JPH01113762A - Toner for developing electrostatic image - Google Patents

Abstract

PURPOSE:To improve developing effect and cleaning effect of a toner for developing electrostatic images, and to obtain picture images contg. no black spots many times repeatedly by incorporating fine inorganic particles and fine org. particles having a smaller particles size than a binder resin particles into binder resin particles contg. a charge controlling agent. CONSTITUTION:The title toner is prepd. by mixing binder resin particles (A) contg. a dispersed charge controlling agent (a) with inorg. fine particles (B) and fine org. particles (C) having a smaller particle size than said binder resin particles. The charge controlling agent (a) is pref. selected from electron acceptive compds. such as azo type electron acceptive compds. salicylic acid type metal complex electron acceptive compds., etc., or electron donative compds. such as nigrosine dye, amine compd. type electron donative compds. Further, the particle (B) is pref. silica or surface-treated silica, and the particle (C) as pref. poly(methyl methacrylate) particle having >=3mum mean particle size of the primary particles, which is larger than that of the particle (B).

Description

Detailed Description of the Invention [Industrial Application Field] The present invention is directed to developing an electrostatic latent image formed on the surface of a latent image carrier in, for example, electrophotography, electrostatic recording, electrostatic printing, etc. This invention relates to toner for developing electrostatic images.

[Technology background]

In general, in electrophotography, a latent image carrier having a photosensitive layer made of a photoconductive material is given an electrostatic charge, and then the surface of the latent image carrier is exposed to light. A corresponding electrostatic latent image is formed, and this electrostatic latent image is developed by the developer conveyed to the development area by the developer conveyance carrier to form a toner image. This toner image is transferred to a transfer material such as paper and then fixed by heating, pressure, etc. to form a copy image. On the other hand, after the transfer process, the latent image carrier is neutralized, and the remaining developer after transfer is cleaned, and then the latent image carrier is used for forming the next copy image.

However, in order to achieve good development, it is required that the developer transport carrier stably transport an appropriate amount of toner to the development area, and for this purpose, the toner must have high fluidity. It is said that From this point of view, toners have conventionally been prepared by adding and mixing fine silica powder to binder resin particles.

On the other hand, in order to form an image with excellent fine line reproducibility, the toner is required to have excellent triboelectric charging properties, and in particular, the triboelectric charging distribution is required to be narrow and sharp.

From this point of view, conventionally, a technique has been proposed in which a charge control agent is contained in binder resin particles constituting a toner.

[Problem that the invention seeks to solve]

However, in toners mixed with fine silica powder, the fine silica powder is quite hard, so when cleaning the residual toner with a cleaning blade placed in contact with the latent image carrier with a large pressure contact force, the fine silica powder is caught between the cleaning blade and the latent image carrier, and the surface of the latent image carrier is rubbed, resulting in a problem in that the surface of the latent image carrier is likely to be damaged. When the surface of the latent image carrier is damaged in this way, fine silica powder, etc. is embedded in the wound and cannot be cleaned. There is a problem in that this adheres and is fixed, resulting in black spot-like stains (black spots) on the image.

In addition, especially in toners containing a charge control agent in the binder resin particles, the soft and highly adhesive charge control agent is easily released from the binder resin particles and adheres to the surface of the latent image carrier, causing the image As the formation of the toner is repeated, a filming phenomenon occurs in which the charge control agent adheres to the surface of the developer transport carrier and forms a film, and as a result, the ability of the developer transport carrier to transport the toner deteriorates and the toner is transported to the development area. There is a problem that the amount of toner gradually decreases, resulting in a decrease in image density.

In addition, toner containing fine silica powder has a large electrostatic adhesion force to the latent image carrier.
There is a problem in that the transfer rate of a toner image formed by development onto a transfer material is generally low, resulting in a decrease in image density.

Particularly, when the toner is used as a one-component developer, since the toner contains magnetic powder, the weight of the toner increases, resulting in a further reduction in the transfer rate.

The present invention has been made based on the above-mentioned circumstances, and is capable of improving developability and cleaning performance, and can stably produce images with excellent fine line reproducibility over a large number of times without the occurrence of black spots. An object of the present invention is to provide a toner for developing an electrostatic image that can be formed into an electrostatic image.

