JPH0727284B2 - Toner for electrostatic image development - Google Patents

Description

TECHNICAL FIELD The present invention relates to a toner for developing an electrostatic latent image such as electrophotography and electrostatic recording.

BACKGROUND ART Conventionally, as an electrophotographic method, various methods are described in U.S. Pat.No. 2,297,691, Japanese Patent Publication No. 42-23910, and Japanese Patent Publication No. 43-24748, but in short, they are photoconductive. A uniform electrostatic charge is applied onto the insulating layer, and an electrostatic latent image is formed by irradiating the insulating layer with a light image,
Then, the latent image is developed and visualized by fine powder called toner in the art, and if necessary, the powder image is transferred to paper or the like, and then fixed by heating, pressurizing, or solvent vapor.

As a developing method applied to these electrophotographic methods,
It is roughly classified into a dry development method and a wet development method. The former is further divided into a method of using a two-component developer and a method of using a one-component developer. Depending on the type of carrier that carries the toner, the two-component developing method
Magnet brush method using iron powder carrier, beads,
There are a cascade method using a carrier and a fur brush method using a fur.

The one-component developing method includes a powder cloud method in which toner particles are sprayed, a contact developing method in which toner particles are directly brought into contact with an electrostatic latent image surface (contact development, or toner development). (Also referred to as development), a jumping development method in which toner particles are not directly contacted with the electrostatic latent image surface, but the toner particles are charged and fly toward the latent image surface by the electric field of the electrostatic latent image, magnetic conductivity. There is a magnetic dry method in which toner is brought into contact with the electrostatic latent image surface to develop the toner.

As a toner applied to these developing methods, a fine powder in which a dye or a pigment is dispersed in a natural or synthetic resin is conventionally used. For example, particles in which a colorant is dispersed in a binder resin such as polystyrene and finely pulverized to about 1 to 30 μm are used as a toner. A magnetic toner containing magnetic particles such as magnetite is used. In the case of a system using a so-called two-component developer, the toner is usually used by being mixed with carrier particles such as glass beads and iron powder. Further, the toner is given a positive or negative charge depending on the magnetism of the electrostatic latent image to be developed.

By the way, in the conventional toner as described above, it was not possible to obtain preferable chargeability by using the binder resin used alone, so that a dye, a pigment, or a tribocontrol agent that imparts the desired chargeability to the binder resin is obtained. Is added. Nowadays, it is assumed that the dye is a nigrosine-based dye when it is applied with a positive charge to the toner, and when it is applied with a negative charge to the toner, JP-B-45-26478 and JP-B-55. There are metal-containing compounds disclosed in Japanese Patent Publication No. 42752 and the like. It can be judged that these compounds have particularly excellent properties among the conventionally proposed charge control substances in terms of the performance of imparting electric charge to toner particles.

However, as electrophotography and electrostatic recording media become more personalized, faster, and multifunctional, they have better environmental stability, better durability stability, higher density, and less fog. There is a need for toners that give images.

With such miniaturization and personalization, toner has been used more severely under high temperature and high humidity in Southeast Asia or under low temperature and low humidity in North America. However, it must provide stable and high-quality images.

Further, with the increase in the speed of the medium in the previous term, the toner is required to endure a large amount of use at one time or continuous use for a long time and provide a stable high-quality image.

OBJECT OF THE INVENTION It is an object of the present invention to provide an electrostatic charge image developing toner which gives a stable image regardless of humidity.

Still another object is to provide an electrostatic charge image developing toner which gives a stable image independent of temperature.

Still another object is to provide a toner for developing an electrostatic charge image, which has excellent durability and always gives a stable image even when it is continuously used for a long period of time.

Still another object is to provide a toner for developing an electrostatic charge image, which provides high image quality with excellent resolution and gradation reproducibility.

Still another object is to provide a toner that always has a high density and gives a fog-free image.

SUMMARY OF THE INVENTION As a result of intensive studies conducted by the present inventors for the above purpose, the dispersibility of a monoazo compound metal complex having a specific ligand in a binder resin has a close relationship with the gel-like properties of the binder resin. Furthermore, it was found that the above-mentioned dispersibility is extremely good in a specific gel content of the binder resin.

The toner for developing an electrostatic image of the present invention is based on such knowledge, and more specifically, the monoazo compound metal complex 0.1 to 10 represented by the following general formula (1) is added to 100 parts by weight of the resin component. The binder resin is characterized by containing 10 parts by weight of gel content of the binder resin.

