JPH11102084A - Developing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To keep a stable specific concn. of a toner and to maintain stable negative chargeability by previously feeding a specified starting developer and adding a replenishing developer contg. specified toner particles and fine silica particles mixed as an external additive. SOLUTION: A starting developer contg. toner particles contg. a 2:1 type metallic complex salt compd. represented by formula I and a resin binder and fine silica particles mixed as an external additive is previously fed and a replenishing developer contg. toner particles contg. a 2:1 type metallic complex salt compd. represented by formula II and a resin binder and fine silica particles mixed as an external additive is added so as to carry out replenishment. In the formula I, X is -CONHPh, Y is -SO2 C2 H5 , M is Co and A is an alkali metallic or ammonium ion. In the formula II, X is nitro or halogen, Y is H, halogen or nitro and M is Cr.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a developing method used in an electrophotographic system or an electrostatic recording system.

[0002]

2. Description of the Related Art In an electrophotographic apparatus or an electrostatic recording apparatus, in order to visualize an electrostatic latent image formed on an electrostatic holding member from a photoreceptor or a dielectric, a conventional method has been used.
A two-component developing method using a toner and a carrier and a one-component developing method using a toner also having a carrier function are widely used.

[0003] Such a toner is disclosed in JP-A-5-3134.
As disclosed in Japanese Patent Publication No. 04, generally, a thermoplastic resin, a coloring agent, and other additives such as wax are melt-mixed,
After being uniformly dispersed, the solidified product is pulverized and classified to produce colored fine particles having a desired particle size. Alternatively, a method of adding a polymerization initiator to a synthetic resin monomer, further mixing a colorant, and other additives such as a wax, and suspending the mixture in water to polymerize the mixture to produce colored fine particles having a desired particle size. Can be.

[0004] Since the electrostatic holder can be charged positively or negatively, a positive or negative electrostatic latent image is obtained by exposure under the original. Developing with a positively charged toner on a negative electrostatic latent image produces a positive-positive image consistent with the original. On the other hand, when development is performed on the positive electrostatic latent image with negatively charged toner, a positive-negative image is obtained. Thus, there are two types of electrophotographic toner, positively charged toner and negatively charged toner.

[0005] The coloring material mixed with the toner plays an important role as a charge control agent in terms of its electrostatic properties as well as coloring. In particular, many dyes and pigments conventionally used as colorants are positively charged, and even if they are negatively charged, their chargeability is weak. For this reason, when a conventional negatively charged toner is used, fogging or the like occurs, and it has been difficult to obtain a clear image.

Examples of such negatively chargeable dyes include nigrosine dyes, azine dyes, metal complex salts of monoazo dyes, metal complex salts of salicylic acid, metal complex salts of naphthoic acid, metal complex salts of dicarboxylic acid, and copper phthalocyanine pigment. Can be Above all, metal complex salts of monoazo dyes are widely used for black toners because of their high ability to impart electric charge by triboelectric charging.

For example, Japanese Patent Publication No. 41-6397, Japanese Patent Publication No. 41-12915, and Japanese Patent Publication No. 41-20
No. 153, JP-B-43-27596, JP-B-51-29827, JP-A-47-5637, JP-A-49-21151, and JP-A-49-27.
No. 229 discloses an example in which a negatively charged 2: 1 type metal complex dye is used for a toner.

However, these dyes not only have a low negative charge performance in essence, but also have poor compatibility with a binder resin and are not uniformly dispersed in toner particles, so that practical negative chargeability can be obtained at all. I couldn't.

Further, in the conventional developer, if another developer having a different component is mixed, the charging characteristics and life of the developer are deteriorated, and the image obtained using such a developer has a poor image characteristic. It decreases significantly. Therefore, in the conventional developing device, only one developer of the same type as the initially supplied developer can be supplied to one developer container.

[0010]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a developer having a negative charge property and a developer even if developers containing other components are mixed with each other. It is an object of the present invention to provide a developing method using a combination of developers that has a stable toner specific concentration, has long-term life characteristics, and can obtain a clear image without causing image defects such as fog.

[0011]

According to the present invention, first, in a developing method for developing an electrostatic latent image formed on an image carrier using a developer, the developing agent has the following general formula (I). 1)

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(Where X represents a —CONHPh group, Y represents a —SO ₂ C ₂ H ₅ group, M represents a cobalt atom, and A represents an alkali metal or ammonium ion). A starting developer containing toner particles containing a metal complex salt compound and a binder resin, and silica fine particles mixed as an external additive is supplied in advance, and the following general formula (2)

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(Where X is a nitro group or a halogen atom, Y is a hydrogen atom, a halogen atom, or a nitro group, M is a chromium atom, and A is an alkali metal or ammonium ion). A developing method characterized by adding a replenishment developer containing toner particles containing a type 1 metal complex salt compound and a binder resin, and silica fine particles mixed as an external additive to supplement the consumed developer. I do.

