Electrophotographic toner

Description

[0001] The present invention relates to an electrophotographic toner containing a specific azo-type metal complex salt as charge control agent to be used for an image forming apparatus such as an electrostatic copying apparatus, a laser printer or the like.

[0002] In the image forming apparatus above-mentioned, an electrostatic latent image formed on the surface of a photoreceptor by exposure to light is let come in contact with an electrophotographic developer by a developping device. Toner in the electrophotographic developer is electrostatically sticked to the electrostatic latent image. This causes the electrostatic latent image to be turned into a toner image. Then, the toner image is transferred to paper from the surface of the photoreceptor and fixed on the paper, thus achieving image forming.

[0003] As an electrophotographic toner, there may be generally used toner particles containing a binder resin, a coloring agent such as carbon black or the like, an electric charge controlling agent, a release agent, a flowability imparting agent as necessary and the like. As the electric charge controlling agent, there is generally used an azo-type metal complex salt dye (azo-type chromium dye or the like).

[0004] Such a complex salt dye is disclosed in EP-A-0,141,377.

[0005] Another azo-type metal complex salt dye for use as an electric charge controlling agent is disclosed in EP-A-0,393,479. This document is considered prior art under Article 54(3) EPC. The disclosed dye comprises a metal group which may be chromium or a cobalt atom. The cation may comprise a sodium or potassium ion.

[0006] The United States Patent US-A-4,954,409 discloses a developer comprising a toner having a colourant and a carrier having a core material. The toner comprises a chromium complex salt of 0,0'-dihydroxyazo dye. The complex has a cation which may be hydrogen, an alkali metal, aliphatic ammonium or a pyridinium cation.

[0007] The European patent application EP-A-0,291,930 discloses a toner for developing an electrostatic image comprising an azo-type metal complex salt dye. The metal may scandium, venedium, manganese or zinc. The cation may be hydrogen, sodium, potassium, ammonium or an organic ammonium.

[0008] To improve the flowability of the toner particles, silica fine powder, particularly hydrophobic silica fine powder, is generally mixed with and dispersed in the toner particles.

[0009] However, such a conventional electrophotographic toner presents the problems that the electric charge characteristics are not stabilized to provoke fog, decrease in image density, toner scattering or a so-called letter dispersion, i.e., spots as formed by the toner scattering around reproduced letters, so that stable images cannot be obtained. In particular, when a black toner containing carbon black as a coloring agent is used, the problems above-mentioned are remarkable.

[0010] It is an object of the present invention to provide an electrophotographic toner with which there can be obtained stable images free from fog, decrease in image density, letter dispersion, toner scattering and the like.

[0011] To achieve the object above-mentioned, the inventors have studied hard and paid their attention to the pH value of an azo-type metal complex salt dye used as the electric charge controlling agent. The inventors have found the fact that the electric charge characteristics and humidity resistance of a toner and dispersibility of the electric charge controlling agent in the resin vary with this pH value to cause a variety of problems such as defective image (insufficient image density, fog and the like), toner scattering and the like.

[0012] An electrophotographic toner is provided in accordance with the present invention as defined in claim 1. The electric charge controlling agent is a compound represented by the following general formula (1) and presenting a pH value in a range from 3 to 5:

wherein R¹, R², R³ and R⁴ may be the same as or different from one another, and each is a hydrogen atom, a halogen atom or the following group:

wherein R⁵ and R⁶ may be the same as or different from one another, and each is an alkyl or aryl group, and R¹, R², R³ and R⁴ are not all simultaneously a hydrogen atom; Y is a Cr, Fe, Co, Zn or Ti atom; Z⁺ is a cation selected from the group consisting of an ammonium ion and a hydrogen ion.

[0013] For a toner containing carbon black as the coloring agent, it is preferable to use carbon black of which pH value is in a range from 6 to 11, in addition to the use of the electric charge controlling agent having a pH in the range mentioned earlier.

[0014] When hydrophobic silica fine powder is mixed with and dispersed in toner particles containing, as the electric charge controlling agent, the compound (1) having a pH value in a range from 3 to 5, the pH value of the hydrophobic silica is preferably in a range from 3.5 to 4.5.

