EP0945766B1

EP0945766B1 - Black non-magnetic composite particles for black toner and black toner using the same

Info

Publication number: EP0945766B1
Application number: EP19990302317
Authority: EP
Inventors: Kazuyuki Hayashi; Hiroko Morii; Yasuyuki Tanaka; Seiji Ishitani
Original assignee: Toda Kogyo Corp
Current assignee: Toda Kogyo Corp
Priority date: 1998-03-26
Filing date: 1999-03-25
Publication date: 2003-05-14
Anticipated expiration: 2019-03-25
Also published as: EP0945766A2; DE69907795T2; EP0945766A3; DE69907795D1

Description

The present invention relates to black non-magnetic composite particles for a black toner and a black toner using the black non-magnetic composite particles and to a process to produce them.
In conventional electrophotographic developing processes, a black toner prepared by mixing and dispersing non-magnetic black pigments such as carbon black in a binder resin, has been widely used as a developer.
Recent developing systems have been generally classified into one-component developing methods and two-component developing methods.
In the two-component developing methods, the black toner and carrier are brought into frictional contact with each other to impart an electrostatic charge having a reverse sign to that of an electrostatic latent image to the black toner, so that the black toner is attached onto the surface of the electrostatic latent image due to an electrostatic attracting force therebetween, thereby neutralizing opposite electrostatic charges on the black toner and the electrostatic latent image.
On the other hand, in the one-component developing methods, since no carrier is used therein, it is not necessary to control a density of the black toner. Besides, a developing apparatus used therefor can be miniaturized due to its simple structure. However, since the one-component developing methods are inferior in developing performance or quality to the two-component developing methods, high techniques have now been required to obtain the same developing performance or quality as those of the two-component developing methods. As one of the one-component developing methods, there is known a so-called insulated non-magnetic toner developing method using a high-resistant or insulated black toner prepared by dispersing carbon black fine particles in a binder resin without using magnetic particles.
In the case where the black toners used in the above two-component developing method and the insulated non-magnetic toner developing method, are applied to a currently predominant PPC system of copiers, both types of the black toners are required to exhibit a good insulating property or a high resistance, specifically to have a volume resistivity as high as not less than 10¹² Ω·cm.
Also, it is known that the behavior (movement) of a developer in a developing apparatus is strongly governed by the flowability thereof, for example, the flowability of the developer has strong influences on the frictional charging properties between the black toner and the carrier in the case of the two-component developing method, or on the charging property of the black toner on a sleeve in the case of the one-component developing method. Recently, with the enhancement in image quality such as image density, or tone gradation or in developing speed in the developing apparatus, it has been strongly demanded to increase the flowability of the black toner.
With the recent tendency of reducing a particle size of the black toner, it has been more strongly required to enhance the flowability thereof.
With respect to such a fact, in "Comprehensive Data Collection for Development and Utilization of Toner Materials", published by Japan Scientific Information Co., Ltd., page 121, it has been described that "With extensive development of printers such as IPC, a high image quality has been required. In particular, it has been demanded to develop high-precision or high-definition printers. In Table 1, there is shown a relationship between image definitions obtained by using various toners. As is apparent from Table 1, the smaller the particle size of wet toner, the higher the image definition becomes. When a dry toner is used, it is also required to reduce the particle size of the toner for enhancing the image definition. ··· As to toners having a small particle size, it has been reported that by using toners having a particle size of 8.5 to 11 µm, fogs on a background area as well as toner consumption can be reduced. Further, it has been proposed that by using polyester-based toners having a particle size of 6 to 10 µm, an image quality, a charging stability and lifetime of the developer can be improved. However, when such toners having a small particle size are used, it has been required to solve many problems, e.g., those problems concerning productivity, sharpness of particle size distribution, improvement in flowability, etc.".
Also, the black toner has been required to show a high blackness and a high image density of line images and solid area images on copies.
With respect to this fact, on page 272 of the above-mentioned "Comprehensive Data Collection for Development and Utilization of Toner Materials", it has been described that "Powder development is characterized by a high image density. However, the image density as well as the fog density as described hereinafter, have strong influences on image characteristics".
As described above, it has been strongly demanded to enhance various properties of the black toner. It is known that the black toner, especially black pigments exposed to the surface of the black toner, have large influences on developing characteristics. There is a close relationship between properties of the black toner and those of the black pigments mixed and dispersed in the black toner.
That is, the flowability of the black toner considerably depends upon the surface condition of the black pigments exposed to the surface of the black toner. Therefore, the black pigments themselves have been strongly required to show an excellent flowability. Further, the blackness and density of the black toner also considerably depend upon the blackness and density of the black pigments contained in the black toner.
At present, as the black pigments for black toner, there may be mainly used carbon black fine particles (Japanese Patent No. 2715336 and Japanese Patent Application Laid-Open (KOKAI) No. 10-39546(1998)).
There have now been most strongly demanded black non-magnetic particles for black toner which can show not only excellent flowability and blackness, but also an excellent dispersibility in a binder resin. However, such black non-magnetic particles capable of satisfying all of these properties have not been obtained.
Namely, in the case where the above-mentioned carbon black fine particles are used as the black particles for black toner, the amount of the carbon black used must be restricted in order to obtain a black toner having a volume resistivity of not less than 10¹² Ω·cm. For this reason, there arises a problem that a sufficient blackness and a sufficient flowability cannot be obtained.
Further, there have been pointed out problems concerning safety and hygiene. These facts are explained below.