[Means for solving problems]

The electrostatic image developing toner of the present invention comprises binder resin particles in which a charge control agent is dispersed in a binder resin, inorganic fine particles, and organic fine particles having a smaller diameter than the binder resin particles. It is characterized by being

[Function and effect of the invention]

According to the present invention, since the binder resin particles contain a charge control agent dispersed therein, the triboelectric charging properties of the toner are stabilized, and the triboelectric charging distribution is narrow and sharp, resulting in a marked improvement in fine line reproducibility. Moreover, since inorganic fine particles and organic fine particles are contained together with the binder resin particles, good developing performance is exhibited due to the effect of improving the fluidity of the toner by the inorganic fine particles, and the so-called lubricating effect is achieved by the organic fine particles. As a result of this action, the physical adhesion of the toner to the latent image carrier is weakened, and the residual toner can be easily cleaned. Therefore, it is possible to achieve good cleaning with a small pressure contact force of the cleaning blade against the latent image carrier, and as a result, damage to the surface of the latent image carrier due to inorganic fine particles can be prevented, and there is no black spot. Images can be stably formed many times.

The so-called lubricating action of the organic fine particles suppresses the occurrence of the filming phenomenon of the developer transport carrier due to toner substances, and the organic fine particles also provide appropriate polishing performance, which temporarily controls the charge on the developer transport carrier. Even if the agent adheres, it can be easily removed.
As a result, even when an image is formed many times, the ability of the developer transport carrier to transport the toner to the development/image area is stable, and a decrease in image density does not occur.

[Specific structure of the invention]

In the present invention, electrostatic images are produced by using as essential components binder resin particles in which a charge control agent is dispersed and contained in the binder resin, inorganic fine particles, and organic fine particles smaller in diameter than the binder resin particles. Consists of developing toner. The electrostatic image developing toner of the present invention can be applied to either a one-component developer not mixed with a carrier or a two-component developer mixed with a carrier.

The organic fine particles have a smaller diameter than the binder resin particles, and for example, the average diameter of secondary particles (particles separated into individual unit particles) is preferably 0.01 to 5 IIM, particularly 0.1 The thickness is preferably about 2.0 um. When the average diameter of the organic fine particles is too large, the fluidity of the toner decreases and the amount of toner conveyed to the development area becomes insufficient, which tends to cause a decrease in image density. On the other hand, if the average diameter of the organic fine particles is too small, sufficient leaning properties cannot be obtained.

The proportion of organic fine particles is 0.01 to 3% by weight of the entire toner.
is preferable, and particularly preferably 0.1 to 2% by weight.

When the proportion of organic fine particles is too small, the fluidity of the toner decreases and the amount of toner conveyed to the development area becomes insufficient, which tends to cause a decrease in image density. On the other hand, if the average diameter of the organic fine particles is too large, sufficient leaning properties cannot be obtained.

The organic substance for forming the organic fine particles is not particularly limited, but vinyl polymers are preferred because they are relatively hard and provide appropriate polishing performance.

Such vinyl polymers can be produced by various polymerization methods such as emulsion polymerization and suspension polymerization, but the emulsion polymerization method is preferred because small-diameter, spherical organic fine particles can be efficiently obtained. In particular, in systems where the monomer itself for obtaining the vinyl polymer has an emulsifying effect, it is preferable to obtain the vinyl polymer by emulsion polymerization without using an emulsifier.

Examples of the vinyl polymer include acrylic polymers, styrene polymers, vinyl group-containing fluororesins, and among them, acrylic polymers are preferred.

Acrylic polymers are homopolymers or copolymers obtained by polymerizing monomers mainly selected from acrylic acid, acrylic acid esters, methacrylic acid, and methacrylic esters.

Acrylic monomers used to obtain such acrylic polymers include acrylic acid, methyl acrylate,
Ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, lauryl acrylate, 2-ethylhexy/lz acrylate, stearyl acrylate, 2-acrylate Chlorethyl, pheninope acrylate α-methyl chloroacrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, lauryl methacrylate , 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and the like.

Among the acrylic polymers, polymethyl methacrylate is particularly preferred. With polymethyl methacrylate, uniform and small-diameter organic fine particles can be easily obtained,
In addition, it is possible to obtain a suitable polishing performance and suitably weaken the physical adhesion of the toner to the latent image bearing member or the developer transporting carrier, so that an excellent effect can be exhibited.