[0015] The pH value above-mentioned may be measured in accordance with the method set forth in JIS K 6221. More specifically, 10 g of a sample is added to 100 ml of distilled water. The sample-water mixture is then boiled for 15 minutes and cooled to a room temperature, after which pH value is measured.

[0016] Since the compound of the general formula (1) presents a pH value in a range from 3 to 5, it can be uniformly dispersed, as the electric charge controlling agent, in the binder resin of the toner. Accordingly, the electrophotographic toner in accordance with the present invention can be stabilized in electric charge characteristics.

[0017] If the pH value of the compound (1) is less than 3, the toner is lowered in humidity resistance. If the pH value is greater than 5, the dispersibility of the compound (1) in the binder resin is defective. In both cases above-mentioned, there are caused the problems such as decrease in image density, letter dispersion, toner scattering and the like.

[0018] The pH value of the compound of the general formula (1) is greatly influenced by the polar group connected to this compound. When the polar group is an electron attractive group (e.g., a halogen atom), the pH value is liable to decrease. It is therefore required to select the respective groups such that the pH value is located in the range above-mentioned. Table 1 shows the relationship between the combination of the substituting groups and the pH value. It is however noted that the pH value varies with a trace amount of a by-product included in the course of production of the compound (1) or with the presence of unreacted substances, and is therefore not a definite value.

Table 1

R1	R2	R3	R4	Y	Z+	pH
Cl	H	H	Cl	Cr	H+	3.1 - 4.9
H	H	*1	Cl	Fe	H+	3.6 - 4.9

*1 -SO2N(CH3)2

[0019] When there is used, as the coloring agent, carbon black of which pH value is less than 6, the humidity resistance of the toner is not sufficient. When there is used, as the coloring agent, carbon black of which pH value is greater than 11, the dispersibility of the compound (1) and the carbon black in the binder resin is lowered. In both cases above-mentioned, there are caused the problems of fog, decrease in image density, letter dispersion, toner scattering and the like.

[0020] When hydrophobic silica fine powder is to be mixed with and dispersed in toner particles containing, as the electric charge controlling agent, the compound (1) of which pH value is in a range from 3 to 5, it is preferable to use hydrophobic silica fine powder of which pH value is in a range from 3.5 to 4.5. In this case, the electric charge characteristics are stabilized to produce stable images. More specifically, if the pH values of the compound of the general formula (1) and the hydrophobic silica fine powder are below the ranges above-mentioned, the amount of negative electric charge becomes great, causing the toner to be separated from the carrier with difficulty. This provokes the problem of decrease in image density. If both pH values exceed the ranges above-mentioned, the amount of negative electric charge becomes small, causing the toner to be insufficiently sticked to the carrier. This provokes the problem of toner scattering, fog or the like.

[0021] Examples of the halogen atom include a fluorine atom, a chloride atom, a bromine atom and an iodine atom.

[0022] Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl and hexyl groups, each having 1 to 6 carbon atoms.

[0023] Examples of the aryl group include phenyl, tolyl, xylyl, biphenyl, naphthyl, antolyl and phenantolyl groups.

[0024] As the electric charge controlling agent, the compound (1) is used in an amount from 0.5 to 8 parts by weight, preferably from 1 to 3 parts by weight, for 100 parts by weight of binder resin. If the blending ratio of the compound (1) is smaller than the range above-mentioned, the electric charge characteristics become unstable. If the blending ratio of the compound (1) is greater than the range above-mentioned, the carrier is sticked to the toner, thereby to provoke toner scattering, fog and the like.

[0025] The toner is produced by a method of mixing a binder resin, a coloring agent, the compound (1) as an electric charge controlling agent, a release agent (an off-set preventive agent) and an additive such as a flowability imparting agent or the like to be used as necessary, and pulverizing the mixture into particles having a predetermined particle size. More specifically, the toner is produced by previously mixing and kneading the components above-mentioned uniformly with the use of a dry blender, a Henschel mixer, a ball mill or the like, uniformly melting and kneading the resultant mixture with the use of a kneading device such as a Banbury mixer, a roll, a single- or double-shaft extruding kneader or the like, cooling and grinding the resultant kneaded body, and classifying the resultant ground pieces as necessary. The toner may also be produced by suspension polymerization or the like.

