JP2001022133A - Electrostatic image developing carrier, two-component developer and developing device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a developer capable of giving a stable image with an extremely fast rise of charge, a high charge amount of a toner, a low possibility of toner fusion to a carrier, and a stable image. It is intended to provide a career to be carried out. A carrier having a resin coating layer composed of a core material and a resin composition, wherein the resin coating layer contains at least a quaternary ammonium salt compound that is positively charged with respect to iron powder. It is characterized by being formed from an object.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a carrier for developing an electrostatic image, a two-component developer having the carrier, and a developing device using the developer.

[0002]

2. Description of the Related Art U.S. Pat.
7, 691, JP-B-42-23910, JP-B-43-24748, and the like, various methods are described. In any of these methods, a photoconductive layer is formed on a photoconductive layer according to an original. An electrostatic latent image is formed by irradiating the image, and then a fine colored powder called a toner having a polarity opposite to that of the electrostatic latent image is deposited on the electrostatic latent image to develop the electrostatic latent image. After the transfer of the toner image onto a transfer material such as paper, the toner image is fixed by heat, pressure, solvent vapor or the like to obtain a copy.

In the process of developing the electrostatic latent image, toner particles charged to the opposite polarity to the latent image are attracted by electrostatic attraction and adhered on the electrostatic latent image (reversal development). In the case of (1), a toner having a triboelectric charge having the same polarity as the charge of the latent image is used). Generally, the method of developing such an electrostatic latent image using the toner is roughly divided into a small amount of toner dispersed in a medium called a carrier. There are a method using a so-called two-component developer and a method using a so-called one-component developer using a toner alone without using a carrier.

[0004] In general, carriers constituting such a two-component developer are roughly classified into conductive carriers and insulating carriers. Oxidized or unoxidized iron powder is usually used as the conductive carrier. However, in a developer containing the iron powder carrier, the triboelectric charging property with respect to the toner is unstable and is formed by the developer. There is a problem that fogging occurs in the visible image. That is, with the use of the developer,
Since toner particles adhere to the surface of iron powder carrier particles, the electrical resistance of the carrier particles increases, the bias current decreases, and the triboelectrification becomes unstable, resulting in a reduction in the image density of the visible image formed. The fog increases. A typical example of the insulating carrier is a carrier obtained by uniformly covering the surface of a carrier core material made of a ferromagnetic material such as iron, nickel, or ferrite with an insulating resin. In a developer using this carrier, toner particles are less likely to fuse to the surface of the carrier than in the case of a conductive carrier, and have excellent durability and a long service life. It has the advantage of being suitable.

However, in this insulating carrier, toner is not fused to the surface of the carrier, that is, so-called toner spent is not generated, and a desired sufficient amount of triboelectric charge is imparted to a specific toner used together with the carrier. In addition, the coating layer covering the surface of the carrier core material is required to have sufficient abrasion resistance and strong adhesion to the core material.
That is, the carrier is rubbed with other carrier particles and toner particles in the developing device. However, when toner spent occurs on the carrier surface, the original frictional charging ability of the carrier coating layer cannot be exhibited, and the charging characteristics are unstable. It will be something. Further, if the carrier coating layer does not have sufficient film strength and adhesion to the core material, the coating film may be peeled off or missing from the core material, resulting in a decrease in the ability to impart charge to the toner.

Further, the surface resistance of a carrier coated with an insulating resin is generally liable to change with changes in environmental conditions such as low temperature, low humidity, and high temperature and high humidity. As a result, for example, under low temperature and low humidity, the resistance increases due to a decrease in the amount of water and the image density decreases due to charge-up, and under high temperature and high humidity, the resistance decreases due to an increase in the amount of water supply, and fog and scattering occur due to a decrease in tribo. Will be generated. Therefore, it is an important characteristic of the carrier that the surface resistance of the carrier does not depend on environmental fluctuations. However, at present, a carrier coated with an insulating resin having a satisfactory level has not been found yet.

Conventionally, as a technique for solving such a drawback,
A coated carrier coated with a fluoropolymer is proposed in U.S. Pat. No. 3,922,382, but in the above-mentioned proposed technique, the film-forming property of the fluoropolymer is poor, and the carrier surface is only partially covered. The coating cannot be performed, and the charging characteristics become unstable. Further, in order to improve the film forming property of a fluorine-containing polymer, a method of coating by mixing with a polymer having a relatively good film forming property is also disclosed in US Pat. No. 4,297,427.
And Japanese Patent Application Laid-Open No. 54-110839. However, it is thought that any of these can be advantageously used for a positive toner because a fluorine-based polymer having a strong negative property as a charging component is used as a component, but a desired moderate size is obtained for a negative donor. Is expected to be difficult to obtain, and even if a sufficient value is obtained as the magnitude of the charge amount, the rising speed of charging is slow, and it is difficult to maintain stable chargeability. Conceivable.

On the other hand, there is a conventionally known method of incorporating a charge control agent or a charge control resin into the toner in order to speed up the rise of the frictional charge of the toner. The rise of the amount cannot be made faster, and conversely, even in an environment such as high temperature and high humidity or low temperature and low humidity, there may be a considerable difference in the amount of triboelectric charge and the rise of charge, which causes fog as an image and low density. For example, it is not sufficient as a method for controlling the charge of the toner. Japanese Patent Application Laid-Open No. 62-75551 also discloses a method of increasing the triboelectric charging property of a toner by adding fine particles positioned in the opposite direction to the toner on the triboelectric series. However, this method alone does not sufficiently control the charge of the toner, and when fine particles charged to the opposite polarity to the toner are added to the toner until the frictional charge amount of the toner is sufficiently controlled, the toner particles conversely become Aggregation deteriorates the fluidity of the toner. As a result, the carrier and the toner cannot be sufficiently mixed, and it is necessary to provide a stronger and more uniform stirring device in the configuration of the developing device. Further, when the fluidity of the toner deteriorates, it may cause an adverse effect on a cleaning device of a copying machine.

