A two-component developer comprising the electrophotographic carrier according to any one of claims 1 to 7 and a toner.