[0026] Examples of the binder resin include styrene resins (monopolymers and copolymers containing styrene or a styrene substituent) such as polystyrene, chloro-polystyrene, poly-α-methylstyrene, a styrene-chloro-styrene copolymer, a styrene-propylene copolymer, a styrene-butadiene copolymer, a styrene-vinyl chloride copolymer, a styrene-vinyl acetate copolymer, a styrene-maleic acid copolymer, a styrene-acrylate copolymer (a styrene-methyl acrylate copolymer, a styrene-ethyl acrylate copolymer, a styrene-butyl acrylate copolymer, a styrene-octyl acrylate copolymer, a styrene-phenyl acrylate copolymer or the like), a styrene-methacrylate copolymer (a styrene-methyl methacrylate copolymer, a styrene-butyl methacrylate copolymer, a styrene-butyl methacrylate copolymer, a styrene-phenyl methacrylate copolymer or the like), a styrene-α-methyl chloroacrylate copolymer, a styrene-acrylonitrile-acrylate copolymer and the like. Examples of the binder resin further include polyvinyl chloride, low-molecular-weight polyethylene, low-molecular-weight polypropylene, an ethylene-ethyl acrylate copolymer, polyvinyl butyral, an ethylene-vinyl acetate copolymer, rosin modified maleic acid resin, phenyl resin, epoxy resin, polyester resin, ionomer resin, polyurethane resin, silicone resin, ketone resin, xylene resin, polyamid resin and the like. The examples above-mentioned may be used alone or in combination of plural types. In the examples above-mentioned, there may be preferably used styrene resin, particularly a styrene-(meth)acrylate copolymer and more particularly a styrene-methyl methacrylate-butylacrylate copolymer. In particular, there may be preferably used a styrene-methyl methacrylate-butylacrylate copolymer containing 75 to 85 % by weight of styrene, 0.5 to 5 % by weight of methylmethacrylate and 10 to 20 % by weight of butylacrylate.

[0027] Examples of the coloring agent include: a black coloring agent such as carbon black (furnace black, channel black, thermal, gas black, oil black, acetylene black), lamp black, aniline black or the like; a brown coloring agent as obtained by mixing red, yellow and black coloring agents. Of these, the black coloring agent may be particularly suitably used. The coloring agent may be used in an amount of 1 to 20 parts by weight and preferably 3 to 15 parts by weight for 100 parts by weights of the binder resin.

[0028] Examples of the release agent (off-set preventing agent) include aliphatic hydrocarbon, aliphatic metal salts, higher fatty acids, fatty esters, its partially saponified substances, silicone oil, a variety of waxes and the like. Of these, there is preferably used a low-molecular-weight aliphatic hydrocarbon of which weight average molecular weight is from about 1,000 to about 10,000. More specifically, there is suitably used one or a combination of plural types of a low-molecular-weight polypropylene, low-molecular-weight polyethylene, paraffin wax, a low-molecular-weight olefin polymer composed of an olefin unit having 4 or more carbon atoms and the like. The release agent may be used in an amount of 0.1 to 10 parts by weight and preferably from 1 to 5 parts by weight for 100 parts by weight of the binder resin.

[0029] As conventionally done, the toner particles may have sizes in a range from 3 to 35 µm and preferably from 5 to 25 µm, but it is preferable that the distribution of toner particle sizes satisfies the following formula:

[wherein N is the percentage by the number of toner particles of which sizes as measured with a coulter counter exceed 16 µm, and C is surface dye density (g/g) of the toner particles]

[0030] When the distribution of toner particle sizes is in the range above-mentioned, it is possible, in view of the relationship with the surface dye density, to further eliminate variations in electric charging characteristics of the toner.

[0031] To obtain toner particles presenting a distribution of particle sizes which satisfies the formula above-mentioned, the ground toner particles may be classified to remove particles having sizes greater than 16 µm, or toner particles may be ground such that the peak of the toner particle-size distribution is shifted to a smaller-size zone to reduce the content of particles having sizes greater than 16 µm.