Various attempts have been made to control the surface resistance. For example, Japanese Patent Application Laid-Open No. Sho 62-22925
No. 6 proposes a carrier in which the resistance under a high temperature and a high humidity is less reduced by attaching a water-soluble quaternary ammonium salt to the surface of the ferrite particles. However, when a water-soluble quaternary ammonium salt is used, the quaternary ammonium salt on the surface of the ferrite particles elutes or desorbs due to long-term storage under high temperature and high humidity, or durability, and the properties of untreated ferrite particles. Has the drawback of gradually approaching. In addition, since the coating is not coated with a resin, the quaternary ammonium salt on the surface of the ferrite particles is easily desorbed not only in high-temperature and high-humidity but also in a normal environment at normal temperature and normal humidity. Compared to a coated carrier, there is a problem that the carrier is less susceptible to so-called toner spent in which a film is formed on the carrier surface by a toner, and the life of the developer is short. Furthermore, if not covered with an insulating resin to some extent, iron oxide powder and ferrite particles as well as a developing system in which a bias voltage is applied, even if ferrite particles are applied, may cause current leakage or carrier adhesion to the photoreceptor. is there.

As described above, with respect to the durability and toner-spent resistance of the carrier, there is no known method which is better than coating with an insulating resin.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems, to make the rise of charge extremely fast, to keep the charge amount of the toner high, and to make the toner on the carrier An object of the present invention is to provide a carrier that forms a developer that does not easily cause fusing and provides a stable image, a two-component developer having the carrier, and a developing device.

Another object of the present invention is to provide a developing apparatus which can obtain a good image not only under normal temperature and normal humidity but also in an environment such as high temperature and high humidity.

[0013] Furthermore, an object of the present invention is to provide excellent durability,
An object of the present invention is to provide a carrier that constitutes a developer that gives stable images without problems such as a decrease in density and fog over a long period of time, a two-component developer having the carrier, and a developing device.

[0014]

The above objects can be attained by the present invention described below.

That is, the present invention provides a carrier having a resin coating layer comprising a core material and a resin composition, wherein the resin coating layer comprises a quaternary ammonium salt compound which is positively charged with respect to iron powder. A carrier for developing an electrostatic image, characterized by being formed from a resin composition containing at least.

Further, the present invention is a two-component developer comprising a toner and a carrier having the above constitution.

Further, the present invention comprises a container for accommodating at least a developer and a developer carrying member for carrying and transporting the developer, wherein a developing area between the latent image holding member and the developer carrying member opposed thereto is provided. In a developing device for developing a latent image formed on a latent image holding member with a developer carried on the developer carrying member, the developer is a two-component developer having a toner and a carrier having the above configuration. A developing device characterized in that:

The present inventors have conducted intensive studies on the above-mentioned problems, and as a result, in a carrier having a resin coating layer coated with a resin composition, at least -NH- or -NH ₂ is contained in the resin structure. By using a carrier for electrophotography comprising a resin composition containing at least a binder resin and a quaternary ammonium salt compound which is positively chargeable with respect to iron powder, binding of the coating layer is achieved. It was found that the negative charge imparting property of the resin itself was reduced and the positive charge imparting property was improved.

Here, the relationship between the developer and the carrier coating layer in the developing device will be described.

For the positive polarity toner, by using the carrier having the above characteristics, tribo can be uniformly and sufficiently applied to the toner, and the charge amount of the toner can be kept high. Further, since the mechanical strength and abrasion resistance of the coating layer itself are improved as compared with the case where the charge-imparting particles are conventionally added, long-term durability can be provided and a good image can be stably provided for a long time. The inventors have found that it becomes possible to accomplish the present invention.
For the negative polarity toner, if a carrier having the above characteristics is used, the triboelectric charging property can be controlled by setting the addition amount of the quaternary ammonium salt to an appropriate amount.
Therefore, it is possible to effectively prevent generation of a developer having an excessively negative charge and strong adhesion of the developer to the carrier surface. Further, since the mechanical strength and abrasion resistance of the coating layer itself are improved as compared with the case where the charge-imparting particles are conventionally added, long-term durability can be provided and a good image can be stably provided for a long time. The inventors have found that it becomes possible to accomplish the present invention.

In the present invention, when a carrier having the above-mentioned structure is used, a clear reason for obtaining good positive charge imparting property to the toner is not clear, but the present invention is not limited thereto. The quaternary ammonium salt compound, which is itself positively chargeable with respect to iron powder, is added to the resin, dispersed more uniformly, and incorporated into the structure of the resin by forming a resin composition. At that time, the original structure of the quaternary ammonium salt having positive polarity is lost,
It is considered that the chargeability of the resin into which the quaternary ammonium salt has been incorporated becomes uniform and has a sufficient negative chargeability, so that the toner has good positive chargeability. Therefore, if a carrier formed using such a material is used, the toner can be suitably charged.

[0022]

Next, the present invention will be described in more detail with reference to preferred embodiments.

The resin material of the coating layer of the present invention has at least -NH ₂ group, = NH group,
It preferably has any structure of a —NH— bond. Examples of the substance having an -NH ₂ group include a primary amine represented by R-NH ₂ or a polyamine having the same, a primary amide represented by RCO-NH ₂ or a polyamide having the same, or the like having a = NH group. As the substance, a secondary amine represented by R = NH or a polyamine having them, a secondary amine represented by (RCO) ₂ 2NH
Amides or polyamides containing them, such as -NH
Examples of the substance having a bond include, in addition to the above-described polyamines and polyamides, polyurethanes having a -NHCOO- bond, and the like. One or more of the above substances may be contained as a copolymer, The resin synthesized is preferably used. Among them, a phenol resin, a polyamide resin, a urethane resin, and the like using ammonia as a catalyst, which are used in Examples described later, are preferable.

As a phenol resin constituting the coating resin used in the present invention, as a result of intensive studies by the present inventors, the use of a phenol resin in which a nitrogen-containing compound is used as a catalyst in the production process makes it possible to heat the phenol resin. It was found that the quaternary ammonium salt compound was easily incorporated into the structure of the phenol resin during curing. Therefore, by using such a phenol resin as one of the materials constituting the coating layer on the carrier in the present invention, a favorable positive-applied developing device can be obtained.