The present invention secondly provides a developing method for developing an electrostatic latent image formed on an image carrier using a developer, wherein the developer is represented by the above general formula (2). A toner particle containing a 2: 1 type metal complex compound and a binder resin, and a starting developer containing silica fine particles mixed as an external additive are stored in advance, and the following general formula (3)

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(Wherein, X is a nitro group or a halogen atom, Y is a hydrogen atom, a halogen atom, or a nitro group, M is a cobalt atom, and A is an alkali metal or ammonium ion). Toner particles containing a type 1 metal complex compound and a binder resin, and a replenishment developer containing silica fine particles mixed as an external additive,
There is provided a developing method characterized by being added to supplement a consumed developer.

Thirdly, the present invention relates to a developing method for developing an electrostatic latent image formed on an image carrier using a developer, wherein the developer is represented by the general formula (2). A toner particle containing a 2: 1 type metal complex salt compound and a binder resin, and a starting developer containing silica fine particles mixed as an external additive are stored in advance, and a 2: 1 type compound represented by the above general formula (1) is contained. There is provided a developing method characterized by adding toner particles containing a metal complex salt compound and a binder resin, and a replenishment developer containing silica fine particles mixed as an external additive, in order to supplement the consumed developer.

Fourth, the present invention provides a developing method for developing an electrostatic latent image formed on an image carrier using a developer, wherein the developer is represented by the above general formula (1). A toner developer containing a 2: 1 type metal complex salt compound and a binder resin, and a starting developer containing silica fine particles mixed as an external additive are contained in advance, and a 2: 1 type compound represented by the following general formula (3) is contained. A developing method characterized by adding toner particles containing a metal complex salt compound and a binder resin, and a replenishment developer containing silica fine particles mixed as an external additive to supplement the consumed developer.

Fifth, the present invention provides a developing method for developing an electrostatic latent image formed on an image carrier using a developer, wherein the developer is represented by the general formula (3). A toner particle containing a 2: 1 type metal complex salt compound and a binder resin, and a starting developer containing silica fine particles mixed as an external additive are previously contained, and a 2: 1 type compound represented by the above general formula (1) is contained. There is provided a developing method characterized by adding toner particles containing a metal complex salt compound and a binder resin, and a replenishment developer containing silica fine particles mixed as an external additive, in order to supplement the consumed developer.

Sixth, the present invention provides a developing method for developing an electrostatic latent image formed on an image carrier using a developer, wherein the developer is represented by the general formula (3). A toner developer containing a 2: 1 type metal complex salt compound and a binder resin, and a starting developer containing silica fine particles mixed as an external additive are contained in advance, and a 2: 1 type compound represented by the above general formula (2) is contained. There is provided a developing method characterized by adding toner particles containing a metal complex salt compound and a binder resin, and a replenishment developer containing silica fine particles mixed as an external additive, in order to supplement the consumed developer.

[0020]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present inventors have paid attention to the charge characteristics of a dye used as a charge control agent in a developer, and have a negative charge characteristic and a compatibility with a binder resin used. Consider a combination of a developer containing a very good dye and a developer containing another dye that can be mixed with this developer,
The present invention has been made.

In the developing method of the present invention, a developer is supplied from a developer container onto a developer carrying member arranged opposite to an image carrying member, and an electrostatic latent image formed on the image carrying member is supplied. By developing the image using the developer, in the repetition of the developing process of forming a developer image on the image carrier, the starting developer supplied to the developing device in advance and the consumed developer are supplemented. Use two developers selected from the following three developers containing a dye having a negative charge characteristic and having good compatibility with a binder resin to be used. I do.

I) First developer The following general formula (1)

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(Wherein X represents a —CONHPh group, Y represents a —SO ₂ C ₂ H ₅ group, M represents a cobalt atom, and A represents an alkali metal or ammonium ion). A developer in which silica fine particles are added as an external additive to toner particles containing a metal complex salt compound and a binder resin.

Ii) Second developer The following general formula (2)

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(Where X is a nitro group or a halogen atom, Y is a hydrogen atom, a halogen atom, or a nitro group, M is a chromium atom, and A is an alkali metal or ammonium ion). A developer obtained by adding silica fine particles as an external additive to toner particles containing a type 1 metal complex compound and a binder resin.

Iii) Third developer The following general formula (3)

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(Where X represents a nitro group or a halogen atom, Y represents a hydrogen atom, a halogen atom, or a nitro group, M represents a cobalt atom, and A represents an alkali metal or ammonium ion). A developer obtained by adding silica fine particles as an external additive to toner particles containing a type 1 metal complex compound and a binder resin.