[0032] According to the present invention, as the hydrophobic silica fine powder to be mixed with and dispersed in the toner particles, there may be used silica fine powder of which surface is treated with, for example, a (poly)alkyl group, a (poly)alkylsilil group, a (poly)alkylsilane or silicone oil. Preferably, there may be used silica fine powder of which surface has been treated with a compound having a polymethylsilil group such that the powder becomes hydrophobic. Such powder is higher in hydrophobic nature than conventional silica fine powder treated with a compound having a low-molecular-weight alkyl group.

[0033] As a commercially available product of such silica fine powder, there may be mentioned "Cabosil TS720" manufactured by Cabot Co., Ltd. This product is hydrophobic fumed silica fine powder, which is obtained by treating high-purity fumed silica fine powder (99.8% SiO₂) with an organic silicone compound, and on the surface of which a polymethylsilil group is present to increase the hydrophobic nature of the surface of the silica fine powder.

[0034] The particle sizes of the silica fine powder so treated as to be hydrophobic are suitably in a range from 0.01 to 0.04 µm.

[0035] The pH value of the hydrophobic silica fine powder varies with a variety of factors which are not always clarified. However, it is known that the surface functional group is influenced by reaction byproducts.

[0036] The hydrophobic silica fine powder may be added in an amount of 0.01 to 5 % by weight and preferably from 0.05 to 1 % by weight for the total amount of toner. If the amount of the hydrophobic silica fine powder is greater than the range above-mentioned, the amount of electric charge is excessive. If this amount is smaller than the range above-mentioned, the effect of improving the toner flowability cannot be expected.

Examples

[0037] The following description will discuss in more detail the electrophotographic toner in accordance with the present invention with reference to Examples and Comparative Examples.

Examples 1 to 7 and Comparative Examples 1 to 8

[0038] 

(Component)	(% by Weight)
Styrene-acrylic copolymer	86
Carbon black	10
Off-set preventive agent (Low-molecular-weight polypropylene)	2
Charge controlling agent (Compound (1))	1.5
Hydrophobic silica	0.5

[0039] The components above-mentioned were mixed. The mixture was molten and kneaded with a double-shaft kneader, and then cooled, ground and classified to prepare toner particles having the average particle size of 10 µm. Table 2 shows the substituting groups contained in the compounds (1) used, as the electric charge controlling agent, in Examples 1 to 7 and Comparative Examples 1 to 8. Table 3 shows the pH values of carbon black and the compounds (1) used. Each pH value was measured in the manner that 10 g of a sample was added to 100 ml of distilled water and the sample-water mixture was then boiled for 15 minutes on a hot plate and cooled to a room temperature, after which pH value was measured with a glass electrode pH meter. The pH value of the hydrophobic silica fine powder used was 4.1.

[0040] The moisture contents of the resultant electrophotographic toners thus obtained were measured under the condition of ambient temperature/ambient humidity (temperature : 20°C, humidity : 65%, hereinafter referred to as N/N) and under the condition of high temperature/high humidity (temperature : 35°C, humidity : 85%, hereinafter referred to as H/H), respectively, according to the Karl Fischer method. Table 3 shows the results.

[0041] The following evaluation tests were conducted on the electrophotographic toners obtained in Example 1 to 7 and Comparative Examples 1 to 8. Table 3 shows the test results.

(1) Test of Dispersibility

[0042] The circumference of each of the electrophotographic toners was covered with and solidified by epoxy resin. Each of the toners as cut with a microtome was observed with a transmission-type electro microscope. The toner dispersibility was evaluated according to the following criteria:

ⓞ :

Extremely finely dispersed

O :

Substantially finely dispersed

Δ :

Some large particles observed

X :

Many large particles observed

(2) Test of Image Density

[0043] Each of the electrophotographic toners was mixed with a carrier to prepare a developer having a toner density of 3%. With an electrophotographic copying apparatus (DC-7085 manufactured by Mita Industrial Co., Ltd.) using (i) each developer above-mentioned as a start developer and (ii) the same toner as that contained in the start developer as a resupply toner, a solid-black document was continuously copied for 150,000 pieces under the condition of ambient temperature/ambient humidity (N/N), i.e., temperature of 20°C and humidity of 65%, except that intermediate 8000 copied pieces from 16001st piece to 24000th piece were taken at temperature of 35°C and humidity of 85% (H/H). Every thousandth copied pieces were extracted, as samples, from 150,000 copied pieces for each of the developers and were measured as to the density values thereof with a reflection densitometer (TC-6D manufactured by Tokyo Denshoku Co., Ltd.). The averages were calculated for these samples for all the developers.