The carbon black fine particles themselves are a conductive material. Therefore, when the carbon black fine particles are used in a large amount in order to enhance the blackness of the black toner, the volume resistivity of the obtained black toner is reduced, so that the toner can be no longer used as a high-resistant or insulated toner. On the contrary, when the amount of the carbon black fine particles used is reduced from the standpoint of a high volume resistivity, the blackness of the black toner is deteriorated. Besides, due to the fact that the carbon black fine particles are those particles having an average particle size as fine as 0.010 to 0.060 µm, the carbon black fine particles are buried within each black toner particle, and the amount of the carbon black fine particles exposed to the surface of each black toner particle is reduced, thereby causing a tendency that the flowability thereof is also deteriorated.
Further, since the specific gravity of the carbon black fine particles is extremely low, i.e., as low as 1.80 to 1.85, the carbon black fine particles are deteriorated in handling property. In addition, when the black toner is prepared by dispersing such carbon black fine particles in a binder resin, the bulk specific gravity of the obtained black toner becomes considerably low. Therefore, the obtained toner tends to be scattered around, and deteriorated in flowability.
Furthermore, it has been reported that substances which are possible carcinogens and which are produced in the course of production of the carbon black fine particles, are disadvantageously incorporated as impurities in the carbon black fine particles. Thus, it has been pointed out that the black toner using such carbon black fine particles has a problem concerning safety.
It is an object of the present invention to provide black non-magnetic composite particles for black toners, which are not only excellent in flowability and blackness, but also can show an excellent dispersibility in a binder resin.
It is another object of the present invention to provide a high-resistant or insulated non-magnetic black toner which is excellent in flowability and blackness.
According to the present invention, there are provided black non-magnetic composite particles for a black toner composition, comprising:
(a) hematite and/or iron oxide hydroxide particles having an average particle diameter of from 0.055 to 0.95 µm;
(b) a coating on the surface of said hematite and/or iron oxide hydroxide particles, comprising at least one organosilicon compound selected from:
(1) organosilane compounds obtainable by drying or heat-treating alkoxysilane compounds,
(2) polysiloxanes or modified polysiloxanes, and
(3) fluoroalkyl organosilane compounds obtainable by drying or heat-treating fluoroalkylsilane compounds; and
(c) carbon black fine particles adhered on said coating wherein said adhered carbon black is obtainable by mixing and stirring from 1 to 25 parts by weight, per 100 parts by weight of said hematite and/or iron oxide hydroxide particles, of carbon black fine particles having an average particle size of 0.002 to 0.05 µm with said hematite and/or iron oxide hydroxide particles having a surface coating of a said alkoxysilane compound, a said polysiloxane or modified polysiloxane and/or a said fluoroalkylsilane compound.
According to the present invention, there is also provided:

a method of producing the black non-magnetic composite particles of the invention, which process comprises:
(a) mixing and stirring said hematite and/or iron oxide hydroxide particles together with at least one silicon-containing compound selected from:
(1) alkoxysilane compounds,
(2) polysiloxanes or modified polysiloxanes, and
(3) fluoroalkylsilane compounds,
(b) adding carbon black fine particles having an average particle size of 0.002 to 0.05 µm in an amount of 1 to 25 parts by weight based on 100 parts by weight of said hematite and/or iron oxide hydroxide particles, thereby obtaining mixed particles;
(c) mixing and stirring said mixed particles; and
(d) drying or heat-treating, thereby adhering said carbon black on the surface of the coating comprising the organosilicon compound;
a black toner composition comprising a binder resin and black non-magnetic composite particles according to the invention; and
a method for production of a black toner, which method comprises mixing black non-magnetic composite particles according to the invention with a binder resin and processing the resulting mixture thereby to form the toner.

In the accompanying drawings:

Fig. 1 is an electron micrograph (x 20,000) showing a particle structure of granular manganese-containing hematite particles used in Example 1.
Fig. 2 is an electron micrograph (x 20,000) showing a particle structure of carbon black fine particles used in Example 1.
Fig. 3 is an electron micrograph (x 20,000) showing a particle structure of black non-magnetic composite particles obtained in Example 1.
Fig. 4 is an electron micrograph (x 20,000) showing a particle structure of mixed particles composed of the granular manganese-containing hematite particles and the carbon black fine particles, for comparison.
The present invention is now described in detail below.
First, the black non-magnetic composite particles according to the present invention are described.
The black non-magnetic composite particles according to the present invention, comprise hematite particles or iron oxide hydroxide particles as core particles having an average paricle diameter of 0.055 to 095 µm, a coating comprising an organosilicon compound which is formed on the surface of each hematite particle or iron oxide hydroxide particle, and carbon black adhered on the coating comprising the organosilicon compound.
As the core particles in the present invention, there may be exemplified hematite particles, iron oxide hydroxide particles or mixed particles thereof. In the consideration of blackness of the obtained black non-magnetic composite particles, black hematite particles, black iron oxide hydroxide particles or mixed particles thereof are preferred. As the iron oxide hydroxide particles, there may be exemplified goethite particles, lepidicrosite particles.
As the black hematite particles, there may be exemplified manganese-containing hematite particles which contain manganese in an amount of 5 to 40 % by weight, preferably 10 to 20 % by weight (calculated as Mn) based on the weight of the manganese-containing hematite particles. As the black iron oxide hydroxide particles, there may be exemplified manganese-containing iron oxide hydroxide particles such as manganese-containing goethite particles, which contain manganese in an amount of 5 to 40 % by weight, preferably 10 to 20 % by weight (calculated as Mn) based on the weight of the manganese-containing iron oxide hydroxide particles.
As the core particles, from the standpoint of the particle shape thereof, there may be used any isotropic particles such as spherical particles, granular particles or polyhedral particles, e.g., hexahedral particles or octahedral particles, or any anisotropic particles having an aspect ratio (average major axial diameter/average minor axial diameter, hereinafter referred to merely as "aspect ratio") of not less than 2.0:1, such as acicular particles, spindle-shaped particles or rice grain-shaped particles. In the consideration of the flowability of the obtained black non-magnetic composite particles, the isotropic particles are preferably used as the core particles. Among these isotropic particles, the spherical particles and the granular particles are more preferred.