Furthermore, since there is no risk of inhibiting the triboelectric charging properties of the toner, stable developing performance can be obtained.

The acrylic polymer may be copolymerized with other monomers, if necessary.

In this case, it is preferable to use the acrylic monomer in a proportion of 50% by weight or more in the monomer composition. Such other monomers include styrene, 0-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-nitylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene. , p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p-methoxystyrene, p - Styrenic monomers such as phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene,
Acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide; Vinyl esters such as vinyl acetate, vinyl acetate, and vinyl benzoate; Vinyl ethers such as vinyl methyl ether and vinyl ethyl ether; Vinyl ketones such as vinyl methyl ketone; Dienes such as butadiene and isoprene; unsaturated carboxylic acids such as maleic acid and fumaric acid; and others.

The inorganic fine particles preferably have an average diameter of secondary particles (particles separated into individual unit particles) of 2 μm or less, particularly preferably 1 μm or less. When the average diameter of the inorganic fine particles is too large, the surface of the latent image carrier is likely to be damaged.

The proportion of the inorganic fine particles is preferably 0.05 to 2.0% by weight, particularly preferably 0.1 to 1.0% by weight, based on the total toner. When the proportion of inorganic fine particles is too small, the fluidity of the toner decreases, while when the proportion is too large, the surface of the latent image carrier is likely to be damaged.

The constituent materials of the inorganic fine particles are not particularly limited, but include, for example, oxides such as silica, titanium oxide, aluminum oxide, zirconium oxide, barium titanate, lead titanate, and barium carbonate; nitrides such as silicon nitride and boron nitride; and carbide. Carbides such as silicon, aluminum carbide, titanium carbide;
Others can be mentioned. These inorganic fine particles may be surface-treated.

Particularly preferred are silica fine particles or surface-treated silica fine particles. As the surface treatment agent, for example, a silane coupling agent, a titanium coupling agent, etc. can be used. The surface-treated silica fine particles are highly stable against environmental changes such as temperature and humidity, so that the environmental dependence of the triboelectric charging property of the toner can be suppressed to a small level.

Two or more types of inorganic fine particles may be used in combination. In this case, it is preferable to always use silica fine particles or surface-treated silica fine particles.

The above organic fine particles and inorganic fine particles are preferably used by being added to and mixed with the binder resin particles from the outside. Specifically, by mixing binder resin particles, organic fine particles, and inorganic fine particles using a mixing device such as a V-type blender, organic fine particles and inorganic fine particles are present on the surface of the binder resin particles. It is preferable to let

The binder resin particles contain a charge control agent dispersed as an essential component in the binder resin, and optionally contain a magnetic material, a colorant, an offset inhibitor, and the like.

Charge control agents include electron-accepting compounds such as azo metal complexes, salicylic acid-based metal complexes, and naphthoic acid-based metal complexes, or electron-donating compounds such as nigrosine dyes, amine compounds, and quaternary ammonium salt compounds. Preferably selected.

The proportion of the charge control agent is 0.5 to 5% by weight of the binder resin particles.
is preferable, particularly preferably 1 to 3% by weight.

When the proportion of the charge control agent is excessive, the amount of charge becomes excessive and the image density decreases. On the other hand, if the proportion of the charge control agent is too small, sufficient triboelectric charging properties cannot be obtained.

As the azo metal complex, for example, one represented by the following formula 1 is preferable.

- Formula 1 (where X and X12 represent hydrogen, a lower alkyl group, a lower alkoxy group, a nitro group, or a halogen,
n4 represents l or 2, m represents an integer from 1 to 3, m
, n and Xll, X12 may be the same or different, M represents chromium, cobalt or iron, and Y, - represents a counter ion. ) Specifically, those shown by the following structural formulas can be mentioned, but are not limited thereto.

Structural formula Δ-1 Structural formula A-2 Structural formula A-:3 Structural formula-4 Structural formula A-5 Structural formula A-6 As the salicylic acid metal complex, a metal complex of salicylic acid or alkyl salicylic acid is preferable.

Among the metal complexes of alkyl salicylic acid, especially those with 5 carbon atoms
Those having the following lower alkyl groups are preferred. Also,
As the metal of the metal complex, chromium is preferable. Specifically, those represented by the following structural formula can be mentioned, but the metal complex is not limited thereto.