(3) Test of Fog Density

[0044] With the use of the reflection densitometer above-mentioned, the density of the blank spaces of each sample obtained in Test of Image Density was measured to measure fog density. The averages were calculated for the samples for all the developers.

(4) Test of Letter Dispersion

[0045] All the samples obtained in Test of Image Density were visually checked for a so-called letter dispersion of toner spots.

(5) Test of Toner Scattering

[0046] For each developer, there were checked (i) the blank spaces of the reproduced image of the 150,000th piece, and (ii) the inside of the copying apparatus after 150,000 copies had been taken. The toner dispersibility was evaluated according to the following criteria:

	Apparatus Inside	Reproduced Image
ⓞ :	No toner scattering observed	No toner scattering observed
O :	Some toner scattering observed	"
Δ :	Toner scattering observed	Sporadic toner scattering observed
X :	Many toner scattering observed	Continuous toner scattering observed

Table 3

(3/3)
	Fog Density		Letter Dispersion	Toner Scattering	Total Evaluation
	N/H	H/H
Example 1	0.002	0.004	None	ⓞ	ⓞ
Example 2	0.003	0.004	None	ⓞ	ⓞ
Example 3	0.001	0.003	None	ⓞ	ⓞ
Example 4	0.001	0.002	None	ⓞ	ⓞ
Example 5	0.003	0.004	Little	O	O
Example 6	0.002	0.004	Little	O	O
Example 7	0.001	0.003	None	O	ⓞ
Comp. Ex.1	0.011	0.019	Sporadic	X	X
Comp. Ex.2	0.012	0.017	Sporadic	Δ	X
Comp. Ex.3	0.014	0.022	Continuous	X	X
Comp. Ex.4	0.016	0.026	Continuous	X	X
Comp. Ex.5	0.013	0.023	Sporadic	Δ	X
Comp. Ex.6	0.012	0.022	Sporadic	X	X
Comp. Ex.7	0.014	0.021	Sporadic	Δ	X
Comp. Ex.8	0.011	0.023	Sporadic	Δ	X
"Comp. Ex." means "Comparative Example".

[0047] It is understood from Table 3 that each of the electrophotographic toners of Examples 1 to 7 containing, as the electric charge controlling agent, the compound (1) presenting a pH value in a range from 3 to 5, is superior in dispersibility to the electrophotographic toners of Comparative Examples 1 to 8 containing a compound presenting a pH value which deviates from the range above-mentioned. Further, each of the toners of Examples 1 to 7 presents less variations of moisture content under both conditions of ambient temperature/ambient humidity (N/N) and high temperature/high humidity (H/H), and is therefore excellent in humidity resistance.

[0048] It is also understood that the reproduced images obtained with the use of the electrophotographic toners of Examples 1 to 7 are superior in any of image density, fog density, letter dispersion and toner scattering to the reproduced images obtained with the use of the electrophotographic toners of Comparative Examples 1 to 8.

[0049] It is also understood that variations between reproduced images obtained under the ambient temperature/ambient humidity (N/N) condition and reproduced images obtained under the high temperature/high humidity (H/H) condition both with the use of each of the electrophotographic toners of Examples 1 to 7, are less than variations between reproduced images obtained under the ambient temperature/ambient humidity (N/N) condition and reproduced images obtained under the high temperature/high humidity (H/H) condition both with the use of each of the electrophotographic toners of Comparative Examples 1 to 8. Thus, stable reproduced images can be obtained with the toners of Examples 1 to 7.