In the case of the isotropic hematite particles or iron oxide hydroxide particles as core particles, the average particle size (diameter) thereof is 0.055 to 0.95 µm, preferably 0.065 to 0.75 µm, more preferably 0.065 to 0.45 µm. The ratio of an average particle length to an average particle breadth thereof is usually not less than 1.0:1 and less than 2.0:1, preferably 1.0:1 to 1.8:1, more preferably 1.0:1 to 1.5:1.
In the case of the anisotropic hematite particles or iron oxide hydroxide particles as core particles, the average major axial diameter thereof is 0.055 to 0.95 µm, preferably 0.065 to 0.75 µm, more preferably 0.065 to 0.45 µm. The aspect ratio (average major axial diameter/average minor axial diameter) thereof is 2.0:1 to 20.0:1, preferably 2.0:1 to 15.o:1, more preferably 2.0:1 to 10.0:1.
When the average particle diameter of the hematite particles or iron oxide hydroxide particles is more than 0.95 µm, the obtained black non-magnetic composite particles are coarse particles and are deteriorated in tinting strength. On the other hand, when the average particle diameter is less than 0.055 µm, the intermolecular force between the particles is increased due to the reduction in particle diameter, so that agglomeration of the particles tends to be caused. As a result, it becomes difficult to uniformly coat the surface of the hematite particles or iron oxide hydroxide particle with the organosilicon compounds, and uniformly adhere the carbon black fine particles on the surface of the coating comprising the organosilicon compounds.
Further, in the case where the upper limit of the aspect ratio of the anisotropic hematite particles or iron oxide hydroxide particles exceeds 20.0:1, the particles tend to be entangled with each other, and it also becomes difficult to uniformly coat the surfaces of the hematite particles or iron oxide hydroxide particles with the organosilicon compounds, and uniformly adhere the carbon black fine particles on the surface of the coating composed of the organosilicon compounds.
As to the particle diameter distribution of the hematite particles or iron oxide hydroxide particles, the geometrical standard deviation value thereof is preferably not more than 2.0, more preferably not more than 1.8, still more preferably not more than 1.6. When the geometrical standard deviation value thereof is more than 2.0, coarse particles are contained therein, so that the particles are inhibited from being uniformly dispersed. As a result, it also becomes difficult to uniformly coat the surfaces of the hematite particles or iron oxide hydroxide particles with the organosilicon compounds, and uniformly adhere the carbon black fine particles on the surface of the coating composed of the organosilicon compounds. The lower limit of the geometrical standard deviation value is 1.01. It is industrially difficult to obtain particles having a geometrical standard deviation value of less than 1.01.
The BET specific surface area of the hematite particles or iron oxide hydroxide particles thereof is not less than 0.5 m²/g. When the BET specific surface area is less than 0.5 m²/g, the hematite particles or iron oxide hydroxide particles may become coarse particles, or the sintering between the particles may be caused, so that the obtained black non-magnetic composite particles also may become coarse particles and tend to be deteriorated in tinting strength. In the consideration of the tinting strength of the obtained black non-magnetic composite particles, the BET specific surface area of the hematite particles or iron oxide hydroxide particles is preferably not less than 1.0 m²/g, more preferably 3.0 m²/g. Further, in the consideration of uniformly coating the surfaces of the hematite particles or iron oxide hydroxide particles with the organosilicon compounds, and uniformly adhering the carbon black fine particles on a coat composed of the organosilicon compounds, the upper limit of the BET specific surface area of the hematite particles or iron oxide hydroxide particles, is usually 70 m²/g, preferably 50 m²/g, more preferably 20 m²/g.
As to the fluidity of the hematite particles or iron oxide hydroxide particles, the fluidity index thereof is about 25 to about 44. Among the hematite particles or iron oxide hydroxide particles having various shapes, the spherical particles are excellent in fluidity, for example, the fluidity index thereof is about 30 to about 44.
As to the blackness of the core particles, in the case of the hematite particles, the lower limit thereof is usually 18.0 when represented by L* value, and the upper limit thereof is usually 36.0, preferably 34.0 when represented by L* value. In the case of the iron oxide hydroxide particles such as the goethite particles, the lower limit thereof is usually more than 18.0 when represented by L* value, and the upper limit thereof is usually 38.0, preferably 36.0 when represented by L* value.
In the case of the black hematite particles, the lower limit thereof is usually 18.0 when represented by L* value, and the upper limit thereof is usually 28.0, preferably 25.0 when represented by L* value. In the case of the black iron oxide hydroxide particles such as the goethite particles, the lower limit thereof is usually more than 18.0 when represented by L* value, and the upper limit thereof is usually 30.0, preferably 28.0 when represented by L* value.
When the L* value exceeds the above-mentioned upper limit, the lightness of the particles is increased, so that it is difficult to obtain black non-magnetic composite particles having a sufficient blackness.
The particle shape and particle diameter of the black non-magnetic composite particles according to the present invention are considerably varied depending upon those of the hematite particles or iron oxide hydroxide particles as core particles. The black non-magnetic composite particles have a similar particle shape to that of the hematite particles or iron oxide hydroxide particles as core particle, and a slightly larger particle size than that of the hematite particles or iron oxide hydroxide particles as core particles.