According to the combination of the starting developer and the replenishing developer using these developers, the present invention is divided into the following six.

In the first invention, the first developer is used as a starting developer, and the second developer is used as a replenishment developer.

In the second invention, a second developer is used as a starting developer, and a third developer is used as a replenishment developer.

In the third invention, the second developer is used as a starting developer, and the first developer is used as a replenishment developer.

In the fourth invention, the first developer is used as a starting developer, and the third developer is used as a replenishing developer.

In the fifth invention, a third developer is used as a starting developer, and a first developer is used as a replenishment developer.

In the sixth invention, a third developer is used as a starting developer, and a second developer is used as a replenishing developer.

In the present invention, a replenishment developer using a charge control agent different from the starting developer is used in the repetition of the developing process by continuous copying, and the replenishing developer has a rapid mixing characteristic with the starting developer. The charge control agent contained in the replenishment developer imparts a stable negative charge to the mixture of the starting developer and the replenishment developer, or promotes the application thereof, and a stable triboelectrification characteristic is obtained over a long period of time. . That is, the new developer to be added is quickly negatively charged, and the predetermined charge amount and charge distribution are quickly achieved. Also, they are of opposite polarity, ie, never or minimally positively charged.

In the present invention, ferrite particles represented by the following general formula (4) (MO) _x (Fe ₂ O ₃ ) _Y (4) are preferably used as a carrier. By combining this carrier with the dye used in the present invention, the property of the toner to be electrostatically negatively charged is further improved.

The carrier particles preferably used in the present invention are of a ferrite type and have a Fe ₂ O ₃ content of at least 40 mol%.
Is preferable. (MO) _X is, for example, NiO, CuO, MgO, ZnO, MnCO ₃ , Ba
CO ₃ , SrCO ₃ , Li ₂ (CO ₃ ), CdO and the like can be mentioned.

[0038] In the carrier, Si is used as an additive.
O ₂ , CaCO ₃ , TiO ₂ , SnO ₂ , PbO, V ₂
O ₅ , Bi ₂ O ₃ , Al ₂ O ₃ or the like can be used.

Further, the surface of the carrier is preferably coated with a resin composition comprising a silicone resin.

As the silicone resin, a silicone resin having a low surface tension is preferable, and a resin whose substituent is a methyl group, a phenyl group or an ethyl group is preferable. Further, as the modified silicone resin, for example, alkyd modified,
Modified silicone resins such as epoxy-modified, acrylic-modified, polyester-modified, phenol-modified, melanin-modified, and urethane-modified can be used.

Since the silicone resin-coated carrier has sufficient durability and stable triboelectricity, it is possible to obtain a developer with little environmental dependency and a long service life.

The toner particles used in the present invention are prepared by adding the dye of any of the above formulas (1) to (3) in a weight ratio of 0.5 to 5% by weight with respect to the synthetic resin. It can be produced by a pulverization method of kneading, pulverization and classification, or a polymerization method such as suspension polymerization and emulsion polymerization.

When the amount of the dye is less than 0.5% by weight, the effect of controlling the charge when added is apt to be insufficient, and when the amount is more than 5% by weight, excess dye bleeds, The charging tends to increase or decrease, making it difficult to stabilize.

Further, other colorants,
Alternatively, carbon black or the like may be added.

The silica fine particles used in the present invention include silicon dioxide, aluminum silicate, sodium silicate, zinc silicate, magnesium silicate and the like. In addition to the silica fine particles, inorganic oxide fine particles may be used. Examples of the inorganic oxide fine particles include zinc oxide, titanium oxide, aluminum oxide, zirconium oxide, strontium titanate, and barium titanate. Other cleaning aids include polymethyl methacrylate,
Resin fine powder such as polyvinylidene fluoride and polytetrafluoroethylene may be used. These external additives
Surface treatment such as hydrophobization may be performed.

The content of the silica fine particles contained in the developer used in the present invention varies depending on the contained 2: 1 type metal complex salt compound, and is preferably combined in an appropriate amount. As a result, there is an effect that the charge potential level of each developer can be made uniform, and the rapid mixing characteristics of the replenishment developer with the starting developer can be further improved.

Further, as other known charge control agents,
For example, the metal chelate of alkyl salicylic acid, chlorinated polyester, polyester having an excess acid group, chlorinated polyolefin, metal salt of fatty acid, fatty acid soap, etc. can be prepared by converting the above general formula (1), general formula (2) or general formula (3). Can be used in combination so as not to affect the charge control agent of the compound represented by

Further, as the binder resin used in the present invention, a copolymer of styrene and its substitute, which can be used as a binder resin for a developer, and an acrylic resin can be used.