[0050] It is also understood that, out of the electrophotographic toners of Examples 1 to 7, the toners of Examples 1 to 4 and 7 using carbon black presenting a pH value in a range from 6 to 11 are particularly excellent.

Examples 8 to 11

[0051] 

(Component)	(% by Weight)
Styrene-acrylic copolymer	85
Carbon black	10
Off-set preventive agent (Low-molecular-weight polypropylene)	3
Chromium-containing azo dye (pH 4.9)	2

[0052] The components above-mentioned were molten and kneaded with a double-shaft kneader, and then prepared as toner particles having the average toner particle size of 10 µm with a jetmil. Table 4 shows the groups contained in the chromium-containing azo dye used as the electric charge controlling agent. The pH value of the carbon black was 8.5.

[0053] Silica fine powder so treated as to be hydrophobic (particle size of 0.02 µm, pH of 3.7, Cabosil TS-720 manufactured by Cabot Co., Ltd.) was mixed with and dispersed in the toner particles thus prepared in an amount of 0.5 % by weight for the total amount of the toner particles, thus preparing a toner.

Examples 8 to 11 and Comparative Examples 9 to 16

[0054] Toners were prepared in the same manner as in Example 1 except that there were used (i) metal-containing azo dyes which respectively contained groups shown in Table 4 and of which pH values are shown in Table 6 and (ii) hydrophobic silica fine powders of which pH values are shown in Table 6.

Table 4

	Groups of Compound (1)
	R1	R2	R3	R4	Y	Z+
Examples 8	Cl	H	H	Cl	Cr	H+
Examples 9	Cl	H	H	Cl	Cr	H+
Examples 10	Cl	H	H	Cl	Cr	H+
Examples 11	Cl	H	H	Cl	Cr	H+
Comparative Examples 9	Cl	H	H	Cl	Cr	NH4+
Comparative Examples 10	Cl	Cl	Cl	H	Fe	Na+
Comparative Examples 11	H	Cl	Cl	Cl	Co	K+
Comparative Examples 12	H	H	Br	H	Zn	NH4+
Comparative Examples 13	H	Cl	Br	H	Co	H+
Comparative Examples 14	Cl	H	Cl	Cl	Zn	K+
Comparative Examples 15	Cl	H	H	Cl	Cr	H+
Comparative Examples 16	Cl	H	H	Cl	Cr	H+

Evaluation Tests

[0055] Ferrite carrier having the average particle size of 80 µm was blended with each of the toners of Examples 8 to 11 and Comparative Examples 9 to 16. Each mixture was uniformly mixed and agitated to prepare a two-component developer presenting toner density of 4%. With the use of an electrophotographic copying apparatus (DC-3255 manufactured by Mita Industrial Co., Ltd.) using each of the developers thus prepared, an original document was copied totally 80,000 pieces under different operating conditions under which a predetermined number of copied pieces were respectively taken. All the copied pieces were checked for image density, fog density, amount of electric charge and toner scattering for each of the operating conditions. More specifically, the copying operation was carried out with the operating condition changed in the order shown in Table 5 for a predetermined number of pieces, and the reproduced images were checked for the items above-mentioned. It is however noted that the measured values of the images reproduced under the N/N condition were those obtained after 80,000 pieces were copied.

Table 5

Copying Order	Mark	Operating Condition	Number of Copied Pieces
1	N/N	Ambient Temp. & Ambient Humidity (20°C & 65%)	8,000
2	L/L	Low Temp. & Low Humidity (10°C & 45%)	8,000
3	H/H	High Temp. & High Humidity (35°C & 85%)	8,000
4	N/N	Ambient Temp. & Ambient Humidity (20°C & 65%)	56,000

[0056] The respective tests were conducted in the following manners.

(1) Measurement of Image Density (I.D.)

[0057] Each image density was measured with the use of a reflection densitometer (TC-6D manufactured by Tokyo Denshoku Co., Ltd.)

(2) Measurement of Fog Density (F.D.)

[0058] With the use of the reflection densitometer above-mentioned, the density of blank portions of each reproduced image was measured and defined as fog density.

(3) Amount of Electric Charge

[0059] The amount of electric charge was measured with a blow-off electric charge measuring instrument manufactured by Toshiba Chemical Co., Ltd.