More specifically, when the isotropic hematite particles or iron oxide hydroxide particles are used as core particles, the obtained black non-magnetic composite particles according to the present invention, have an average particle diameter of usually 0.06 to 1.0 µm, preferably 0.07 to 0.8 µm, more preferably 0.07 to 0.5 µm and a ratio of an average particle length to an average particle breadth of usually not less than 1.0 and less than 2.0, preferably 1.0 to 1.8, more preferably 1.0 to 1.5. When the anisotropic hematite particles or iron oxide hydroxide particles are used as core particles, the obtained black non-magnetic composite particles according to the present invention, have an average particle diameter of usually 0.06 to 1.0 µm, preferably 0.07 to 0.8 µm, more preferably 0.07 to 0.5 µm, and the aspect ratio of usually 2.0:1 to 20.0:1, preferably 2.0: 1 to 15.0:1, more preferably 2.0:1 to 10.0:1.
When the average particle diameter of the black non-magnetic composite particles is more than 1.0 µm, the obtained black non-magnetic composite particles may be coarse particles, and deteriorated in tinting strength. On the other hand, when the average particle diameter thereof is less than 0.06 µm, the black non-magnetic composite particles tends to be agglomerated by the increase of intermolecular force due to the reduction in particle size, thereby deteriorating the dispersibility in a binder resin upon production of the black toner.
When the aspect ratio is more than 20.0:1, the black non-magnetic composite particles may be entangled with each other in the binder resin, so that the dispersibility in binder resin tends to be deteriorated.
The geometrical standard deviation value of the black non-magnetic composite particles according to the present invention is preferably not more than 2.0, more preferably 1.01 to 1.8, still more preferably 1.01 to 1.6. The lower limit of the geometrical standard deviation value thereof is preferably 1.01. When the geometrical standard deviation value thereof is more than 2.0, the tinting strength of the black non-magnetic composite particles is likely to be deteriorated due to the existence of coarse particles therein. It is industrially difficult to obtain such particles having a geometrical standard deviation of less than 1.01.
The BET specific surface area of the black non-magnetic composite particles according to the present invention, is usually 1 to 200 m²/g, preferably 2 to 150 m²/g, more preferably 2.5 to 100 m²/g. When the BET specific surface area thereof is less than 1 m²/g, the obtained black non-magnetic composite particles may be coarse, and the sintering between the particles is caused, thereby deteriorating the tinting strength. On the other hand, when the BET specific surface area is more than 200 m²/g, the black non-magnetic composite particles tend to be agglomerated together by the increase in intermolecular force due to the reduction in particle diameter, thereby deteriorating the dispersibility in a binder resin upon production of the black toner.
As to the fluidity of the black non-magnetic composite particles according to the present invention, the fluidity index thereof is preferably 45 to 80, more preferably 46 to 80, still more preferably 47 to 80. When the fluidity index thereof is less than 45, the fluidity of the black non-magnetic composite particles becomes insufficient, thereby failing to improve the fluidity of the finally obtained black toner. Further, in the production process of the black toner, there tend to be caused defects such as clogging of hopper, etc., thereby deteriorating the handling property or workability.
As to the blackness of the black non-magnetic composite particles according to the present invention, in the case the hematite particles are used as core particles, the upper limit of the blackness of the black non-magnetic composite particles is usually 20.0, preferably 19.0, more preferably 18.5 when represented by L* value. In the case the iron oxide hydroxide particles such as the goethite particles are used as core particles, the upper limit of the blackness of the black non-magnetic composite particles is usually 20.0, preferably 19.5, more preferably 19.0 when represented by L* value.
In the case the black hematite particles are used as core particles, the upper limit of the blackness of the black non-magnetic composite particles is usually 20.0, preferably 18.5, more preferably 18.0 when represented by L* value. In the case the black iron oxide hydroxide particles such as the goethite particles are used as core particles, the upper limit of the blackness of the black non-magnetic composite particles is usually 20.0, preferably 19.0, more preferably 18.5 when represented by L* value.
When the L* value thereof is more than 20.0, the lightness of the obtained black non-magnetic composite particles becomes high, so that the black non-magnetic composite particles having a sufficient blackness cannot be obtained. The lower limit of the blackness thereof is 15 when represented by L* value.
The dispersibility in binder resin of the black non-magnetic composite particles according to the present invention, is preferably 4th or 5th rank, more preferably 5th rank when evaluated by the method described hereinafter.
The percentage of desorption of carbon black fine particles from the black non-magnetic composite particles according to the present invention, is preferably not more than 20 %, more preferably not more than 10 %. When the desorption percentage of the carbon black fine particles is more than 20 %, the desorbed carbon black fine particles tend to inhibit the black non-magnetic composite particles from being uniformly dispersed in the binder resin upon production of the black toner.
The coating formed on the surfaces of the core particles comprises at least one organosilicon compound selected from the group consisting of (1) organosilane compounds obtained by drying or heat-treating alkoxysilane compounds; (2) polysiloxanes, or modified polysiloxanes selected from the group consisting of (2-A) polysiloxanes modified with at least one compound selected from the group consisting of polyethers, polyesters and epoxy compounds (hereinafter referred to merely as "modified polysiloxanes"), and (2-B) polysiloxanes whose molecular terminal is modified with at least one group selected from the group consisting of carboxylic acid groups, alcohol groups and a hydroxyl group; and (3) fluoroalkyl organosilane compounds obtained by drying or heat-treating fluoroalkylsilane compounds.
The organosilane compounds (1) can be produced by drying or heat-treating alkoxysilane compounds represented by the formula (I): R¹ _aSiX_4-a wherein R¹ is C₆H₅-, (CH₃)₂CHCH₂- or n-C_bH_2b+1- (wherein b is an integer of 1 to 18); X is CH₃O- or C₂H₅O-; and a is an integer of 0 to 3.
The drying or heat-treatment of the alkoxysilane compounds is conducted, for example, at a temperature of usually 40 to 200°C, preferably 60 to 150°C for usually 10 minutes to 12 hours, preferably 30 minutes to 3 hours.