Examples of the nitrogen-containing compound used as a catalyst in the production process of the phenolic resin used in the present invention include, for example, acidic catalysts such as ammonium sulfate, ammonium phosphate, ammonium sulfamate, ammonium carbonate, ammonium acetate and ammonium maleate. Ammonium or amino salts of the following; and as the basic catalyst, ammonia or dimethylamine;
Diethylamine, diisopropylamine, diisobutylamine, diamylamine, trimethylamine, triethylamine, tri-n-butylamine, triamylamine,
Dimethylbenzylamine, diethylbenzylamine, dimethylaniline, diethylaniline, n, n-di-n-butylaniline, n, n-diamylaniline, n, n-dit-amylaniline, n-methylethanolamine, n
-Ethylethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, diethylethanolamine, ethyldiethanolamine, n-
Amino compounds such as butyldiethanolamine, di-n-butylethanolamine, triisopropanolamine, ethylenediamine, hexamethylenetetraamine, pyridine, α-picoline, β-picoline, γ-picoline, 2,4
-Pyridine and derivatives thereof such as lutidine and 2,6-lutidine, quinoline compounds, imidazole, 2-methylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 2-phenyl- There are nitrogen-containing heterocyclic compounds such as imidazole and derivatives thereof such as 4-methylimidazole and 2-heptadecylimidazole.

As the polyamide resin constituting the coating resin used in the present invention, for example, nylon 6, 66, 610, 11, 12, 9, 13, Q2 nylon or the like, or nylon containing these as a main component is used. Any of copolymers, N-alkyl-modified nylon, N-alkoxyalkyl-modified nylon and the like can be suitably used. Furthermore, various resins modified with a polyamide such as a polyamide-modified phenolic resin, or a resin containing a polyamide resin component, such as an epoxy resin using a polyamide resin as a curing agent, may be used. It can be suitably used.

As the urethane resin constituting the coating resin used in the present invention, any resin containing a urethane bond can be suitably used. This urethane bond is obtained by a polymerization addition reaction between a polyisocyanate and a polyol.

As a polyisocyanate which is a main raw material of the polyurethane resin, diphenylenemethane-4,
4′-diisocyanate (MDI), isophorone diisocyanate (IPDI), polymethylene polyphenyl polyisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, 1,5-naphthalene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, carbodiimide-modified diphenylmethane
4,4'-diisocyanate, trimethylhexamethylene diisocyanate, orthotoluidine diisocyanate, naphthylene diisocyanate, xylene diisocyanate, paraphenylene diisocyanate, lysine diisocyanate methyl ester, dimethyl diisocyanate and the like can be used.

Examples of the polyol which is a main raw material of the polyurethane resin include polyester polyols such as polyethylene adipate ester, polybutylene adipate ester, polydiethylene glycol adipate ester, polyhexene adipate ester and polycaprolactone ester, polytetramethylene glycol, polypropylene glycol and the like. And the like can be used.

As the quaternary ammonium salt compound having the above-mentioned function, which is preferably used in the present invention, those having a positive charge property on iron powder are used. For example, a compound represented by the following general formula (I) can be mentioned.

[0031]

Embedded image (In the formula, R ₁ , R ₂ , R ₃ and R ₄ each represent an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an aralkyl group. or it may be different .X ^- represents an anion of acid).

On the other hand, a fluorine-containing quaternary ammonium salt compound itself having a negative charge property with respect to iron powder, for example, represented by the following formula (II) was examined. It was found that the desired object of the present invention was not achieved by the addition of. That is, since the compound represented by the following formula (II) has a fluorine resin atom having a strong electron-withdrawing property in the structure, the compound itself has a negative charge property with respect to iron powder. Even if a resin composition obtained by dispersing the compound in a resin is used as a coating resin, and this is heated and dried to form a coating layer on the carrier core material, itself is positively charged with respect to iron powder. As high as in the case of the present invention in which a resin containing a quaternary ammonium salt compound is used as the coating resin, a high triboelectric charging property to a positively chargeable developer could not be obtained.

[0033]

Embedded image

Further, as an additive for improving the positive charge imparting property of the resin, which is a coating forming material used for forming the resin coating layer, to the positive toner, the iron powder used in the present invention itself is used in the form of iron powder. On the other hand, as a material other than the quaternary ammonium salt compound which is positively chargeable, for example, particles of negative silica or negative Teflon (registered trademark) can be considered. It is necessary to add these in large amounts in order to obtain, which tends to cause a decrease in strength as a coating layer. In addition, when a chromium complex of azonaphthol containing chlorophenol, an iron complex of azonaphthol containing chlorphenol and anilide, a chromium ditertiarybutylsalicylate complex, which is generally used as a negative charge control agent, and the like, the positive polarity toner is also added. Can improve the charge-imparting property of the polyamide resin film to some extent, but it is not as remarkable as the specific quaternary ammonium salt compound used in the present invention. Further, the above-described negative charge control agents are hardly dispersed in the polyamide resin depending on the material, and as a result, similarly to the above, there is a case where the strength of the coating layer is easily reduced.

On the other hand, when the resin composition is formed by adding the specific quaternary ammonium salt compound used in the present invention to the resin, the quaternary ammonium salt compound is incorporated into the structure of the resin. In particular, when used as a resin composition (paint) containing at least a resin and a quaternary ammonium salt compound which is positively charged with respect to iron powder, for example, using methanol or the like as a solvent, the resin is added to the resin. Of the quaternary ammonium salt is very good, and the effect is remarkable. For this reason, unlike the case of the above-mentioned particle-added system such as the negative silica particles or the negative Teflon particles, the positive triboelectric charge-imparting property to the positive toner is improved not partially but in the entire coating layer. Further, unlike the particle-added coating film, the workability is not impaired and the strength of the coating layer is not reduced.