[In the formula, R ¹ represents alkyl, alkenyl, aralkyl or aryl having 5 to 18 carbon atoms, and R ² represents hydrogen, halogen, nitro, cyano, or 1 to 18 carbon atoms.
Number of alkoxy, or represents a carboxy ester, R ³ represents hydrogen, halogen, nitro, cyano, carboxy ester, alkyl having 1 to 18 carbon atoms, alkenyl, aralkyl, aryl or alkoxy, l is 1 to 4 Represents an integer, and n and k are (n + k) =
1 to 4 and represents 0 or a positive integer, and m is n + k + m
Represents an integer of 4 and R ¹ , R ² and R ³ are the same or different substituents, and when l, m and (n + k) are integers of 2 or more, a plurality of
R ¹ , R ² or R ³ are respectively the same or different substituents, X represents —O—, —COO— or —S—, and Y represents —O—, —COO—, —S. - or -NR ⁴ - (wherein, R ⁴
Represents an alkyl having 1 to 4 carbon atoms. ), M represents Cr, Co or Fe, and A represents hydrogen, Na, K, ammonium, or organic ammonium. According to the knowledge of the present inventors, the monoazo compound metal complex represented by the general formula (1) is thermally and temporally stable in itself, and has a low hygroscopic property. In this case, not only is it a high-quality charge control agent that gives a developer having excellent electrophotographic properties even under low humidity, but it also exhibits extremely good dispersibility with respect to a binder resin having a specific glucontent. This is because when the above-mentioned monoazo compound metal complex (having a group having a relatively large number of carbon atoms as R ¹ ) is used together with a binder resin containing a specific amount of gel, the metal complex is subjected to a suitable shearing, It is presumed that the dispersion in the coating resin is very good.

In the toner of the present invention, the characteristics of the charge control agent itself and the good dispersibility of the charge control agent in the binder resin are combined, so that the toner of the present invention can be used between toner particles or with toner. The amount of triboelectrification between carriers and between a toner and a toner carrier such as a sleeve in the case of one-component development is stable, and the triboelectrification amount distribution is sharp and uniform, which is suitable for the developing system used. The toner becomes controllable.

Therefore, the toner of the present invention can be stably negatively charged in any environment and can provide a stable image for a long period of time.

Hereinafter, the present invention will be described in more detail. In the following description, “part” and “%” representing the quantitative ratio are based on weight unless otherwise specified.

DETAILED DESCRIPTION OF THE INVENTION The toner for developing an electrostatic image of the present invention contains, as essential components, a metal complex of a monoad compound represented by the following general formula (1) and a binder resin having a specific gel content.

In the above general formula (1), R1 represents an alkyl, alkenyl, aralkyl or aryl group having 5 to 18 carbon atoms, which is an alkyl group having 5 to 10 carbon atoms or an alkenyl group having 5 to 10 carbon atoms. It is preferable.

R ² is hydrogen, halogen, nitro, cyan, carbon number 1-18
Represents an alkoxy group or a carboxyester group, but is preferably a hydrogen atom, a halogen atom, a nitro group or an alkoxy group having 1 to 4 carbon atoms.

R ³ represents hydrogen, halogen, nitro, cyano, carboxyester, an alkyl, alkenyl, aralkyl, aryl or alkoxy group having 1 to 18 carbon atoms, but hydrogen, halogen, nitro, alkyl having 1 to 10 carbon atoms A group, an alkenyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms is preferable.

l represents an integer of 1 to 4, n and k are (n + k)
= 0 to a positive integer of 1 to 4, m is n + k +
It represents an integer such that m = 4, 1 is preferably 1 or 2, (n + k) is preferably 1 to 3, and m is preferably 1 or 2.

R ¹ , R ² and R ³ are the same or different substituents.

When l, m and (n + k) are integers of 2 or more,
A plurality of R ¹ , R ^{2 and} R ³ are the same or different substituents, respectively.

X represents -O-, -COO- or -S-, but -O-
Alternatively, it is preferably —COO—.

Y is —O—, —COO—, —S— or —MR ⁴ — (wherein R ⁴
Represents an alkyl group having 1 to 4 carbon atoms. ), But is preferably —O— or —COO—.

M represents Cr, Co or Fe.

A represents hydrogen, Na, K, ammonium or organic ammonium, preferably hydrogen, Na, K or organic ammonium.

The monoazo compound metal complex (1) used in the toner of the present invention is obtained by treating a metallizable azo compound with a metal-imparting agent by a known method, and the counter ion is changed depending on the subsequent treatment conditions. be able to.