Specific examples of the alkoxysilane compounds may include methyl triethoxysilane, dimethyl diethoxysilane, tetraethoxysilane, phenyl triethyoxysilane, diphenyl diethoxysilane, methyl trimethoxysilane, dimethyl dimethoxysilane, tetramethoxysilane, phenyl trimethoxysilane, diphenyl dimethoxysilane, isobutyl trimethoxysilane, decyl trimethoxysilane or the like. Among these alkoxysilane compounds, in view of the desorption percentage and the adhering effect of carbon black fine particles, methyl triethoxysilane, phenyl triethyoxysilane, methyl trimethoxysilane, dimethyl dimethoxysilane and isobutyl trimethoxysilane are preferred, and methyl triethoxysilane and methyl trimethoxysilane are more preferred.
As the polysiloxanes (2), there may be used those compounds represented by the formula (II):
wherein R² is H- or CH₃-, and d is an integer of 15 to 450.
Among these polysiloxanes, in view of the desorption percentage and the adhering effect of carbon black fine particles, polysiloxanes having methyl hydrogen siloxane units are preferred.
As the modified polysiloxanes (2-A), there may be used:
(a) polysiloxanes modified with polyethers represented by the formula (III):
wherein R³ is -(-CH₂-)_h-; R⁴ is -(-CH₂-)_i-CH₃; R⁵ is -OH, -COOH, -CH=CH₂, -C(CH₃)=CH₂ or -(-CH₂-)_j-CH₃; R⁶ is -(-CH₂-)_k-CH₃; g and h are an integer of 1 to 15; i, j and k are an integer of 0 to 15; e is an integer of 1 to 50; and f is an integer of 1 to 300;
(b) polysiloxanes modified with polyesters represented by the formula (IV):
wherein R⁷, R⁸ and R⁹ are -(-CH₂-)_q- and may be the same or different; R¹⁰ is -OH, -COOH, -CH=CH₂, -C(CH₃)=CH₂ or -(-CH₂-)_r-CH₃; R¹¹ is -(-CH₂-)_s-CH₃; n and q are an integer of 1 to 15; r and s are an integer of 0 to 15; e' is an integer of 1 to 50; and f' is an integer of 1 to 300;
(c) polysiloxanes modified with epoxy compounds represented by the formula (V):
wherein R¹² is -(-CH₂-)_v-; v is an integer of 1 to 15; t is an integer of 1 to 50; and u is an integer of 1 to 300; or a mixture thereof.
Among these modified polysiloxanes (2-A), in view of the desorption percentage and the adhering effect of carbon black fine particles, the polysiloxanes modified with the polyethers represented by the formula (III), are preferred.
As the terminal-modified polysiloxanes (2-B), there may be used those represented by the formula (VI):
wherein R¹³ and R¹⁴ are -OH, R¹⁶OH or R¹⁷COOH and may be the same or different; R¹⁵ is -CH₃ or -C₆H₅; R¹⁶ and R¹⁷ are -(-CH₂-)_y-; y is an integer of 1 to 15; w is an integer of 1 to 200; and x is an integer of 0 to 100.
Among these terminal-modified polysiloxanes, in view of the desorption percentage and the adhering effect of carbon black fine. particles, the polysiloxanes whose terminals are modified with carboxylic acid groups are preferred.
The fluoroalkyl organosilane compounds (3) may be produced by drying or heat-treating fluoroalkylsilane compounds represented by the formula (VII): CF₃(CF₂)_zCH₂CH₂(R¹⁸)_a'SiX_4-a' wherein R¹⁸ is CH₃-, C₂H₅-, CH₃O- or C₂H₅O-; X is CH₃O- or C₂H₅O-; and z is an integer of 0 to 15; and a' is an integer of 0 to 3.
The drying or the heat-treatment of the fluoroalkylsilane compounds may be conducted, for example, at a temperature of usually 40 to 200°C, preferably 60 to 150°C for usually 10 minutes to 12 hours, preferably 30 minutes to 3 hours.
Specific examples of the fluoroalkylsilane compounds may include trifluoropropyl trimethoxysilane, tridecafluorooctyl trimethoxysilane, heptadecafluorodecyl trimethoxysilane, heptadecafluorodecylmethyl dimethoxysilane, trifluoropropyl triethoxysilane, tridecafluorooctyl triethoxysilane, heptadecafluorodecyl triethoxysilane, heptadecafluorodecylmethyl diethoxysilane or the like. Among these fluoroalkylsilane compounds, in view of the desorption percentage and the adhering effect of carbon black fine particles, trifluoropropyl trimethoxysilane, tridecafluorooctyl trimethoxysilane and heptadecafluorodecyl trimethoxysilane are preferred, and trifluoropropyl trimethoxysilane and tridecafluorooctyl trimethoxysilane are more preferred.
The coating amount of the organosilicon compounds is usually 0.02 to 5.0 % by weight, preferably 0.03 to 2.0 by weight, more preferably 0.05 to 1.5 % by weight (calculated as Si) based on the weight of the hematite particles or iron oxide hydroxide particles coated with the organosilicon compounds.
When the coating amount of the organosilicon compounds is less than 0.02 % by weight, it becomes difficult to adhere the carbon black fine particles on the surfaces of the hematite particles or iron oxide hydroxide particles in such an amount enough to improve the fluidity and blackness of the obtained black non-magnetic composite particles.
On the other hand, when the coating amount of the organosilicon compounds is more than 5.0 % by weight, a sufficient amount of the carbon black fine particles can be adhered on the surfaces of the hematite particles or iron oxide hydroxide particles. However, the use of such unnecessarily large amount of the organosilicon compounds is meaningless because the effect of enhancing the fluidity and blackness of the obtained black non-magnetic composite particles is already saturated.