Therefore, by using a developer having a carrier provided with a coating layer formed of the above-described resin in a developing device, it is possible to use not only under normal temperature and normal humidity but also under high temperature and high humidity or low humidity. It is possible to provide a good image even below. Further, a stable image can be provided even in long-term durability.

Specific examples of the quaternary ammonium salt compound suitably used in the present invention, which itself is positively charged with respect to iron powder, include the following compounds. The present invention is not limited to these.

[0038]

Embedded image

The fourth type used in the present invention as described above
The addition amount of the quaternary ammonium salt compound is preferably 1 to 100 parts by weight based on 100 parts by weight of the coating resin of the carrier. If the amount is less than 1 part by weight, no improvement in the charge imparting property by addition is observed, and if it exceeds 100 parts by weight, dispersion in the resin becomes poor, and the coating strength tends to decrease.

As the carrier core material used in the present invention, general materials such as iron powder and ferrite are used, and the particle size is 10 to 1000 μm, preferably 20 to 200 μm.
m is appropriate.

The method of coating the surface of the carrier core material with the resin in which the quaternary ammonium salt is dispersed is as follows.
The resin is dissolved in a solvent, a quaternary ammonium salt is further added, the mixture is sufficiently dispersed with a disperser, the core material is immersed in the solution, and the mixture is agitated if necessary. And high-temperature baking.

The coating layer of the present invention may contain a conductive substance and a lubricating substance, if necessary. Examples of such materials include molybdenum disulfide, boron nitride, mica, graphite, graphite fluoride, silver-niobium selenide, calcium chloride-graphite, talc, teflon,
Examples include fluorinated polymers such as PVDF, and fatty acid metal salts such as zinc stearate, magnesium stearate, aluminum stearate, and zinc palmitate. Among them, graphite is preferably used because it has conductivity as well as lubricity.

Next, the toner used for obtaining a visible image by the developer carrier or the developing device of the present invention will be described.

The toner is roughly classified into a dry toner and a wet toner. However, the dry toner is mainly used at present because the problem of solvent evaporation is large. Toner mainly consists of melt-kneading materials such as binder resin, release agent, charge control agent and colorant, cooling and solidifying the melt, pulverizing it, and then classifying it to obtain a fine powder with uniform particle size distribution. It is.

As the binder resin used for the toner, generally known resins can be used. For example, styrene,
Styrenes such as α-methylstyrene and p-chlorostyrene and substituted polymers thereof; styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-
Ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer,
Styrene-dimethylaminoethyl copolymer, styrene-
Methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl methyl ketone Styrene-based copolymers such as copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-maleic acid copolymers, styrene-maleic acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, Polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, phenolic resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, paraffin wax, carnauba wax, etc. single Or in combination can be used.

The toner can contain a pigment as a colorant. For example, carbon black, nigrosine dye, lamp black, Sudan Black SM, Fast, Yellow G, Benzidine Yellow, Pigment Yellow, India First Orange, Irgazine Red, Paranitroaniline Red, Toluidine Red, Carmine FB, Permanent Bordeaux FR
R, Pigment Orange R, Risor Red 2G,
Lake Red C, Rhodamine FB, Rhodamine B Lake, Methyl Bio Red B Lake, Phthalocyanine
Blue, Pigment Blue, Brilliant Green B, Phthalocyanine Green, Oil Yellow GG, Pomelo First Yellow CGG, Kaya Set Y96
3, Kaya Set YG, Pomelo First Orange R
R, Oil Scarlet, Orazol Brown B,
Pomelo First Scarlet CG, Oil Pink O
P is mentioned, and it is possible to select and use them appropriately from these.

When the toner is used as a magnetic toner, a magnetic powder is contained in the toner. As such magnetic powder, a substance which is magnetized in a magnetic field is used, and powder of ferromagnetic metal such as iron, cobalt, nickel, etc.
Or these metals aluminum, cobalt, copper, lead,
Magnesium, tin, zinc, antimony, beryllium,
Alloys of metals such as bismuth, calcium, manganese, selenium, titanium, tungsten, vanadium and mixtures thereof, or iron oxides such as magnetite, hematite, ferrite, and silicon, aluminum, magnesium, etc. on or in the surface of or inside magnetic iron oxide Those containing compounds such as metal oxides, hydrated oxides, and hydroxides are preferably used. The content of these magnetic powders is preferably about 15 to 70% by weight based on the weight of the toner.

In some cases, various release agents are added to the toner and contained therein. Examples of such release agents include polyfluoroethylene, fluororesin, fluorocarbon oil, silicone oil, and low molecular weight polyethylene. , Low molecular weight polypropylene and various waxes. Further, if necessary, various charge control agents may be added in order to facilitate positive or negative charging.

Next, an example of a developing device incorporating the carrier of the present invention will be described.

FIG. 1 shows an example of a two-component developing apparatus using a carrier. In the developing chamber 45 of the developing container 12, a non-magnetic developing sleeve (developer carrier) 21 as a developer carrier is opposed to the electrostatic latent image carrier 11 rotated in the direction of arrow a.
A magnetic roller 22 as a magnetic field generating means is immovably installed in the developing sleeve 21, and the magnetic roller 22 is sequentially moved from a position substantially at the top in the rotational direction of the arrow b.
1, N1, S2, N2, N3 are magnetized. In the developing chamber 45, a two-component developer 41 in which the toner 40 and the magnetic carrier 43 are mixed is accommodated. This developer 4
When the toner 1 is sent into the stirring chamber 42 of the developing container 12 through one opening (not shown) of the partition 48 which is open at the upper end at one end of the developing chamber 45, the toner 40 supplied from the toner chamber 47 into the stirring chamber 42 Is supplied to the other end of the stirring chamber 42 while being mixed by the first developer stirring and conveying means 50 in the stirring chamber 42. The developer 41 conveyed to the other end of the stirring chamber 42 is returned to the developing chamber 45 through the other opening (not shown) of the partition 48, where the second developer stirring and conveying means 51 in the developing chamber 45 , Transport means 5 in the upper part of the developing chamber 45
The developer is transported to the developing sleeve 21 while being agitated and transported by a third developer agitating / transporting unit 52 that transports the developer in a direction opposite to the transport direction of the developer 1.