For example, 4-t-amyl-6-nitro-2-aminophenol is diazotized, β-naphthol is coupled, treated with an inorganic chromium salt, and then filtered at a pH of 3 or less, and the precipitate is separated at pH 6 to 7 positions. The complex compound represented by the following formula (2) is obtained by washing until it becomes.

Other specific examples of the compound of the general formula (1) used in the present invention include those represented by the following formula (3) or (4), which are synthesized by the same method as the compound of the above formula (2). To be done.

As a method of incorporating the metal complex compound represented by the general formula (1) into the developer, there is a method of adding it inside the developer. The amount of the compound (1) used depends on the kind of the binder resin,
The presence or absence of additives used as necessary, which is determined by the toner production method including the dispersion method, is not uniquely limited, but preferably the binder resin 100
It is used in the range of 0.1 to 10 parts (more preferably 0.5 to 5 parts) per part.

Further, conventionally known charge control agents, cross-linking agents, colorants and the like can also be used in combination with the compound represented by the formula (1).

Further, in this case, when the gel content of the binder resin of the toner containing the binder resin and the compound (1) is 10 to 70 wt%, preferably 10 to 60 wt%, more preferably 10 to 50 wt%, The compound represented by (1) is well dispersed in the toner, and the charge control action of the compound (1) is exhibited well.

When the gel content is less than 10 wt%, the dispersion of the compound represented by the formula (1) is poor, the toner particles are dispersed, the durability is reduced, and the image density is reduced or fogging occurs during use. There are drawbacks. Further, when the gel content exceeds 70 wt%, there are problems in production such as improper fixing and unsuccessful kneading when a toner is obtained by a kneading method.

Here, the gel content in the present invention is the ratio of the polymer portion in the binder resin which becomes insoluble in the solvent. In the present invention, the value measured as follows is used as the gel content.

That is, a certain amount of toner (W ₁ g) is weighed and G-
Soxhlet extractor is used with the glass filter of No. 3, soluble components in the polymer are removed by the solvent, and the sample remaining unextracted is dried and weighed (W ₂ g).

If the weight of the inorganic solid components such as magnetic substance and silica contained in the toner is W ₃ , the gel content is {(W ₂ −W ₃ ) /
It is calculated as (W ₁ −W ₃ )} × 100 (%).

Toluene is suitable as the solvent used above, and extraction is performed for about 50 hours here.

The toner of the present invention has a molecular weight of the tetarahydrofuran-soluble component of Wn (number average molecular weight) of 2000 to 20,000, Mw (weight average molecular weight) of 50,000 to 5,000,000, and further 50,000 to 3,000,0.
It is preferably 00.

In the present invention, the values of Mn and Mw are gel permeation
The value calculated from the value measured by chromatography is used. The measurement conditions were as follows: Tetrahydrofuran was used as a solvent at a flow rate of 1 ml / min at a temperature of 25 ° C and a sample concentration of 8
Measure by injecting 0.5 ml of a sample solution of tetrahydrofuran at mg / ml. As the column, a plurality of commercially available polystyrene gel columns are preferably combined in order to accurately measure the molecular weight region of 10 ³ to 2 × 10 ⁶ , for example, μ-styrogel 500, 10 manufactured by waters. ^3, 10 ^4, 10 ⁵ combination or, manufactured by Showa Denko KK of shodex combination of a-802, 803, 804, 805 is good.

In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of the calibration curve prepared from several kinds of monodisperse polystyrene standard samples and the count number. The standard polystyrene sample for preparing the calibration curve is, for example, Pressure Cheical Co. or Toray Soda Kogyo Co., Ltd. and has a molecular weight of 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10.
⁴ , 5.1 x 10 ⁴ , 1.1 x 10 ⁵ , 3.9 x 10 ⁵ , 8.6 x 10 ⁵ , 2 x 1
It is suitable to use a standard polystyrene sample of 0 ⁶ , 4.48 × 10 ⁶ and at least about 10 points. An R1 (refractive index) detector is used as the outstanding device.

Further, the acid value of the soluble component of the toner of the present invention is preferably from 1 to 60, more preferably from 5 to 40.

When the soluble component of the toner has an acid value, the charge control action of the compound represented by the formula (1) is most effectively exerted, so that the toner exhibits a good negative chargeability and a better developability. It can be shown to give a high quality image.

In the present invention, the acid value is a numerical value represented by mg of potassium hydroxide required to neutralize 1 g of a sample and is measured as follows.