As the carbon black fine particles used in the black non-magnetic composite particles according to the present invention, there may be exemplified commercially available carbon black particles such as furnace black, channel black or the like. Specific examples of the commercially available carbon black particles usable in the present invention, may include MA100, MA7, #1000, #2400B, #30, MA8, MA11, #50, #52, #45, #2200B, MA600, etc. (tradenames; produced by Mitsubishi Chemical Corp.), Seast9H, Seast7H, Seast6, Seast3H, Seast300, SeastFM, etc. (tradenames; produced by Tokai Carbon Co., Ltd.) or the like. In the consideration of compatibility with the organosilicon compounds, MA100, MA7, #1000, #2400B and #30 are preferred.
The average particle size of the carbon black fine particles is usually about 0.002 to about 0.05 µm, preferably about 0.002 to about 0.035 µm.
When the average particle size of the carbon black fine particles is less than 0.002 µm, the carbon black fine particles are too fine to be well handled.
On the other hand, when the average particle size of the carbon black fine particles is more than 0.05 µm, the particle size of the carbon black fine particles becomes much larger than that of the hematite particles or iron oxide hydroxide particles as core particles, thereby causing insufficient adhesion of the carbon black fine particles onto the coating composed of the organosilicon compounds, and increasing the desorption percentage of the carbon black fine particles. As a result, the obtained black non-magnetic composite particles tend to be deteriorated in dispersibility in a binder resin upon the production of black toner.
The ratio of the average particle size of the hematite particles or iron oxide hydroxide particles to that of the carbon black fine particles is preferably not less than 2:1. When the ratio is less than 2:1, the particle size of the carbon black fine particles becomes considerably larger as compared to that of the hematite particles or iron oxide hydroxide particles as core particles, thereby causing insufficient adhesion of the carbon black fine particles onto the coat composed of the organosilicon compounds, and increasing the desorption percentage of the carbon black fine particles. As a result, the obtained black non-magnetic composite particles tend to be deteriorated in dispersibility in a binder resin upon the production of black toner.
The amount of the carbon black fine particles adhered is 1 to 25 parts by weight based on 100 parts by weight of the hematite particles or iron oxide hydroxide particles as core particles.
When the amount of the carbon black fine particles adhered is less than 1 part by weight, the amount of the carbon black fine particles adhered is insufficient, so that it becomes difficult to obtain black non-magnetic composite particles having a sufficient fluidity and blackness.
On the other hand, when the amount of the carbon black fine particles adhered is more than 25 parts by weight, the obtained black non-magnetic composite particles can show a sufficient fluidity and blackness. However, since the amount of the carbon black fine particles adhered is considerably large, the carbon black fine particles tend to be desorbed from the coating composed of the organosilicon compound. As a result, the obtained black non-magnetic composite particles tend to be deteriorated in dispersibility in a binder resin upon the production of black toner.
In the black non-magnetic composite particles according to the present invention, at least a part of the surface of the hematite particle or iron oxide hydroxide particle as core particle may be preliminarily coated with at least one compound selected from the group consisting of hydroxides of aluminum, oxides of aluminum, hydroxides of silicon and oxides of silicon (hereinafter referred to as "coat composed of hydroxides and/or oxides of aluminum and/or silicon"). In this case, the obtained black non-magnetic composite particles can show a higher dispersibility in a binder resin as compared to in the case where the hematite particles or iron oxide hydroxide particles are uncoated with hydroxides and/or oxides of aluminum and/or silicon.
The coating amount of the hydroxides and/or oxides of aluminum and/or silicon is preferably 0.01 to 50 % by weight (calculated as Al, SiO₂ or a sum of Al and SiO₂) based on the weight of the hematite particles or iron oxide hydroxide particles as core particles.
When the coating amount of the hydroxides and/or oxides of aluminum and/or silicon is less than 0.01 % by weight, the effect of enhancing the dispersibility of the obtained black non-magnetic composite particles in a binder resin upon the production of black toner may not be obtained.
On the other hand, when the coating amount of the hydroxides and/or oxides of aluminum and/or silicon is more than 50 % by weight, the obtained black non-magnetic composite particles can exhibit a good dispersibility in a binder resin upon the production of black toner. However, the use of such unnecessarily large coating amount of the hydroxides and/or oxides of aluminum and/or silicon is meaningless.
The particle size, geometrical standard deviation, BET specific surface area, fluidity, blackness L* value and desorption percentage of carbon black fine particles of the black non-magnetic composite particles wherein the surface of the core particle is coated with the hydroxides and/or oxides of aluminum and/or silicon according to the present invention, are substantially the same as those of the black non-magnetic composite particles wherein the core particle is uncoated with the hydroxides and/or oxides of aluminum and/or silicon according to the present invention.
The black non-magnetic composite particles according to the present invention can be produced by the following method.
The granular hematite particles as the isotropic core particles according to the present invention can be produced by heating, in air at a temperature of 750 to 1,000°C, granular magnetite particles which are obtained by a so-called wet oxidation method, i.e., by passing an oxygen-containing gas through a suspension containing a ferrous hydroxide colloid obtained by reacting an aqueous ferrous salt solution with alkali hydroxide. (Refer to Japanese Patent Publication (KOKOKU) No. 44-668)
The granular manganese-containing hematite particles as the isotropic core particles according to the present invention, can be produced by heating, in air at a temperature of 750 to 1,000°C, (a) coated magnetite particles which are obtained by first producing granular magnetite particles by a so-called wet oxidation method, i.e., by passing an oxygen-containing gas through a suspension containing a ferrous hydroxide colloid obtained by reacting an aqueous ferrous salt solution with alkali hydroxide, and then coating the obtained granular magnetite particles with a manganese compound in an amount of 8 to 150 atm % (calculated as Mn) based on whole Fe, or (b) magnetite particles containing manganese in an amount of 8 to 150 atm % (calculated as Mn) based on whole Fe, which are obtained by conducting the above wet oxidation method in the presence of manganese. In the consideration of blackness of the obtained manganese-containing hematite particles, it is preferred to use the manganese-containing magnetite particles (b). (Refer to Japanese Patent Application Laid-open (KOKAI) No. 4-144924)
The acicular or spindle-shaped hematite particles as the anisotropic core particles according to the present invention, can be produced by heating acicular or spindle-shaped iron oxide hydroxide particles obtained by the method described hereinafter, in air at a temperature of 400 to 800°C.