As the naphthoic acid metal complex, for example, one represented by the following formula 2 is preferable.

- Formula 2 (However, R21 represents a benzene ring or a cyclohexene ring which may have an alkyl group having 4 to 9 carbon atoms, and R
o and R23 represent hydrogen, an alkyl group having 4 to 9 carbon atoms, or a substituent which may form a benzene ring or a cyclohexene ring which may have an alkyl group having 4 to 9 carbon atoms; M is chromium; , represents cobalt or iron, Y
21. represents a counter ion. ) The naphthoic acid metal complex represented by formula 2 is a metal complex of compounds A and B in formula 2,
If compounds A and B are the same, a symmetrical metal complex will be obtained, and if compounds A and B are different, an asymmetrical metal complex will be formed.

Compound A used to form the naphthoic acid metal complex represented by formula 2 is 2-hydroxy-3-naphthoic acid, alkyl (4 to 9 carbon atoms)-2-hydroxy-3-naphthoic acid, , 5, 6.7.8-Tetrahydro-2-hydroxy-3-naphthoic acid, alkyl (
Carbon number 4-9)-5,6゜7.8-tetrahydro-2
-hydroxy-3-naphthoic acid, l-hydroxy-2-
Examples include naphthoic acid, alkyl (4 to 9 carbon atoms)-1-hydroxy-2-naphthoic acid, and 5.6.7.8-tetrahydro-1-hydroxy-2-naphthoic acid. In addition, as compound B, alkyl (carbon number 4 to
9) Salicylic acid, 3,5-dialkyl (4 to 9 carbon atoms)
Salicylic acid, 2-hydroxy-3-naphthoic acid, alkyl (4-9 carbon atoms)-2-hydroxy-3-naphthoic acid, 5.6,7.8-tetrahydro-2-hydroxy-
3-naphthoic acid, alkyl (4 to 9 carbon atoms) -5,6
, 7,8-tetrahydro-2-hydroxy-3-naphthoic acid, ■-hydroxy-2-naphthoic acid, alkyl (
C4-9)-1-hydroxy-2-naphthoic acid, 5
．． 6,7.8-tetrahydro-1-hydroxy-2-
Examples include naphthoic acid.

Specific examples of naphthoic acid metal complexes include those represented by the following structural formula, but are not limited thereto.

Nigrosine dye is a general term for alcohol soluble nigrosine dyes and basic nigrosine derivatives.
Specifically, for example, "Nigrosine" (manufactured by Ikeda Chemical Co., Ltd.),
"Orient Spirit Black ABJ, r Orient Spirit Black SBJ (manufactured by Orient Chemical Co., Ltd.), "Spirit Black Nα85
0”, “Spirit Black Nα900”, “Spirit Black Nα920”, “Spirit Black Nα980J (manufactured by Sumitomo Chemical Co., Ltd.), “Nigrosine
Nigrosine Base NBJ (manufactured by William Limited), Nigrosine Base GBJ
(manufactured by Falpenfabriken Bayer Akchengesellschaft), "Nigrosine Base LKJ"
(manufactured by BAZUF), "Nigrosine Base Ex",
Examples include "Nigrosine Base SO" (manufactured by Orient Chemical Co., Ltd.).

Examples of the amine compound include, but are not limited to, those represented by the following structural formula.

Structural formula D-1 Structural formula D-2 Structural formula D-3 Structural formula D-4 Examples of quaternary ammonium salt compounds include the following -
The one represented by Formula 3 can be preferably used.

General formula 3 (However, R3+ is an alkyl group having 1 to 8 carbon atoms, R52
and Rff3 each represent an alkyl group having 1 to 18 carbon atoms, R5 represents an alkyl group having 1 to 8 carbon atoms or a benzyl group, and Y31e represents a counter ion. ) Specific examples of quaternary ammonium salt compounds include those represented by the following structural formula, but are not limited thereto.

Structural Formula E-1 Structural Formula E-2 Structural Formula E-3 Structural Formula E-4 Structural Formula E-5 The binder resin is not particularly limited, and various resins can be used. Specifically, styrene resins, acrylic resins, styrene-acrylic copolymer resins, epoxy resins, polyester resins, etc. can be mentioned.