That is, 2 g of the soluble component is dissolved in 200 g of a mixed solvent of toluene / ethanol = 2/1, and titrated with 0.1N potassium hydroxide solution using phenolphthalein as an indicator.

On the other hand, as the binder resin used in the present invention, the monomer component is styrene, O-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene. , 3,4
-Dichlorostyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonyl Styrene and its derivatives such as styrene, pn-decylstyrene, pn-dodecylstyrene; ethylene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; vinyl chloride, vinylidene chloride, vinyl bromide, fluorine Vinyl halides such as vinyl chloride; Vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n methacrylate -Octyl, dodecyl methacrylate, methacrylic acid Α-methylene aliphatic monocarboxylic acid esters such as 2-ethylhexyl, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, n-butyl acrylate, Acrylic esters such as isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate; vinyl methyl ether, vinyl ethyl Vinyl ether bonds such as ether and vinyl isobutyl ether; vinyl ketones such as butynyl methyl ketone, vinyl hexyl ketone, and methyl isopropenyl ketone; N-vinyl pyrrole, N-vinyl carba N-vinyl compounds such as sol, N-vinylindole, N-vinylpyrrolidone; vinylnaphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide; acrylic acid, methacrylic acid, maleic acid, fumaric acid A vinyl compound derivative having a carboxyl group such as; maleic acid half ester, fumaric acid half ester such as half ester;
Examples thereof include homopolymers and copolymers which are vinyl compounds such as maleic anhydride, maleic acid ester, and fumaric acid ester derivative :.

It is preferable that these vinyl-based polymers are crosslinked from the viewpoint of offset resistance of the toner.

In addition, polyester, polyurethane, epoxy resin,
Polyvinyl butyral, polyacrylic acid resin, rosin,
It is also possible to use modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax and the like.

Among the resins such as the vinyl-based polymers and polyesters listed above, styrene-acrylic acid ester copolymers, styrene-methacrylic acid ester copolymers, styrene-acrylic acid ester-maleic acid half ester copolymers,
A styrene resin such as styrene-methacrylic acid ester-maleic acid half ester; and a polyester resin are preferably used as the binder resin from the viewpoints of development durability and fixing property.

The above-mentioned resins such as vinyl polymer and polyester can be used alone or in combination of two or more as a binder resin.

The toner of the present invention can be used as a magnetic toner by further containing a magnetic material. The magnetic material contained in the magnetic toner of the present invention includes magnetite, hematite, iron oxide such as ferrite, metals such as cobalt and nickel, or aluminum, cobalt, copper, lead, magnesium, tin and zinc of these metals. , Antimony, beryllium, bismuth, cadmium, calcium,
Examples thereof include alloys with metals such as manganese, selenium, titanium, tungsten, and vanadium, and mixtures thereof.

The average particle size of these ferromagnetic materials is preferably about 0.1 to 2 μ, and the magnetic characteristics when 10 KOe is applied have a coercive force of 50 to 1 μm.
50Oe, saturation magnetization 50-200emu / g (further 50-100emu / g),
Those having a residual magnetization of 3 to 20 meu / g are preferably used.

The amount of the magnetic material contained in the toner is preferably about 20 to 200 parts per 100 parts of the resin component, and particularly preferably 40 to 150 parts per 100 parts of the resin component.

If desired, the toner of the present invention may be mixed with an additive. Examples of the additive include lubricants such as Teflon and zinc stearate, abrasives such as cerium oxide and silicon carbide, fluidity imparting agents such as colloidal silica and aluminum oxide, anti-caking agents, or carbon black and tin oxide. And the like, or fixing aids such as low molecular weight polyethylene.

To prepare the toner for developing an electrostatic image according to the present invention, the metal complex compound represented by the formula (1) and a vinyl-based or non-vinyl-based thermoplastic resin (a pigment or a dye as a colorant, a magnetic material, if necessary) are used. Materials, additives, etc.) are thoroughly mixed with a ball mill or other mixer before heating rolls,
While using a heat kneader such as a kneader or an extruder to melt, knead and knead the meat to make the resins compatible with each other,
A toner having an average particle size of 5 to 20 μm can be obtained by dispersing or dissolving a charge control agent or the like, cooling and solidifying, and then pulverizing and classifying.

When the toner of the present invention is used as a two-component developer, this toner is used as a mixture with carrier powder.

As the carrier that can be used in the present invention, all known carriers can be used, for example, iron powder, ferrite powder, magnetic powder such as nickel powder, glass beads, etc., and their surfaces treated with a resin or the like. Something is included.