The acicular or spindle-shaped iron oxide hydroxide particles as the anisotropic core particles according to the present invention, can be produced by passing an oxygen-containing gas through a suspension containing either ferrous hydroxide colloid, iron carbonate or iron-containing precipitates obtained by reacting an aqueous ferrous salt solution with alkali hydroxide, alkali carbonate or both of alkali hydroxide and alkali carbonate, and then subjecting the obtained iron oxide hydroxide particles to filtration, washing with water and drying. (Refer to Japanese Patent Publication (KOKOKU) No. 39-5610)
The acicular or spindle-shaped manganese-containing hematite particles as the anisotropic core particles according to the present invention, can be produced by heating, in air at a temperature of 400 to 800°C, acicular or spindle-shaped iron oxide hydroxide particles containing manganese in an amount of 8 to 150 atomic % based on whole Fe, which are obtained by the method described hereinafter. (Refer to Japanese Patent Application Laid-open (KOKAI) Nos. 6-263449 and 8-259237)
The acicular or spindle-shaped manganese-containing iron oxide hydroxide particles as the anisotropic core particles according to the present invention, can be produced by passing an oxygen-containing gas through a suspension containing either ferrous hydroxide colloid, iron carbonate or iron-containing precipitates obtained by reacting an aqueous ferrous salt solution with alkali hydroxide, alkali carbonate or both of alkali hydroxide and alkali carbonate, in the presence of manganese in an amount of 8 to 150 atm % (calculated as Mn) based on whole Fe, and then subjecting the obtained iron oxide hydroxide particles to filtration, washing with water and drying.
The coat of the hematite particles or iron oxide hydroxide particles with the alkoxysilane compounds, the polysiloxanes, the modified polysiloxanes, the terminal-modified polysiloxanes or the fluoroalkylsilane compounds, can be conducted by mechanically mixing and stirring the hematite particles or iron oxide hydroxide particles together with the alkoxysilane compounds, the polysiloxanes, the modified polysiloxanes, the terminal-modified polysiloxanes or the fluoroalkylsilane compounds; or by mechanically mixing and stirring both the components together while spraying the alkoxysilane compounds, the polysiloxanes, the modified polysiloxanes, the terminal-modified polysiloxanes or the fluoroalkylsilane compounds onto the hematite particles or iron oxide hydroxide particles. In these cases, substantially whole amount of the alkoxysilane compounds, the polysiloxanes, the modified polysiloxanes, the terminal-modified polysiloxanes or the fluoroalkylsilane compounds added can be applied onto the surfaces of the hematite particles or iron oxide hydroxide particles.
In order to uniformly coat the surfaces of the hematite particles or iron oxide hydroxide particles with the alkoxysilane compounds, the polysiloxanes, the modified polysiloxanes, the terminal-modified polysiloxanes or the fluoroalkylsilane compounds, it is preferred that the hematite particles or iron oxide hydroxide particles are preliminarily diaggregated by using a pulverizer. As the apparatuses for the mixing and stirring, there may be used an edge runner, a Henschel mixer or the like.
The conditions for the mixing and stirring such as mixing ratio, linear load, stirring speed or mixing and stirring time, may be appropriately adjusted so as to coat the surfaces of the hematite particles or iron oxide hydroxide particles with the alkoxysilane compounds, the polysiloxanes, the modified polysiloxanes, the terminal-modified polysiloxanes or the fluoroalkylsilane compounds as uniformly as possible. The mixing and stirring time for the coating treatment is, for example, preferably not less than 20 minutes.
The amount of the alkoxysilane compounds, the polysiloxanes, the modified polysiloxanes, the terminal-modified polysiloxanes or the fluoroalkylsilane compounds added, is preferably 0.15 to 45 parts by weight based on 100 parts by weight of the hematite particles or iron oxide hydroxide particles. When the amount of the organosilicon compounds added is less than 0.15 part by weight, it may become difficult to adhere the carbon black fine particles in such an amount enough to improve the blackness and flowability of the obtained black non-magnetic composite particles. On the other hand, when the amount of the organosilicon compounds added is more than 45 parts by weight, a sufficient amount of the carbon black fine particles can be adhered on the surface of the coating, but it is meaningless because the blackness and flowability of the black composite particles cannot be further improved by using such an excess amount of the organosilicon compounds.
Next, the carbon black fine particles are added to the hematite particles or iron oxide hydroxide particles coated with the organosilicon compounds, and the resultant mixture is mixed and stirred to adhere the carbon black fine particles on the surfaces of the coating composed of the organosilicon compounds, and then dried or heat-treated.
In the case where the alkoxysilane compounds (1) and the fluoroalkylsilane compounds (3) are used as the coating compound, after the carbon black fine particles are adhered on the surface of the coating, the resultant composite particles are dried or heat-treated, for example, at a temperature of usually 40 to 200°C, preferably 60 to 150°C for usually 10 minutes to 12 hours, preferably 30 minutes to 3 hours, thereby forming a coating composed of the organosilane compounds (1) and the fluoroalkyl organosilane compounds (3), respectively.