The developer 41 supplied to the developing sleeve 21
The developer regulating member blade 2, which is magnetically constrained by the magnetic force of the magnet roller 22, is carried on the developing sleeve 21, and is provided substantially on the top of the developing sleeve 21.
3, the developing unit 101 is formed in a thin layer of the developer 41 on the developing sleeve 21 and faces the latent image holding member 11 with the rotation of the developing sleeve 21 in the direction of arrow b.
, Where it is subjected to development of the electrostatic latent image on the latent image holding member 11. Residual developer 4 not consumed in development
1 is collected in the developing container 12 by the rotation of the developing sleeve 21.

In the developing container 12, the remnant developer 41 remaining magnetically constrained on the developing sleeve 21 by the repulsive magnetic field between N2 and N3 having the same polarity is peeled off. In order to prevent toner scattering when the developer 41 rises along the line of magnetic force due to the magnetic pole N2, an elastic seal member 31 is provided at the lower part of the developing container 12 such that one end thereof contacts the developer 41. Fixed and installed.

FIG. 1 is only a schematic example, and it goes without saying that there are various forms in the shape of the container, the presence or absence of the stirring member, the arrangement of the magnetic poles, and the like.

[0054]

The present invention will be described more specifically below with reference to examples and comparative examples. Tables 1 and 2 collectively show the configurations of the coated carriers obtained in the examples and comparative examples.

<Example 1>

[0056]

Embedded image

The triboelectric charge of the quaternary ammonium salt compound (1) with iron powder was determined by a blow-off method using a commercially available triboelectric charge measuring device (TB-200, manufactured by Toshiba Chemical). Met.

100 parts by weight of phenol resin produced using ammonia as a catalyst (solid content 50%) 20 parts by weight of quaternary ammonium salt compound (1) 30 parts by weight of methanol

Glass beads having a diameter of 3 mm were added as media particles to the above-mentioned materials, and dispersed by a sand mill for 1 hour.
The beads were separated using a sieve and the solid content was reduced to 20 with IPA.
% To obtain a carrier coating solution.

For 1 kg of a carrier core material of spherical ferrite having an average particle diameter of 100 μm, 100 g of the above coating agent
To form a coating layer using a Nauta mixer at the ratio of
Subsequently, the conductive coating layer was cured by heating at 140 ° C. for 1 hour in a hot-air drying furnace to prepare a coated carrier C-1.

On the other hand, a toner was prepared as follows.・ Styrene-acrylic acid-2-ethylhexyl methacrylate 100 parts by weight Dimethylaminoethyl copolymer (copolymerization ratio = 80: 15: 5) ・ Copper phthalocyanine pigment 5 parts by weight ・ Low molecular weight polypropylene 4 parts by weight

After sufficiently premixing the above-mentioned substances, they are melt-kneaded, cooled, and then cooled to a particle size of about 1 to 2 m using a hammer mill.
m. Next, it was pulverized by a pulverizer using an air jet method. Further, the obtained finely pulverized product was classified using an elbow jet classifier to obtain a positively chargeable cyan fine powder having a weight average particle size of 8.2 μm.
100 parts by weight of the cyan fine powder and 0.8 parts by weight of positively charged hydrophobic colloidal silica treated with an amino-modified silicone oil were mixed by a Henschel mixer,
A cyan toner A was prepared.

The amount of triboelectric charge on the toner A and the coat carrier C-1 was measured using an apparatus as shown in FIG. The toner and the carrier are mixed so that the toner becomes 5% by weight, and mixed with a Turbula mixer for 60 seconds. In the apparatus shown in FIG. 2, this developer is put into a metal container 2 having a 500-mesh conductive screen 3 attached to the bottom, and is sucked by a suction machine 1 through a suction port 7 to obtain a weight difference between before and after suction and the container. The amount of triboelectric charge is determined from the potential stored in the capacitor 8 connected to the capacitor 2. At this time, the suction pressure is 250 mmH
g. With this method, the frictional charge amount of the toner or the carrier is calculated using the following equation.

[0064]

(Equation 1) (Where W1 is the weight before suction, W2 is the weight after suction, C is the capacity of the capacitor, and V is the potential stored in the capacitor.)

FIG. 3 shows a graph of the charge amount versus the amount of the quaternary ammonium salt compound added to the toner A and the resin used for the carrier coating layer of the present invention, measured by the above method. As shown in the figure, an amino group or ＮＨNH, -NH
No change in the charge amount due to the addition of the PMMA resin containing no-was not observed.

Using a developer obtained by mixing the carrier C-1 and the toner A so as to have a toner concentration of 5% by weight, H /
Continuous image output of 10,000 sheets under H (high temperature and high humidity) and N / L (normal temperature and low humidity) environment
An image output test was performed using a blue developing device of the modified machine. Table 3 shows the evaluation results at this time.

[Evaluation] (1) Image Density The image density was measured by using a reflection densitometer RD918 (manufactured by Macbeth) to measure the density of solid black portions.

(2) Tribo To measure the tribo value of the suction method on the developer carrying member, a measuring container having a cylindrical filter paper was used, a metal suction port was fitted along the shape of the surface of the developer carrying member, and an image was formed. Immediately after formation (5
The pressure is adjusted so that the developer layer on the surface of the developer carrying member (preferably within minutes) can be uniformly sucked without excess or shortage, and the developer is sucked. The charge Q of the developer sucked at this time is changed to 6
16 Digital Electrometer (KEITHLEY
Q / M (mC / kg)
Was calculated by

(3) Contamination Resistance of Coating Layer The carrier surface after durability was observed by SEM to evaluate the degree of toner contamination. : Slight contamination is observed. ○ △: Slight contamination is observed. Δ: Contamination is partially observed. X: Remarkable contamination is observed.