These resins may be used in combination.

The styrene/acrylic copolymer resin used as the binder resin is a resin made of a copolymer of a styrene monomer and an acrylic monomer. Styrene monomers include styrene, 0-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-methylstyrene, -tert-butylstyrene, p-n-
hexylstyrene, p-n-octylstyrene, p-n
-nonylstyrene, p n-decylstyrene, p-n-
Examples include dodecylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, and 3°4-dichlorostyrene.

Acrylic monomers include acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, and n-acrylate.
-Octyl, dodecyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, methacrylate Propyl acid, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylamino methacrylate Mention may be made of ethyl, acrylonitrile, methacrylonitrile, acrylamide, and others.

Magnetic substances include substances that are strongly magnetized in the direction of a magnetic field, such as metals or alloys that exhibit ferromagnetism such as iron, ferrite, and magnetite, such as iron, nickel, and cobalt, compounds containing these elements, and ferromagnetic elements. Alloys that do not contain manganese and copper but become ferromagnetic through appropriate heat treatment, such as manganese-copper-aluminum, manganese-copper-tin, etc. Alloys called Heusler alloys that contain manganese and copper, dioxide Chromium, and others can be mentioned. The average particle size of the magnetic material is 0.1
It is preferable that it is uniformly dispersed and contained in the form of a fine powder of ~1 p. When the toner is used as a -component developer, the content of the magnetic material is preferably 20 to 80% by weight, particularly preferably 30 to 70% by weight, based on the total toner.

Examples of colorants include carbon black, nigrosine dye, aniline blue, calco oil blue, chrome yellow, ultramarine blue, Denipon oil red, quinoline yellow, methylene blue chloride, phthalocyanine blue, malachite green offsalate,
Mention may be made of lamp black, rose bengal, mixtures thereof, and others.

Examples of anti-offset agents include low softening point polyolefins, high melting point paraffin waxes, silicone resins, fatty acid esters or partially saponified products thereof, fatty acid amide compounds, higher alcohols, and the like.

〔Example〕

Examples of the present invention will be specifically described below, but the present invention is not limited to these Examples.

Example 1 Styrene/acrylic copolymer resin (monomer composition: 65 parts by weight of styrene, 5 parts by weight of α-methylstyrene, 10 parts by weight of methyl methacrylate, 1 part by weight of n-butyl acrylate)
8 parts by weight, 2 parts by weight of divinylbenzene) 46 parts by weight,
Magnetite rE3L-100J (manufactured by Titanium Kogyo Co., Ltd.) 5
0 parts by weight and 2 parts by weight of the charge control agent (naphthoic acid metal complex represented by the above structural formula C-3), kneaded, crushed, and classified to obtain a material with an average particle size of 12Q. A binder resin particle powder was obtained.

Next, using Nauta and Turbular, inorganic fine particle powder r'R-972J (hydrophobic silica fine particles, average diameter of -order particles = 0. Old 6μ scrap 1 manufactured by Nippon Aerosil Co., Ltd.) is added to the binder resin particle powder. 0.4% by weight, organic fine particles powder (polymethyl methacrylate fine particles.

The toner T1 according to the present invention was manufactured by mixing and stirring the following particles (average diameter of the second particle=0.511 M) at a ratio of 0.4% by weight.

Using this toner TI, an electrophotographic copying machine rU-Bix 1200J (Konishi When a photocopying test was carried out 100,000 times under normal conditions using a modified machine (manufactured by Rokusha Kogyo Co., Ltd.), the cleaning performance was good and no black spots were observed in the copied images until the end. In addition, no filming phenomenon of the developer transport carrier was observed until the end, and the toner transport performance was stable and an image with sufficient image density could be formed. Furthermore, the triboelectric charge distribution was narrow and sharp, and an image with excellent fine line reproducibility could be formed to the end.

FIG. 1 shows actual measurement data of fine line reproducibility. In the figure, curve T1 is data for Example 1, and curves t1 and t2 are data for Comparative Examples 1 and 2, which will be described later. Note that M, T, and F refer to response functions, and this M,
A value of T and F of 30% or more is sufficient for practical use.

As can be understood from the results shown in FIG. 1, the toner T1 according to the present invention has extremely excellent fine line reproducibility.