Examples of the copolymer of styrene and its substituted product include polystyrene homopolymer, hydrogenated styrene resin, styrene-isobutylene copolymer, styrene-butadiene copolymer, acrylonitrile-butadiene-styrene terpolymer. Polymer, acrylonitrile-styrene-acrylate terpolymer, styrene-
Acrylonitrile copolymer, acrylonitrile-acrylic rubber-styrene terpolymer, acrylonitrile-chlorinated polystyrene-styrene terpolymer, acrylonitrile-EVA-styrene terpolymer, styrene-p
-Chlorostyrene copolymer, styrene-propylene copolymer, styrene-butadiene rubber, styrene-maleic acid ester copolymer, styrene-isobutylene copolymer, styrene-maleic anhydride copolymer, and the like.

As the acrylic resin, for example,
Polyacrylate, polymethyl methacrylate, polyethyl methacrylate, poly-n-butyl methacrylate, polyglycidyl methacrylate, polyfluorinated acrylate, styrene-methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-ethyl acrylate copolymer And the like.

In addition, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, polyurethane, polyamide, epoxy resin, phenol resin, urea resin, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, fatty acid or Alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, paraffin waxes and the like can be used alone or as a mixture.

Examples of the coloring agent usable in the present invention include carbon black and organic or inorganic pigments and dyes. Although there are no special restrictions, carbon black includes acetylene black, furnace black, thermal black, channel black, Ketjen black, and the like, and face dyes such as First Yellow G, Benzidine Yellow, Indofast Orange,
Irgazine Red, Carmine FB, Permanent Bordeaux FRR, Pigment Orange R, Lisor Red 2
G, lake C, rhodamine FB, rhodamine B lake, phthalocyanine blue, pigment blue, brilliant green B, phthalocyanine green, quinacridone and the like can be used alone or in combination.

A wax can be used for the toner particles used in the present invention. As such a wax, a paraffin having 8 or more carbon atoms, a polyolefin or the like is preferable. For example, low molecular weight polypropylene, low molecular weight polyethylene, liquid paraffin, acid amide, stearic acid wax, montan wax, sasol wax, caster wax, Chlorinated paraffins and the like are preferred. The wax may be mixed and dispersed in advance during the production of the binder resin.

[0054]

The present invention will be described below more specifically with reference to examples.

Production of Developer The toner particles used in the present invention are produced using a binder resin, a colorant and the like, for example, as follows.

First, at least the binder resin 100
Parts, 3 to 10 parts of a carbon black colorant, and 0.5 to 5 parts of a charge control agent selected from the dyes represented by the general formulas (1) to (3) by ball milling and V-mixing. And dispersing using a mixer, Nauta mixer, Henschel mixer or the like. At this time, a wax, an inorganic pigment, or the like may be further added. Next, the mixture is heated and melt-kneaded using a pressure kneader, a roll, a screw type extruder, a Banbury mixer, or the like. The obtained mixture is roughly pulverized using a hammer mill, a jet mill or the like. Next, the mixture is finely pulverized using a jet mill or the like, and then classified into a desired particle size by air classification or the like, and an external additive consisting of 0.1 to 1 part of silica and 100 parts of the particles is fluidized at high speed. The developer used in the present invention is obtained by mixing with a mold mixer or the like.

Such a developer can be applied to all known developing methods. For example, two-component developing methods such as a cascade method, a magnetic brush method, and a microtoning method, one-component developing methods such as a conductive one-component developing method, an insulating one-component developing method, a jumping developing method, a powder cloud method, and a fur brush method. And a non-magnetic one-component developing method in which the toner is electrostatically held on a toner holding member and conveyed to a developing unit to be developed.

Image Output A commercially available copier equipped with a two-component developing device (trade name: Rheodry ED-6550, to evaluate the charge amount distribution of the developer, the change in the charge amount of the developer, the change in image density, etc.) (Manufactured by Toshiba Corporation).

In FIG. 1, an electrostatic charge image is formed on the photosensitive drum 1. A toner container 2 near the photosensitive drum 1 contains a toner and a carrier (developer) 3.
A multi-pole magnet roll 4 and a developing sleeve 5 mounted on the outer periphery of the multi-pole magnet roll 4 are provided on the photosensitive drum 1 side.
The carrier of the developer 3 adheres to the surface of the developing sleeve 5 by the magnetic force of the multi-pole magnet roller 4, and the toner particles adhere to the surface of the carrier to form a toner layer. still,
The toner / carrier concentration ratio of developer 3 was 6.0%.
In FIG. 1, the multipolar magnet roller is fixed, the developing sleeve is rotated counterclockwise, and the developer 3 is conveyed as needed.
The transport amount of the developer 3 is regulated by the regulating blade 6. At the same time, the photosensitive drum 1 is rotated clockwise, and a bias is applied from the power source 7 at a position where the developing sleeve 5 and the photosensitive drum 1 approach each other, so that the electrostatic attraction causes the developing sleeve 5 to move onto the photosensitive drum 1. The toner 3 adheres to the electrostatic image, and development is performed.