(4) Fog Density The reflectance of a solid white portion was measured, and the reflectance of unused paper was measured. The reflectance was measured with TC-6DS (manufactured by Tokyo Denshoku). ◎: 1.5 or less; almost unrecognizable ：: 1.5 to 2.5; cannot be understood without careful attention △: 2.5 to 3.5; fog gradually becomes recognizable △ ×: 3.5 to 4 0.0; fog can be seen at a glance at the lower limit of the practical level. X: 4.0 to 5.0; considerably poor

<Embodiment 2>

[0072]

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When the charge amount of the quaternary ammonium salt compound (2) was measured by blow-off using iron powder in the same manner as in Example 1, the charge amount was positive. In Example 1, 4
A coated carrier C-2 was prepared in the same manner as in Example 1 except that the quaternary ammonium salt compound (2) was used.
While supplying an image. Table 3 shows the evaluation results.

<Embodiment 3>

[0075]

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When the charge amount of the quaternary ammonium salt compound (3) was measured by blow-off using iron powder in the same manner as in Example 1, the charge was positive. In Example 1, 4
A coated carrier C-3 was prepared in the same manner as in Example 1 except that the quaternary ammonium salt compound (3) was used.
While supplying an image. Table 3 shows the evaluation results.

<Embodiment 4>

[0078]

Embedded image

When the charge amount of the quaternary ammonium salt compound (4) was measured by blow-off using iron powder in the same manner as in Example 1, the charge was positive. In Example 1, 4
A coat carrier C-4 was prepared in the same manner as in Example 1 except that the quaternary ammonium salt compound (4) was used.
While supplying an image. Table 3 shows the evaluation results.

Example 5 100 parts by weight of phenol resin produced using trimethylamine as a catalyst (solid content 50%) 20 parts by weight of quaternary ammonium salt compound (1) 30 parts by weight of methanol

Glass beads having a diameter of 3 mm were added as media particles to the above-mentioned material, and dispersed by a sand mill for 1 hour.
The beads were separated using a sieve and the solid content was reduced to 20 with IPA.
% To obtain a carrier coating solution. A coating layer is formed using a Nauter mixer at a ratio of 100 g of the above coating agent to 1 kg of a carrier core material of spherical ferrite having an average particle diameter of 100 μm, and subsequently heated at 140 ° C. for 1 hour in a hot air drying furnace to form a coating layer. Was cured to prepare a coated carrier C-5. This was subjected to an image image output test while supplying toner A in the same manner as in Example 1. Table 3 shows the evaluation results.

<Example 6> A coat carrier C-6 was prepared in the same manner as in Example 5, except that a quaternary ammonium salt compound (2) and a phenol resin produced using hexamethylenetetramine as a catalyst were used. And make
An image image test was performed while supplying the toner A.
Table 3 shows the evaluation results.

<Example 7> A coated carrier C-7 was produced in the same manner as in Example 5, except that a quaternary ammonium salt compound (3) and a phenol resin produced using triethylamine as a catalyst were used. And toner A
While supplying an image. Table 3 shows the evaluation results.

Example 8 A coated carrier C-8 was produced in the same manner as in Example 5, except that the quaternary ammonium salt compound (4) and a phenol resin produced using pyridine as a catalyst were used. Then, an image image output test was performed while supplying the toner A. Table 3 shows the evaluation results.

Example 9 • Nylon copolymer containing 66 nylon as a main component 250 parts by weight (solid content: 20%) • Quaternary ammonium salt compound (1) 20 parts by weight • Methanol 30 parts by weight

Glass beads having a diameter of 3 mm were added as media particles to the above-mentioned materials, and dispersed for 1 hour with a sand mill.
The beads were separated using a sieve and the solid content was reduced to 20 with IPA.
% To obtain a carrier coating solution. A coating layer is formed using a Nauter mixer at a ratio of 100 g of the above coating agent to 1 kg of a carrier core material of spherical ferrite having an average particle diameter of 100 μm, and subsequently heated at 140 ° C. for 1 hour in a hot air drying furnace to form a coating layer. Was cured to prepare a coated carrier C-9. This was subjected to an image image output test while supplying toner A in the same manner as in Example 1. Table 3 shows the evaluation results.

Example 10 A coat carrier C-10 was prepared in the same manner as in Example 9 except that the quaternary ammonium salt compound (2) was used in Example 9, and an image was formed while supplying the toner A. And tested. Table 3 shows the evaluation results.

Example 11 125 parts by weight of urethane resin (solid content 40%) 20 parts by weight of quaternary ammonium salt compound (1) 20 parts by weight of DMF 165 parts by weight

To the above material, glass beads having a diameter of 3 mm were added as media particles and dispersed for 1 hour with a sand mill.
The beads were separated using a sieve to obtain a carrier coating solution. A coating layer is formed using a Nauter mixer at a ratio of 100 g of the above coating agent to 1 kg of a carrier core material of spherical ferrite having an average particle diameter of 100 μm, and subsequently heated at 140 ° C. for 1 hour in a hot air drying furnace to form a coating layer. Was cured to prepare a coated carrier C-11. This was subjected to an image image output test while supplying toner A in the same manner as in Example 1. Table 3 shows the evaluation results.

Example 12 A coated carrier C-12 was prepared in the same manner as in Example 11, except that the quaternary ammonium compound (4) was used, and an image was formed while supplying the toner A. Tested. Table 3 shows the evaluation results.

Example 13 100 parts by weight of phenol resin produced using ammonia as a catalyst (solid content 50%) 10 parts by weight of quaternary ammonium salt compound (1) 30 parts by weight of methanol

Glass beads having a diameter of 3 mm were added to the above materials as media particles, and dispersed for 1 hour by a sand mill.
The beads were separated using a sieve and the solid content was reduced to 20 with IPA.
% To obtain a carrier coating solution. A coating layer is formed using a Nauter mixer at a ratio of 100 g of the above coating agent to 1 kg of a carrier core material of a spherical ferrite having an average particle diameter of 100 μm, and then heated at 140 ° C. for 1 hour in a hot air drying furnace to obtain a conductive material. The coating layer was cured to produce a coated carrier C-13.