Comparative Example 1 For comparison, a comparative toner t1 was produced in the same manner as in Example 1 except that the charge control agent was not used, and the same photo-photography test as in Example 1 was conducted using this toner t1. After 70,000 times, black spots occurred due to poor cleaning. Further, since the triboelectric charging property of the toner is unstable, the toner transportability deteriorates after 50,000 times, and the amount of toner transported to the development area becomes less than half of the initial amount of image formation. Further, when examining the fine line reproducibility, as shown by the curve tl in FIG.
was inferior to

Comparative Example 2 For comparison, a comparative toner t2 was prepared in the same manner as in Example 1 except that organic fine particles and inorganic fine particles were not used.
When the toner t2 was used to conduct the same photo-photography test as in Example 1, it was found that the charge control agent transferred and adhered to the surface of the latent image carrier, contaminating the surface of the latent image carrier. As a result, the potential of the latent image carrier gradually increased, and from around 5,000 times, fog started to appear on the entire copied image.

Further, when the fine line reproducibility was examined, as shown by the curve t2 in FIG. 1, it was considerably inferior to the toner T1 according to the present invention.

Example 2 Toner T2 according to the present invention was produced in the same manner as in Example 1, except that the charge control agent was changed to 2 parts by weight of the nigrosine dye (Grosine SO, manufactured by Orient Co., Ltd.).

Using this toner T2, an electrophotographic copying machine rU-Bix 1200J (Konishi When a photographing test was conducted 50,000 times under normal conditions using a modified machine (manufactured by Rokusha Kogyo Co., Ltd.), the cleaning performance was good and no black spots were observed until the end.

Furthermore, the toner transportability was stable, and an image with sufficient image density could be formed until the end. Furthermore, the triboelectric charge distribution was narrow and sharp, and an image with excellent fine line reproducibility could be formed to the end.

Example 3 Toner T3 according to the present invention was produced in the same manner as in Example 1, except that the charge control agent was changed to 2 parts by weight of a salicylic acid-based metal complex (the salicylic acid-based metal complex represented by the structural formula B-3). Manufactured.

Using this toner T3, 50,0
When the actual photographing test was carried out 00 times, the cleaning performance was good and no black spots were observed until the end. Furthermore, the toner transportability was stable, and an image with sufficient image density could be formed until the end. Furthermore, the triboelectric charge distribution was narrow and sharp, and an image with excellent fine line reproducibility could be formed to the end.

Example 4 The present invention was carried out in the same manner as in Example 2, except that the charge control agent was changed to 2 parts by weight of a quaternary ammonium salt compound (a quaternary ammonium salt compound represented by the above structural formula E-2). Toner T4 according to the invention was manufactured.

Using this toner T4, 50,0
When the actual photographing test was carried out 00 times, the cleaning performance was good and no black spots were observed until the end. Furthermore, the toner transportability was stable, and an image with sufficient image density could be formed until the end. Furthermore, the triboelectric charge distribution was narrow and sharp, and an image with excellent fine line reproducibility could be formed to the end.

Comparative Example 3 For comparison, a comparative toner t3 was produced in the same manner as in Example 4 except that the charge control agent, the sensitive particles, and the inorganic particles were not used. When I did a live-action test, it was 10.0.
After 00 times, the image density becomes 1.0 (relative density) or less,
Also, after 2,000 times, black spots occurred due to poor cleaning. Further, since the triboelectric charging property of the toner is unstable, fogging started to occur in the copied image after 10,000 times.

Example 5 Styrene/acrylic copolymer resin (monomer composition: 65 parts by weight of styrene, 5 parts by weight of α-methylstyrene, 10 parts by weight of methyl methacrylate, 1 part by weight of n-butyl acrylate)
8 parts by weight, 2 parts by weight of divinylbenzene), 10 parts by weight of carbon black "Mogul LJ (manufactured by Capot), and a charge control agent (naphthoic acid metal complex represented by the above structural formula C-3) 2 Mix parts by weight,
The mixture was milled, pulverized, and classified to obtain binder resin particle powder with an average particle size of 12Jr11.

Next, inorganic fine particle powder rR-9724 (hydrophobic silica fine particles, average diameter of secondary particles = 0.016 μm, manufactured by Nippon Aerosil Co., Ltd.) was added to the binder resin particle powder using Nauta and Turbiniller. 4% by weight, organic fine particle powder (polymethyl methacrylate fine particles.