(4) Toner Scattering

[0060] The inside of the copying apparatus and the surface of each reproduced image were visually checked for toner scattering, and evaluated according to the following criteria:

	Apparatus Inside	Reproduced Image
ⓞ :	Substantially no toner scattering observed	No toner scattering observed
O :	Slight toner scattering observed	"
● :	Some toner scattering observed	"
Δ :	Toner scattering observed	Toner scattering observed
X :	Many toner scattering observed	Toner blanking observed

[0061] The test results are shown in Table 6.

[0062] It is apparent from Table 6 that, by adjusting the pH values of the hydrophobic silica fine powder and the electric charge controlling agent within respective predetermined ranges, the electric charge characteristics can be stabilized to remarkably improve the image density and toner scattering.

Claims

1. An electrophotographic toner comprising a binder resin, a coloring agent, an electric charge controlling agent and a release agent, said electric charge controlling agent being represented by the following general formula (1):

wherein R¹, R², R³ and R⁴ may be the same or different, and each is a hydrogen atom, a halogen atom or the following group:

wherein R⁵ and R⁶ may be the same or different, and each is an alkyl or aryl group; Y is a Cr, Fe, Co, Zn or Ti atom; Z⁺ is a cation selected from the group consisting of an ammonium ion, a hydrogen ion, a potassium ion and a sodium ion;

wherein R¹, R², R³ and R⁴ are not simultaneously all a hydrogen atom,

wherein the above components are selected such that the charge controlling agent has a pH in the range of 3 to 5, and

wherein when R¹ and R⁴ are chloro atoms and R² and R³ are hydrogen atoms, Z⁺ is neither sodium nor potassium.

2. An electrophotographic toner according to Claim 1, wherein the compound of the general formula (1) is contained in an amount of 0.5 to 8 parts by weight for 100 parts by weight of binder resin.

3. An electrophotographic toner according to Claim 1, or 2, wherein the distribution of toner particle sizes is in a range represented by the following formula:

wherein N is the percentage of the number of toner particles of which sizes as measured with a coulter counter exceed 16 µm, and C is surface dye density (g/g) of the toner particles.

4. An electrophotographic toner according to Claim 1, 2 or 3, wherein the coloring agent is carbon black of which pH value is in the range of 6 to 11.

5. An electrophotographic toner according to any one of the Claims 1 to 4, wherein hydrophobic silica having a pH value in the range of 3.5 to 4.5 is mixed with and dispersed in said toner.

6. An electrophotographic toner according to Claim 5, wherein the hydrophobic silica is fine powder with a particle size in the range of 0.01 to 0.04 µm.

7. An electrophotographic toner according to Claim 5, wherein the hydrophobic silica is contained in an amount of 0.01 to 5% by weight for the amount of all toner particles.

Ansprüche

1. Elektrophotographischer Toner, der folgendes aufweist: ein Binderharz, ein Farbmittel, ein Mittel zum Steuern der elektrischen Ladung und ein Trennmittel, wobei das Mittel zum Steuern der elektrischen Ladung durch die folgende allgemeine Formel (1) repräsentiert ist:

wobei R¹, R², R³ und R⁴ gleich oder verschieden sein können und jedes ein Wasserstoffatom, ein Halogenatom oder die folgende Gruppe ist:

wobei R⁵ und R⁶ gleich oder verschieden sein können und jedes eine Alkyl- oder Arylgruppe ist; Y ein Cr-, Fe-, Co-, Zn- oder Ti-Atom ist; z⁺ ein Kation ist, das aus der Gruppe ausgewählt ist, die aus einem Ammoniumion, einem Wasserstoffion, einem Kaliumion und einem Natriumion besteht;

wobei R¹, R², R³ und R⁴ nicht gleichzeitig sämtlich ein Wasserstoffatom sind,

wobei die obigen Bestandteile derart ausgewählt sind, daß das die Ladung steuernde Mittel einen pH im Bereich von 3 bis 5 hat, und

wobei, wenn R¹ und R⁴ Chlorogruppen und R² und R³ Wasserstoffatome sind, Z⁺ weder Natrium noch Kalium ist.