The toner of the present invention can be applied to known developing methods such as a two-component developing method and a one-component developing method, but is also preferably used in the developing method described below, for example.

That is, in the developing area where the latent image holding member for holding the latent image and the developer carrying member face each other, the latent image is not applied while applying an alternating electric field between the developer carrying member and the latent image holding member. The toner of the present invention can be preferably used in an image forming method of developing with a magnetic toner.

In such a developing method, the magnetic particles having a true specific gravity of 6 or less and coated with an electrically insulating resin cause the presence of the magnetic particles in the developing area of the developer carrier to be 5 to 100 mg / The magnetic brush is formed to have a size of cm ^2, and the non-magnetic toner is reciprocated between the latent image carrier and the surface of the developer carrier in the developing area, and the surface of the magnetic brush formed on the surface of the developer carrier. While developing, it is preferable to develop the latent image.

EFFECTS OF THE INVENTION As described above, according to the present invention, there is provided a toner for developing an electrostatic charge image in which a binder resin having a specific gel content contains a metal complex having a specific monoazo compound as a ligand. .

The toner of the present invention can be used without particular limitation for development in order to visualize an electrostatic charge image in electrophotography, electrostatic recording, electrostatic printing, etc. by a conventionally known means, and it is excellent as follows. It produces the effect.

(1) The triboelectric charge amount between toner particles is uniform, and the control of the electric charge amount is easy. Further, the triboelectric charge amount does not fluctuate or decrease during long-term continuous use or depending on the environment, and the toner is extremely stable.

(2) A toner which is not affected by humidity and gives a stable image under high humidity and low humidity.

(3) Toner that gives a stable image without being affected by temperature.

(4) A toner which has excellent durability and always gives a stable image even when it is continuously used for a long period of time.

(5) A toner that is excellent in frictional force and gradation reproducibility and always gives a high-quality image with high density and no fog.

Hereinafter, the present invention will be described in more detail with reference to Examples.
This does not limit the invention in any way.

All parts in the following formulations are parts by weight.

Example 1 After premixing the above materials, kneading them with two rolls heated to 150 ° C, cooling, coarsely crushing with a cutter mill, crushing with a fine crusher using a jet stream, and further using an air classifier And classified to obtain a fine powder having an average volume particle size of 11 μm.

This fine powder was thoroughly mixed with 0.4 part of hydrophobic colloidal silica to obtain toner No1.

The physical properties of Toner No. 1 are shown in the table below.

Using a commercially available electronic copying machine (trade name: NP-7550, Canon product) and applying a toner No. 1 of this example, a copying test was carried out, and a very high quality image was obtained. Furthermore, when a repeated copy test of 100,000 sheets was carried out, an image that was stable and faithful to the original was obtained during this test.
The image density was maintained at 1.3 to 1.4, no fog was observed, and the halftone reproducibility was excellent.

15 ℃, 10% RH low temperature, low humidity, and 30 ℃ 90% RH
At high temperature and high humidity, the same results as at normal temperature and normal humidity were obtained.

The charge amount is 1g of toner and iron powder carrier (200 / 300mes
h) 9 g was precisely weighed and thoroughly mixed, and then measured by the blow-off method (TB200 manufactured by Toshiba Chemical Co.).

Comparative Example 1 As a binder resin, a styrene butyl acrylate-monooctyl maleate copolymer having a gel content of 3% (70/20 /
A toner No. 2 having an average volume particle size of 11 μm was obtained in the same manner as in Example 1 except that (10 monomer weight ratio) was used. The physical properties of Toner No. 2 are shown in the table below. With this toner No2,
When the same copying test as in Example 1 was carried out, a good image was obtained in the initial stage, but when 1000 copies were repeated, it was confirmed that the image density decreased to 1.1 to 1.2 and fogging occurred. It was

It was also confirmed that durability was similarly problematic under the environment of 15 ° C. 10% RH and 35 ° C. 90% RH, and the density became 1.0 and the fog increased with repeated copying.

Example 2 Using the above materials, and using an extruder as the kneading device, the average volume particle size was measured in the same manner as in Example 1.
Toner No. 3 of μm was obtained. The physical properties of Toner No. 3 are shown in the table below.

When this toner No. 3 was applied to a commercially available laser beam blinter (trade name, LPB-CX Canon product) and a printout test was carried out, a high-resolution image was obtained, and the image density was increased even after printing 5,000 sheets repeatedly. 1.30 to 1.35
Was maintained and no fogging was observed.