Toner T5 according to the present invention was manufactured by mixing and stirring the following particles (average diameter of secondary particles = 0.5 μm 1) at a ratio of 0.4% by weight.

A two-component developer was prepared by mixing 3 parts by weight of this toner T5 and 97 parts by weight of a carrier made of ferrite powder rF-100J (manufactured by Nippon Tetsuko Co., Ltd.) having an average diameter of 12 On.

Using this two-component developer, an electrophotographic copying machine rU-Bix 1800J for the two-component developer is equipped with a latent image carrier made of a selenium/tellurium photoreceptor and equipped with a cleaning device having a cleaning blade. (manufactured by Konishiroku Photo Industry Co., Ltd.) When a photographic photographing test was conducted 100,000 times under normal conditions using a modified machine, the cleaning performance was good and no black spots were observed until the end. Furthermore, the toner transportability was stable, and an image with sufficient image density could be formed until the end. In addition, the triboelectric charge distribution is narrow and sharp, and the image has excellent fine line reproducibility until the end (M, T, F, values of 10 lines/mm are 30%
above) was able to be formed.

Example 6 The present invention was carried out in the same manner as in Example 5, except that the charge control agent was changed to 3 parts by weight of a quaternary ammonium salt compound (a quaternary ammonium salt compound represented by the above structural formula E-3). Toner T6 according to the invention was manufactured.

A two-component developer was prepared using this toner T6 in the same manner as in Example 5, and a 100,000-time photographic test was conducted in the same manner as in Example 5 using this two-component developer, and the cleaning performance was good. However, no black spots were observed until the end.

Furthermore, the toner transportability was stable, and an image with sufficient image density could be formed until the end. Furthermore, the triboelectric charge distribution was narrow and sharp, and an image with excellent fine line reproducibility could be formed to the end.

Comparative Example 4 For comparison, a comparative toner t4 was prepared in the same manner as in Example 5 except that organic fine particles and inorganic fine particles were not used.
A two-component developer was prepared using this toner t4, and an actual photographic test was conducted using this two-component developer in the same manner as in Example 5. After 10,000 times, the toner transportability was found to be poor. As a result, white streak-like undeveloped areas appeared on the copied image.

Comparative Example 5 For comparison, a comparative toner t5 was produced in the same manner as in Example 5 except that no charge control agent was used, and a two-component developer was prepared using this toner t5. When a live photo test was carried out using the toner in the same manner as in Example 5, the result was 50.00% due to the unstable triboelectric charging properties of the toner.
After the 0th time, the image density started to decrease.

Comparative Example 6 For comparison, a comparative toner t6 was produced in the same manner as in Example 6 except that the charge control agent was not used, and a two-component developer was prepared using this toner t6. When a live photo test was conducted using the toner in the same manner as in Example 6, the result was 50.00 because the triboelectric charging properties of the toner were unstable.
After the 0th time, the image density started to decrease.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing actual measurement data of fine line reproducibility in a real-photograph test.

Claims (1)

[Scope of Claims] 1) Comprising binder resin particles in which a charge control agent is dispersed in a binder resin, inorganic fine particles, and organic fine particles having a smaller diameter than the binder resin particles. An electrostatic image developing toner characterized by: 2) an azo metal complex, a salicylic acid metal complex, a naphthoic acid metal complex, in which the charge control agent is an electron-accepting compound;
The toner for electrostatic image development according to claim 1, wherein the toner is selected from nigrosine dyes, amine compounds, and quaternary ammonium salt compounds, which are electron-donating compounds. 3) For electrostatic image development according to claim 1 or 2, wherein the average diameter of the primary particles of the organic fine particles is 3 μm or less and larger than the average diameter of the primary particles of the inorganic fine particles. toner. 4) The toner for electrostatic image development according to any one of claims 1 to 3, wherein the inorganic fine particles are made of silica or surface-treated silica. 5) The toner for electrostatic image development according to any one of claims 1 to 4, wherein the organic fine particles are made of a vinyl polymer. 6) The toner for electrostatic image development according to claim 5, wherein the vinyl polymer is an acrylic polymer. 7) The toner for electrostatic image development according to claim 6, wherein the acrylic polymer is polymethyl methacrylate.