Example 1 Styrene-acrylic copolymer resin 89% by weight Carbon black 7% by weight Polypropylene 2% by weight The following structural formula (5)

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The above components were mixed, melt-kneaded, finely pulverized and classified to obtain toner particles having an average particle size of 5 to 15 μm. This toner particle 1
A starting toner was obtained by mixing 0.3% by weight of hydrophobic silica and 0.1% by weight of fine alumina particles with 00% by weight.

Further, among the above components, the above structural formula (5)
Instead of the metal-containing complex dye represented by the following formula, the following structural formula (6)

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A replenishment toner was obtained in the same manner as in the metal-containing complex dye represented by the formula (1).

6% by weight of the starting toner was mixed with 94% by weight of a carrier obtained by coating a silicone resin on a ferrite core having an average particle diameter of 43 to 100 μm to prepare a starting developer.

The ferrite core was obtained by pulverizing and mixing 14 mol% of CuO, 16 mol% of ZnO and 70 mol% of Fe ₂ O ₃ in a wet ball mill for 10 hours, and then drying.
It was kept at 950 ° C. for 4 hours. This is wet ball mill 2
It was pulverized for 4 hours and reduced to 5 μm or less. The slurry was granulated, dried, and kept at 1140 ° C. for 6 hours, and then pulverized and classified to have an average particle size of 43 to 100 μm. The composition of this carrier is 14 mol% of CuO, 15 mol% of ZnO, Fe ₂ O
₃ 71 mole%, X / Y was 0.45. to this,
The silicone resin is applied to the carrier using a fluidized bed for 5 minutes.
After coating by weight, baking was performed at 190 ° C. for 3 hours to obtain a resin-coated carrier.

Commercial copying machine (ED-6550, manufactured by Toshiba)
Was charged with the above-mentioned starting developer, and a replenishing hopper was charged with a replenishing toner, and a copying test was performed. The results are shown in Tables 1 to 3. As shown in Tables 1 to 3, when the method of the present invention is used, a clear image having a high density can be obtained even in each environment, and a stable toner specific density in the developer can be obtained even during a continuous copying test. After a copy test of 120,000 sheets (60,000 sheets in low-temperature, low-humidity and high-temperature, high-humidity environmental conditions),
There was no change in the charge amount, and a clear image with high density could be maintained.

After the developer containing the starting toner was stirred for 5 minutes, 1% by weight of an uncharged replenishing toner was further added and mixed for 30 seconds, and the respective charge amounts, charge amount distributions and reverse charge ratios were measured. Was measured. The results are shown in Table 4 below. As shown in Table 4, there was no difference in each charge amount, charge amount distribution, reverse charge ratio, and charge amount distribution peak position, and the mixing of the starting developer and the added replenishment developer was performed quickly. That was shown.

Example 2 Instead of the metal-containing complex dye represented by the structural formula (6),
The following structural formula (7)

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Example 1 except that the metal-containing complex dye represented by the formula (1) was used, and 0.5% by weight of hydrophobic silica and 0.1% by weight of alumina fine particles were mixed with 100% by weight of the obtained replenishment toner particles. In the same manner as in the above, a replenishment toner was obtained.

A starting toner was obtained by using a metal-containing complex dye represented by the following structural formula (6) instead of the metal-containing complex dye represented by the structural formula (5). The obtained starting toner was mixed with the same carrier particles as in Example 1 to prepare a starting developer.

Commercial copying machine (ED-6550, manufactured by Toshiba)
Then, the above-mentioned starting developer was added, and the above-mentioned replenishment toner was put into a replenishment hopper, and a copy test was performed. Tables 1 to 3 show the obtained results. As shown in Tables 1 to 3, a high-density clear image was obtained even in each environment, and during a continuous copy test, the toner density in the developer was kept stable, and 120,000 sheets ( Even after a copying test under environmental conditions of 60,000 sheets at low temperature, low humidity and high temperature and high humidity), a clear image could be maintained at a high density without a change in charge amount.

After the developer containing the starting toner is stirred for 5 minutes, 1% by weight of an uncharged replenishing toner is further added to the starting toner and mixed for 30 seconds. The reverse charging ratio was measured. Table 4 shows the results. As shown in Table 4, there was no difference in the respective charge amounts, charge amount distributions, reverse charge ratios, and charge amount distribution peak positions, and it was confirmed that the developer containing the starting toner and the replenishment toner were rapidly mixed. Indicated.