2. Elektrophotographischer Toner nach Anspruch 1, wobei die Verbindung der allgemeinen Formel (1) in einer Menge von 0,5 bis 8 Gewichtsteilen auf 100 Gewichtsteile Binderharz enthalten ist.

3. Elektrophotographischer Toner nach Anspruch 1 oder 2, wobei die Verteilung von Tonerteilchengrößen in einem Bereich ist, der durch die folgende Formel repräsentiert ist:

wobei N der Prozentsatz der Anzahl von Tonerteilchen ist, deren Größen, gemessen mit einem Coulter-Zähler, 16 µm überschreitet, und C die Oberflächenfarbstoffdichte (g/g) der Tonerteilchen ist.

4. Elektrophotographischer Toner nach Anspruch 1, 2 oder 3, wobei das Farbmittel Ruß ist, dessen pH-Wert im Bereich von 6 bis 11 liegt.

5. Elektrophotographischer Toner nach einem der Ansprüche 1 bis 4, wobei hydrophobes Silicamaterial, das einem pH-Wert im Bereich von 3,5 bis 4,5 hat, mit dem Toner vermischt und darin dispergiert ist.

6. Elektrophotographischer Toner nach Anspruch 5, wobei das hydrophobe Silicamaterial feines Pulver mit einer Teilchengröße im Bereich von 0,01 bis 0,04 µm ist.

7. Elektrophotographischer Toner nach Anspruch 5, wobei das hydrophobe Silicamaterial in einer Menge von 0,01 bis 5 Gew.-% für die Menge aller Tonerteilchen enthalten ist.

Revendications

1. Toner électrophotographique comprenant une résine de liaison, un agent colorant, un agent contrôlant la charge électrique et un agent de relargage, l'agent contrôlant la charge électrique étant représenté par la formule générale suivante (1):

dans laquelle R¹, R², R³ et R⁴ peuvent être les mêmes ou différents, et chacun un atome d'hydrogène, un atome d'halogène ou le groupe suivant :

dans laquelle R⁵ et R⁶ peuvent être les mêmes ou différents, et chacun un groupe alkyle ou aryle ; Y est un atome de Cr, Fe, Co, Zn ou Ti ; Z⁺ est un cation choisi dans le groupe composé des ions ammonium, hydrogène, potassium et sodium ;

dans laquelle R¹, R², R³ et R⁴ ne sont pas tous simultanément des atomes d'hydrogène,

dans laquelle les composants ci-dessus sont choisis de telle sorte que l'agent de contrôle de la charge a un pH dans la gamme de 3 à 5 et,

dans laquelle R¹ et R⁴ sont des groupes chloro et R² et R³ sont des atomes d'hydrogène, Z⁺ n'est ni un sodium, ni un potassium.

2. Toner électrophotographique selon la revendication 1, dans lequel le composé de formule générale (1) est contenu en quantité de 0,5 à 8 parties en poids pour 100 parties en poids de résine de liaison.

3. Toner électrophotographique selon la revendication 1 ou 2, dans lequel la distribution des tailles de particules de toner est comprise dans la gamme représentée par la formule générale :

dans laquelle N est le pourcentage du nombre de particules de toner dont la taille mesurée par un compteur Coulter excède 16 µm et C est la densité de pigment (g/g) en surface des particules de toner.

4. Toner électrophotographique selon la revendication 1, 2 ou 3, dans lequel l'agent colorant est du noir de carbone dont le pH est compris entre 6 et 11.

5. Toner électrophotographique selon l'une des revendications 1 à 4, dans lequel de la silice hydrophobe ayant un pH compris entre 3,5 et 4,5 est mélangée au toner et dispersée dans celui-ci.

6. Toner électrophotographique selon la revendication 5, dans lequel la silice hydrophobe est une fine poudre ayant une taille de particules entre 0,01 et 0,04 µm.

7. Toner électrophotographique selon la revendication 5, dans lequel la silice hydrophobe est contenue en quantité comprise entre 0,01 et 5 % en poids par rapport à la quantité de toutes les particules de toner.