On the other hand, the following toner was used.・ 100 parts by weight of polyester resin ・ 5 parts by weight of phthalocyanine pigment ・ 4 parts by weight of chromium di-tert-butylsalicylate complex

The above materials are kneaded, crushed and classified by a general dry toner production method, and have a volume average particle size of 8.8 μm.
m was obtained as a negative triboelectrically charging cyan powder. Cyan toner B was prepared by mixing 0.5 parts by weight of hydrophobic colloidal silica with 100 parts by weight of the above colored powder.

FIG. 4 is a graph showing the charge amount versus the amount of the quaternary ammonium salt compound added to the toner B and the resin used for the carrier coating layer of the present invention. As shown in the figure, a PMM that does not contain an amino group or = NH, -NH- in the structure
The resin A did not show any change in charge amount due to the addition.

The cyan toner B and the carrier C-1
3 was mixed at a toner concentration of 5% to prepare a developer, and an image image output test was carried out using a color copier CLC-500 manufactured by Canon Inc. fixed at a developing contrast of 350 V while supplying toner B. Table 4 shows the evaluation results.

Example 14 A coat carrier C-14 was prepared in the same manner as in Example 13 except that a quaternary ammonium salt compound (2) and a phenol resin produced using hexamethylenetetramine as a catalyst were used. Was prepared, and an image image test was performed while toner B was supplied. Table 4 shows the evaluation results.

Example 15 A coated carrier C-15 was prepared in the same manner as in Example 13 except that the quaternary ammonium salt compound (3) and a phenol resin produced using triethylamine as a catalyst were used. And
An image image test was performed while supplying the toner B.
Table 4 shows the evaluation results.

Example 16 A coated carrier C-16 was produced in the same manner as in Example 13 except that the quaternary ammonium salt compound (4) and a phenol resin produced using pyridine as a catalyst were used. And toner B
While supplying an image. Table 4 shows the evaluation results.

<Example 17> A coat carrier C-17 was prepared in the same manner as in Example 9 except that the quaternary ammonium salt compound (3) was used in Example 9, and an image was formed while supplying the toner B. And tested. Table 4 shows the evaluation results.

<Example 18> A coat carrier C-18 was prepared in the same manner as in Example 9 except that the quaternary ammonium salt compound (4) was used, and an image was formed while supplying the toner B. And tested. Table 4 shows the evaluation results.

<Example 19> A coated carrier C-19 was prepared in the same manner as in Example 11, except that the quaternary ammonium salt compound (1) was used.
While supplying an image. Table 4 shows the evaluation results.

<Example 20> A coated carrier C-20 was prepared in the same manner as in Example 11, except that the quaternary ammonium salt compound (2) was used.
While supplying an image. Table 4 shows the evaluation results.

Comparative Example 1 A coated carrier D-1 was prepared in the same manner as in Example 1 except that the quaternary ammonium salt compound (1) used in Example 1 was omitted. An image image test was performed while supplying the toner A. Table 3 shows the evaluation results.

Comparative Example 2 A coated carrier D-2 was prepared in the same manner as in Example 9 except that the quaternary ammonium salt compound (1) used in Example 9 was omitted. An image image test was performed while supplying the toner A. Table 3 shows the evaluation results.

Comparative Example 3 Example 11 was repeated except that the quaternary ammonium salt compound (3) used in Example 11 was omitted.
In the same manner as in Example 11, a coat carrier D-3 was prepared, and an image image test was performed while supplying toner A in the same manner as in Example 11. Table 3 shows the evaluation results.

Comparative Example 4 The amount of triboelectric charge of chromium complex of azonaphthol containing chlorophenol with iron powder was determined by a blow-off method in the same manner as in Example 1, and it was found to be negative. A coated carrier D-4 was prepared in the same manner as in Example 1 except that the quaternary ammonium salt compound (1) was replaced with a chromium complex of azonaphthol containing chlorophenol (S) instead of the quaternary ammonium salt compound (1). An image image output test was performed while supplying toner A in the same manner as in Example 1. Table 3 shows the evaluation results.

(Comparative Example 5) The amount of triboelectric charge of nigrosine with iron powder was determined by the blow-off method in the same manner as in Example 1, and was found to be positive. In Example 1, a coat carrier D-5 was prepared in the same manner as in Example 1 except that nigrosine (N) was used instead of the quaternary ammonium salt compound (1).
And an image image test was conducted while supplying toner A in the same manner as in Example 1. Table 3 shows the evaluation results.

(Comparative Example 6)

[0110]

Embedded image

The charge amount of the quaternary ammonium salt compound (II) was measured by blow-off using iron powder in the same manner as in Example 1. As a result, the charge was negative. In Example 1, a coat carrier D-6 was prepared in the same manner as in Example 1 except that the quaternary ammonium salt (II) was used instead of the quaternary ammonium salt compound (1). Image output test while supplying toner A to the toner. Table 3 shows the evaluation results.

(Comparative Example 7) The procedure of Example 9 was repeated, except that the quaternary ammonium salt compound (1) was replaced by a chromium complex (S) of azonaphthol containing chlorophenol. Carrier D-7 was prepared, and an image image test was performed while supplying toner A in the same manner as in Example 9. Table 3 shows the evaluation results.

Comparative Example 8 A coated carrier D-8 was prepared in the same manner as in Example 11, except that nigrosine (N) was used instead of the quaternary ammonium salt compound (1). An image image output test was performed while supplying toner A in the same manner as in Example 11. Table 3 shows the evaluation results.

(Comparative Example 9) In Example 1, instead of the phenol resin produced using ammonia as a catalyst,
A coat carrier D-9 was prepared in the same manner as in Example 1 except that the PMMA resin was used.
While supplying an image. Table 3 shows the evaluation results.

(Comparative Example 10) As a coat carrier,
Coated carrier D-1 produced in the same manner as in Comparative Example 1.
, And an image image output test was performed while supplying toner B by the same operation as in Example 13. Table 4 shows the evaluation results.