Example 3 A starting developer was prepared using the same starting toner and carrier particles as in Example 2.

A replenishment toner was obtained in the same manner as in Example 1, except that the metal-containing complex dye represented by the structural formula (6) was changed to the metal-containing complex dye represented by the structural formula (5). The starting developer obtained was placed in a commercially available copying machine (ED-6550, manufactured by Toshiba), and the replenishing hopper was charged with the replenishing toner, and a copying test was performed. The obtained results are shown in Table 1 below.
And Table 3 below. As shown in Tables 1 to 3, a high-density clear image was obtained even in each environment, and even during a continuous copying test, a stable toner specific concentration in the developer was maintained. Even after the copying test of 60,000 sheets under low and low humidity and high temperature and high humidity environment conditions, there is no change in the charge amount.
A high-density and clear image could be maintained.

After the developer containing the starting toner was stirred for 5 minutes, 1% by weight of an uncharged replenishment toner was further added to the developer, mixed for 30 seconds, and the respective charge amounts and charge amount distributions were changed. And the reverse charge ratio was measured. Table 4 shows the obtained results. As is clear from Table 4, there is no difference in the respective charge amounts, charge amount distributions, reverse charge ratios, and charge amount distribution peak positions, and there is no difference between the developer containing the starting toner and the developer containing the added replenishment toner. This indicated that mixing was rapid.

Example 4 Instead of the metal-containing complex dye represented by the structural formula (6),
The same procedure as in Example 1 was carried out except that the metal-containing complex dye represented by the structural formula (7) was used, and 0.5% by weight of hydrophobic silica and 0.1% by weight of alumina fine particles were mixed with 100% by weight of toner particles. To obtain replenishment toner.

A starting developer was prepared using the same starting toner and carrier particles as in Example 1.

Commercial copying machine (ED-6550, manufactured by Toshiba)
Was charged with the above-mentioned starting developer, and a replenishing hopper was charged with a replenishing toner, and a copying test was performed. The results are shown in Tables 1 to 3. As shown in Tables 1 to 3, a high-density clear image was obtained even in each environment, and a stable toner specific concentration in the developer was maintained even during a continuous copy test.
Further, even after a copy test of 120,000 sheets (60,000 sheets in low-temperature, low-humidity and high-temperature, high-humidity environmental conditions), the charge amount did not change, and a clear image with high density could be maintained.

After the developer containing the starting toner was stirred for 5 minutes, 1% by weight of an uncharged replenishment toner was further added to the developer, mixed for 30 seconds, and the respective charge amounts and charge amount distributions were changed. And the reverse charge ratio was measured. Table 4 shows the obtained results. As is clear from Table 4, there is no difference in the respective charge amounts, charge amount distributions, reverse charge ratios and charge amount distribution peak positions, and the mixing of the developer containing the starting toner and the added first toner is rapid. It was shown that it was done.

Example 5 A replenishment toner was obtained in the same manner as in Example 1 except that the metal-containing complex dye represented by the structural formula (6) was changed to the metal-containing complex dye represented by the structural formula (5). Was. Toner particles were obtained in the same manner as in Example 1, except that the metal-containing complex dye represented by the structural formula (5) was changed to the metal-containing complex dye represented by the structural formula (7). Toner particles 10
A starting toner was obtained in the same manner as in Example 1, except that 0.5% by weight of hydrophobic silica and 0.1% by weight of alumina fine particles were mixed with 0% by weight. The starting developer was prepared using the carrier particles of Example 1.

Commercial copying machine (ED-6550, manufactured by Toshiba)
And the first toner was placed in a replenishing hopper, and a copy test was performed. The results are shown in Tables 1 to 3. As shown in Tables 1 to 3, a high-density clear image was obtained even in each environment, and during a continuous copy test, the toner density in the developer was kept stable, and 120,000 sheets ( Even after a copying test under environmental conditions of 60,000 sheets at low temperature, low humidity and high temperature and high humidity), a clear image could be maintained at a high density without a change in charge amount.

After stirring the developer containing the starting toner for 5 minutes, 1% by weight of an uncharged replenishment toner was further added to the developer and mixed for 30 seconds, and the respective charge amounts, charge amount distributions and The reverse charging ratio was measured. Table 4 shows the obtained results. As shown in Table 4, there is no difference in the respective charge amounts, charge amount distributions, reverse charge ratios, and charge amount distribution peak positions, and the developer containing the starting toner and the added replenishment toner are quickly mixed. That was shown.

Example 6 A replenishment toner was obtained in the same manner as in Example 1 except that the metal-containing complex dye represented by the structural formula (5) was changed to the metal-containing complex dye represented by the structural formula (6). Was.