Furthermore, when the same test was conducted under the conditions of 15 ° C., 10 RH, 35 ° C., and 90% RH, the same result as at room temperature and normal humidity was obtained.

Comparative Example 2 As a binder resin, a styrene-butyl methacrylate-monobutyl maleate copolymer having a gel content of 80% (80
Toner No. 4 having an average volume particle size of 12 μm was obtained in the same manner as in Example 2 except that the ratio of the monomer weight ratio was 15/5/5.

The physical properties of Toner No. 4 are shown in the table below.

In Comparative Example 2, sufficient kneading could not be performed when obtaining Toner No. 4.

When a print test similar to that of Example 2 was conducted using this toner No. 4, a good image was not obtained. Especially, the resolution and fog are bad under high temperature and high humidity (35 ℃, 99% RH).
In terms of long-term durability, it seems that there will be practical problems.

Example 3 Toner No. 5 having an average volume particle size of 11.5 μm was obtained in the same manner as in Example 2 except that the above materials were used. The physical properties of Toner No. 5 are shown in the table below.

Use this toner on a commercially available electronic copier (NR7550, made by Canon)
When No5 was applied and a copy test was performed, high resolution,
Images with high gradation reproducibility are obtained, and even when a 100,000-copy test is repeatedly performed, high image density (1.35 ~
The image of 1.4) was obtained and no fog was observed.

Furthermore, when the same test was performed under the conditions of 15 ° C., 10% RH, and 30 ° C., 90% RH, the same result as under normal temperature and normal humidity was obtained.

Comparative Example 3 Instead of the compound of structural formula (4), a monoazo compound Cr complex Toner No. 6 having an average volume particle size of 11.5 μm was obtained in the same manner as in Example 3 except that 2 parts of was used. The physical properties of Toner No. 6 are shown in the table below.

When this toner No. 6 was used to perform a copying test in the same manner as in Example 3, a good image was obtained up to 100,000 sheets, but the image density was lower than that in Example 3, and was 1.1 to 1.2.

Further, under the environment of 30 ° C. and 90% RH, the density was gradually decreased, and the density was decreased (0.9 to 1.0) in 20,000 copies.

It is considered that this is because the Cr complex is not sufficiently dispersed in the binder as compared with the compound of the structural formula (4).

Example 4 A toner No. 7 having an average volume particle diameter of 12 μm was obtained in the same manner as in Example 1 except that the above materials were used. The physical properties of Toner No. 7 are shown in the table below.

Toner No. 7 was mixed at a ratio of 5 parts with 100 parts of an iron powder carrier having an average particle size of 50 to 80 .mu.m to prepare a developer.
When this developer was applied to a commercially available electronic copying machine (NR5000 Canon) and a durability copying test was performed on 100,000 sheets, stable image density (1.4 to 1.5) and high resolution images were obtained. No fogging was observed.

Further, in the durability copying test under the conditions of 15 ° C., 10% RH, 30 ° C., and 90% RH, excellent images were obtained as under normal temperature and normal humidity.

The physical properties of Toners No. 1 to No. 7 obtained above are summarized in the table below.

Claims (1)

[Claims] 1. A gel content of a binder resin, which comprises 0.1 to 10 parts by weight of a metal complex of a monoazo compound represented by the following general formula (1) with respect to 100 parts by weight of a resin component.
A toner for developing an electrostatic charge image, which comprises 10 to 70% by weight. (In the formula, R ¹ represents alkyl, alkenyl, aralkyl or aryl having 5 to 18 carbon atoms, and R ² represents hydrogen, halogen, nitro, cyano, or 1 to 18 carbon atoms.
Number of alkoxy, or represents a carboxy ester, R ³ represents hydrogen, halogen, nitro, cyano, carboxy ester, alkyl having 1 to 18 carbon atoms, alkenyl, aralkyl, aryl or alkoxy, l is 1 to 4 Represents an integer, and n and k are (n + k) =
Represents 0 or a positive integer of 1 to 4, m is n + k + m
Represents an integer of 4 and R ¹ , R ² and R ³ are the same or different substituents, and when l, m and (n + k) are integers of 2 or more, a plurality of
R ¹ , R ³ or R ³ are respectively the same or different substituents, X represents —O—, —COO— or —S—, and Y represents —O—, —COO—, —S. - or -NR ⁴ - (wherein, R ⁴
Represents an alkyl having 1 to 4 carbon atoms. ), M represents Cr, Co or Fe, and A represents hydrogen, Na, K, ammonium, or organic ammonium. )