(Comparative Example 11) As a coat carrier,
Coated carrier D-5 produced in the same manner as in Comparative Example 5
And an image image output test was conducted while supplying toner B by the same operation as in Example 13. Table 4 shows the evaluation results.

(Comparative Example 12) As a coat carrier,
Coated carrier D-6 produced in the same manner as in Comparative Example 6
, And an image image output test was performed while supplying toner B by the same operation as in Example 13. Table 4 shows the evaluation results.

(Comparative Example 13) As a coat carrier,
Coated carrier D-9 produced in the same manner as in Comparative Example 9
, And an image image output test was performed while supplying toner B by the same operation as in Example 13. Table 4 shows the evaluation results.

[0119]

[Table 1]

[0120]

[Table 2]

[0121]

[Table 3]

[0122]

[Table 4]

[0123]

As described above, according to the present invention,
A binder resin characterized in that at least a contact portion of the carrier with the toner has any one of an -NH ₂ group, an = NH group, and an -NH- bond in the resin structure; By using a carrier characterized by being a resin composition containing at least a quaternary ammonium salt compound having an anti-static property, the ability to impart a positive triboelectric charge to a toner is remarkably improved, and abrasion resistance is improved. And a carrier which has sufficient mechanical strength, does not cause image defects such as unevenness and streaks, and has high environmental stability, a developer having the carrier, and a developing method.

[Brief description of the drawings]

FIG. 1 is a schematic view of a developing device having a carrier having a resin coating layer according to the present invention.

FIG. 2 is a schematic view schematically showing an apparatus for measuring a triboelectric charge amount of a two-component developer with respect to a carrier of a toner.

FIG. 3 is a graph showing the charge amount versus the amount of a quaternary ammonium salt compound added to the toner A and the resin used for the carrier coating layer of the present invention.

FIG. 4 is a graph showing the charge amount versus the amount of a quaternary ammonium salt compound added to the toner B and the resin used for the carrier coating layer of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Suction machine 2 Measuring container 3 Conductive screen 4 Lid 5 Vacuum gauge 6 Air flow control valve 7 Suction port 8 Capacitor 9 Electrometer 11 Latent image holder 12 Developing container 21 Developing sleeve (developer carrier) 22 Magnet roller 23 Developer Control blade 40 Toner 41 Developer 42 Stirring chamber 43 Carrier 45 Developing chamber 47 Toner chamber

Continued on the front page (72) Inventor Masayoshi Shimamura 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Kazuki Saiki 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Naoki Okamoto 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Yasuhide Goseki 3-30-2 Shimomaruko 3-chome, Ota-ku, Tokyo F-term ( Reference) 2H005 AA00 AA21 BA06 BA07 CA15 CA28 DA03 FA02 2H031 AB01 AC01 AC19 AC30 AD01 AD03 AE01 AE02 BA04 2H077 AB01 AB11 AC04 AC16 AD06 AD13 AD32 CA12 EA03 EA15

Claims (16)

[Claims] 1. A carrier having a resin coating layer comprising a core material and a resin composition, wherein the resin coating layer comprises a resin containing at least a quaternary ammonium salt compound which is positively chargeable with respect to iron powder. A carrier for developing an electrostatic image, characterized by being formed from a composition. 2. The electrostatic image according to claim 1, wherein the resin composition has at least one of a —NH ₂ group, a ＮＨNH group, and a —NH— bond in a resin structure. Development carrier. 3. The electrostatic image developing carrier according to claim 1, wherein the resin composition contains a phenol resin. 4. The phenolic resin is a phenolic resin produced using a nitrogen-containing compound as a catalyst, and has any one of an —NH ₂ group, an ＮＨNH group, or an —NH— bond in its structure. The carrier for developing an electrostatic image according to claim 3, wherein: 5. In a two-component developer having a toner and a carrier, the carrier is a carrier having a resin coating layer composed of a core material and a resin composition, and the resin coating layer is provided with respect to iron powder. A two-component developer comprising a resin composition containing at least a positively chargeable quaternary ammonium salt compound. 6. The two-component system according to claim 5, wherein the resin composition has at least one of a —NH ₂ group, a ＮＨNH group, and a —NH— bond in a resin structure. Developer. 7. The two-component developer according to claim 5, wherein the resin composition contains a phenol resin. 8. The phenolic resin is a phenolic resin produced using a nitrogen-containing compound as a catalyst, and has a structure containing any one of an —NH ₂ group, an ＮＨNH group, and an —NH— bond. The two-component developer according to claim 7, wherein 9. The two-component developer according to claim 5, wherein the toner is a positively chargeable toner. 10. A latent image holding member having at least a container for storing the developer and a developer holding member for carrying and transporting the developer, wherein the latent image holding member is located in a developing region between the latent image holding member and the developer holding member facing the latent image holding member. A developing device for developing the latent image formed on the developer carrier with the developer carried on the developer carrier, wherein the developer is a two-component developer having a toner and a carrier, and the carrier is a core material. And a resin coating layer comprising a resin composition, wherein the resin coating layer is formed of a resin composition containing at least a quaternary ammonium salt compound which is positively chargeable with respect to iron powder. A developing device, characterized in that: 11. The developing device according to claim 10, wherein the resin composition has at least one of a —NH ₂ group, a ＮＨNH group, and a —NH— bond in a resin structure. 12. The phenol resin is contained in the resin composition.
3. The developing device according to claim 1. 13. The phenolic resin is a phenolic resin produced using a nitrogen-containing compound as a catalyst, and has a structure containing any one of an —NH ₂ group, an ＮＨNH group, and an —NH— bond. The developing device according to claim 12, wherein 14. The developing device according to claim 10, wherein the toner is a positively chargeable toner. 15. The developing device according to claim 10, wherein the developer layer on the developer carrier is in contact with the latent image holding member. 16. The developing device according to claim 10, wherein the developer layer on the developer carrier is not in contact with the latent image carrier.