A starting developer was prepared using the same starting toner and carrier particles as in Example 5.

Commercial copying machine (ED-6550, manufactured by Toshiba)
And the first toner in a replenishing hopper, and a copying test was performed. The results are shown in Tables 1 to 3. As is clear from Tables 1 to 3,
A clear image of high density was obtained in each environment, and the toner density in the developer was kept stable even during the continuous copying test. Further, 120,000 sheets (at environmental conditions of low temperature and low humidity and high temperature and high humidity) Even after the copy test (60,000 sheets), the charge amount did not change, and a clear image with high density could be maintained.

After the developer containing the starting toner was stirred for 5 minutes, 1% by weight of an uncharged replenishment toner was further added to the developer, mixed for 30 seconds, and each charge amount, charge amount distribution and The reverse charging ratio was measured. The results are shown in Table 4 below. As is clear from Table 4, there is no difference in the respective charge amounts, charge amount distributions, reverse charge ratios, and charge amount distribution peak positions, and the developer containing the starting toner and the replenishment toner toner were rapidly mixed. That was shown.

Comparative Example 1 A negatively charged particle size of 5 was obtained in the same manner as in Example 1 except that the metal-containing complex dye represented by the structural formula (6) was not added.
A replenishment toner of about 15 μm was obtained.

Next, instead of the metal-containing complex dye represented by the structural formula (5), the following structural formula (6) and Example 1 were used.
A resin obtained by subjecting the ferrite core to resin coating and baking in the same manner as in Example 1 using a fluidized bed with a styrene-methyl methacrylate resin having a monomer composition ratio of styrene and methyl methacrylate of 45:55. The starting carrier was prepared by mixing the coated carrier particles.

Commercial copying machine (ED-6550, manufactured by Toshiba)
And the first toner in a supply hopper, and a copy test was performed. The obtained results are shown in Tables 1 to 3 below. As shown in Tables 1 to 3, high density and clear pixels were obtained at the initial stage, but the toner specific density and charge amount were significantly changed by continuous copying tests. It was not possible to maintain a clear image at high humidity, high density and high density.

After the developer containing the starting toner is stirred for 5 minutes, 1% by weight of uncharged replenishment toner particles are further added to the developer and mixed for 30 seconds. The distribution and reverse charge ratio were measured. Table 4 shows the results. As shown in Table 4, each charge amount,
A clear difference was observed in the charge amount distribution, the reverse charge ratio, and the peak position of the charge amount distribution, indicating that the mixing of the developer containing the starting toner and the added replenishment toner was insufficient.

[0091]

[Table 1]

[0092]

[Table 2]

[0093]

[Table 3]

[0094]

[Table 4]

[0095]

According to the present invention, even when a replenishment developer having a different charge control agent from a starting developer is used, the developer exhibits excellent mixing characteristics without being substantially affected by relative humidity. In other words, it is possible to maintain a stable toner specific concentration in the developer and maintain a stable negative charging property. Therefore, a clear image can be obtained having long-term life characteristics.

[Brief description of the drawings]

FIG. 1 is a diagram showing an example of a developing device for applying a method of the present invention.

Claims (13)

[Claims] 1. A developing method for developing an electrostatic latent image formed on an image carrier using a developer, wherein the developer is represented by the following general formula (1): (Where X is a —CONHPh group, Y is —SO ₂ C ₂
(H represents a H ₅ group, M represents a cobalt atom, A represents an alkali metal or ammonium ion), and was mixed as a toner particle containing a 2: 1 type metal complex salt compound and a binder resin, and as an external additive. A starting developer containing silica fine particles is supplied in advance, and the following general formula (2) is used. (Wherein, X is a nitro group or a halogen atom, Y is a hydrogen atom, a halogen atom, or a nitro group, M is a chromium atom, and A represents an alkali metal or ammonium ion). A developing method characterized by adding a replenishing developer containing toner particles containing a complex salt compound and a binder resin, and silica fine particles mixed as an external additive, in order to supplement the consumed developer. 2. The method according to claim 1, wherein the content of the silica fine particles contained in the replenishment developer is equal to or less than the content of the silica fine particles contained in the starting developer. 3. A developing method for developing an electrostatic latent image formed on an image carrier using a developer, wherein the developer is represented by the following general formula (2): (Wherein, X is a nitro group or a halogen atom, Y is a hydrogen atom, a halogen atom, or a nitro group, M is a chromium atom, and A represents an alkali metal or ammonium ion). A toner particle containing a complex salt compound and a binder resin, and a starting developer containing silica fine particles mixed as an external additive are stored in advance, and the following general formula (3): Wherein X is a nitro group or a halogen atom, Y is a hydrogen atom, a halogen atom, or a nitro group, M is a cobalt atom, and A is an alkali metal or ammonium ion. A developing method characterized by adding a replenishing developer containing toner particles containing a complex salt compound and a binder resin, and silica fine particles mixed as an external additive, in order to supplement the consumed developer. 4. The method according to claim 3, wherein the content of the silica fine particles contained in the replenishment developer is larger than the content of the silica fine particles contained in the starting developer. 5. A developing method for developing an electrostatic latent image formed on an image carrier using a developer, wherein the developer is represented by the following general formula (2): (Wherein, X is a nitro group or a halogen atom, Y is a hydrogen atom, a halogen atom, or a nitro group, M is a chromium atom, and A represents an alkali metal or ammonium ion). A toner particle containing a complex salt compound and a binder resin, and a starting developer containing silica fine particles mixed as an external additive are contained in advance, and the following general formula (1): (Wherein, X is -CONHPh group, Y -SO ₂ C
Represents a ₂ H ₅ group, M represents a cobalt atom, and A represents an alkali metal or ammonium ion).
A developing method characterized by adding a replenishment developer containing toner particles containing a metal complex compound and a binder resin and silica fine particles mixed as an external additive in order to supplement the consumed developer. 6. The content of the silica fine particles contained in the replenishment developer is equal to or larger than the content of the silica fine particles contained in the starting developer.
The method described in. 7. A developing method for developing an electrostatic latent image formed on an image carrier using a developer, wherein the developer is represented by the following general formula (1): (Where X is a —CONHPh group, Y is —SO ₂ C ₂
(H represents a H ₅ group, M represents a cobalt atom, A represents an alkali metal or ammonium ion), and was mixed as a toner particle containing a 2: 1 type metal complex salt compound and a binder resin, and as an external additive. A starting developer containing silica fine particles is stored in advance, and is represented by the following general formula (3). Wherein X is a nitro group or a halogen atom, Y is a hydrogen atom, a halogen atom, or a nitro group, M is a cobalt atom, and A is an alkali metal or ammonium ion. A developing method characterized by adding a replenishing developer containing toner particles containing a complex salt compound and a binder resin, and silica fine particles mixed as an external additive, in order to supplement the consumed developer. 8. The method according to claim 7, wherein the content of the silica fine particles contained in the replenishment developer is larger than the content of the silica fine particles contained in the starting developer. 9. A developing method for developing an electrostatic latent image formed on an image carrier using a developer, wherein the developer is represented by the following general formula (3): Wherein X is a nitro group or a halogen atom, Y is a hydrogen atom, a halogen atom, or a nitro group, M is a cobalt atom, and A is an alkali metal or ammonium ion. The toner particles containing the complex salt compound and the binder resin, and the starting developer containing the silica fine particles mixed as an external additive are stored in advance, and the following general formula (1): (Wherein, X is -CONHPh group, Y -SO ₂ C
Represents a ₂ H ₅ group, M represents a cobalt atom, and A represents an alkali metal or ammonium ion).
A developing method characterized by adding a replenishment developer containing toner particles containing a metal complex compound and a binder resin and silica fine particles mixed as an external additive in order to supplement the consumed developer. 10. The method according to claim 9, wherein the content of the silica fine particles contained in the replenishment developer is smaller than the content of the silica fine particles contained in the starting developer. 11. A developing method for developing an electrostatic latent image formed on an image carrier using a developer, wherein the developer is represented by the following general formula (3). Wherein X is a nitro group or a halogen atom, Y is a hydrogen atom, a halogen atom, or a nitro group, M is a cobalt atom, and A is an alkali metal or ammonium ion. A toner particle containing a complex salt compound and a binder resin, and a starting developer containing silica fine particles mixed as an external additive are stored in advance, and the following general formula (2): (Wherein, X is a nitro group or a halogen atom, Y is a hydrogen atom, a halogen atom, or a nitro group, M is a chromium atom, and A represents an alkali metal or ammonium ion). A developing method, comprising: adding toner particles containing a complex salt compound and a binder resin; and a replenishment developer containing silica fine particles mixed as an external additive, in order to supplement the consumed developer. 12. The method according to claim 11, wherein the content of the silica fine particles contained in the replenishment developer is smaller than the content of the silica fine particles contained in the starting developer. 13. The starting developer and the replenishing developer are each represented by the following general formula (4): (MO) _x (Fe ₂ O ₃ ) _Y (4) (where M is Li, Mg, Mn, Fe (II), C
o, one or two or more metals selected from the group consisting of Ni, Cu, Zn, Cd, Sr, and Ba, and the molar ratio X / Y between X and Y is 1.0 or less. The method according to any one of claims 1 to 12, further comprising a carrier in which the magnetic particles to be coated are coated with a resin composition comprising a silicone resin.