It is preferred that the carbon black fine particles are added little by little and slowly, especially about 5 to 60 minutes.
The conditions for mixing and stirring the hematite particles or iron oxide hydroxide particles coated with the organosilicon compounds and the carbon black fine particles, such as mixing ratio, linear load stirring speed or mixing and stirring time, may be appropriately adjusted so as to uniformly adhere the carbon black fine particles on the surface of the coating. The mixing and stirring time for the adhesion treatment is, for example, preferably not less than 20 minutes.
The amount of the carbon black fine particles added, is preferably 1 to 25 parts by weight based on 100 parts by weight of the hematite particles or iron oxide hydroxide particles. When the amount of the carbon black fine particles added is less than 1 part by weight, it may become difficult to adhere the carbon black fine particles in such an amount enough to improve the blackness and flowability of the obtained black non-magnetic composite particles. On the other hand, when the amount of the carbon black fine particles added is more than 25 parts by weight, a sufficient blackness and flowability of the resultant black non-magnetic composite particles can be obtained, but the carbon black fine particles tend to be desorbed from the surface of the coating because of too large amount of the carbon black fine particles adhered, resulting in deteriorated dispersibility in the binder resin upon the production of the black toner.
At least a part of the surface of the hematite particles or iron oxide hydroxide particles may be coated with at least one compound selected from the group consisting of hydroxides of aluminum, oxides of aluminum, hydroxides of silicon and oxides of silicon, if required, prior to mixing and stirring with the alkoxysilane compounds, the polysiloxanes, the modified polysiloxanes, the terminal-modified polysiloxanes or the fluoroalkylsilane compounds.
The coat of the hydroxides and/or oxides of aluminum and/or silicon may be conducted by adding an aluminum compound, a silicon compound or both the compounds to a water suspension in which the hematite particles or iron oxide hydroxide particles are dispersed, followed by mixing and stirring, and further adjusting the pH value of the suspension, if required, thereby coating the surfaces of the hematite particles or iron oxide hydroxide particles with at least one compound selected from the group consisting of hydroxides of aluminum, oxides of aluminum, hydroxides of silicon and oxides of silicon. The thus obtained particles coated with the hydroxides and/or oxides of aluminum and/or silicon are then filtered out, washed with water, dried and pulverized. Further, the particles coated with the hydroxides and/or oxides of aluminum and/or silicon may be subjected to post-treatments such as deaeration treatment and compaction treatment, if required.
As the aluminum compounds, there may be exemplified aluminum salts such as aluminum acetate, aluminum sulfate, aluminum chloride or aluminum nitrate, alkali aluminates such as sodium aluminate, alumina sols or the like.
The amount of the aluminum compound added is 0.01 to 50 % by weight (calculated as Al) based on the weight of the hematite particles or iron oxide hydroxide particles. When the amount of the aluminum compound added is less than 0.01 % by weight, it may be difficult to sufficiently coat the surfaces of the hematite particles or iron oxide hydroxide particles with hydroxides and/or oxides of aluminum, thereby failing to achieve the improvement of the dispersibility in the binder resin upon the production of the black toner. On the other hand, when the amount of the aluminum compound added is more than 50 % by weight, the coating effect is saturated and, therefore, it is meaningless to add such an excess amount of the aluminum compound.
As the silicon compounds, there may be exemplified #3 water glass, sodium orthosilicate, sodium metasilicate, colloidal silica or the like.
The amount of the silicon compound added is 0.01 to 50 % by weight (calculated as SiO₂) based on the weight of the hematite particles or iron oxide hydroxide particles. When the amount of the silicon compound added is less than 0.01 % by weight, it may be difficult to sufficiently coat the surfaces of the hematite particles or iron oxide hydroxide particles with hydroxides and/or oxides of silicon, thereby failing to achieve the improvement of the dispersibility in the binder resin upon the production of the black toner. On the other hand, when the amount of the silicon compound added is more than 50 % by weight, the coating effect is saturated and, therefore, it is meaningless to add such an excess amount of the silicon compound.
In the case where both the aluminum and silicon compounds are used in combination for the coating, the total amount of the aluminum and silicon compounds added is preferably 0.01 to 50 % by weight (calculated as a sum of Al and SiO₂) based on the weight of the hematite particles or iron oxide hydroxide particles.
Next, the black toner according to the present invention is described.
The black toner according to the present invention comprises the black non-magnetic composite particles, and a binder resin. The black toner may further contain a mold release agent, a colorant, a charge-controlling agent and other additives, if necessary.
The black toner according to the present invention has an average particle size of usually 3 to 25 µm, preferably 4 to 18 µm, more preferably 5 to 15 µm.
The amount of the binder resin used in the black toner is usually 50 to 3500 parts by weight, preferably 50 to 2000 parts by weight, more preferably 50 to 1000 parts by weight based on 100 parts by weight of the black non-magnetic composite particles.
As the binder resins, there may be used vinyl-based polymers, i.e., homopolymers or copolymers of vinyl-based monomers such as styrene, alkyl acrylates and alkyl methacrylates. As the styrene monomers, there may be exemplified styrene and substituted styrenes. As the alkyl acrylate monomers, there may be exemplified acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate or the like.
It is preferred that the above copolymers contain styrene-based components in an amount of usually 50 to 95 % by weight.
In the binder resin used in the present invention, the above-mentioned vinyl-based polymers may be used in combination with polyester-based resins, epoxy-based resins, polyurethane-based resins or the like.
As to the fluidity of the black toner according to the present invention, the fluidity index is usually 70 to 100, preferably 71 to 100, more preferably 72 to 100. When the fluidity index is less than 70, the black toner may not show a sufficient fluidity.
The blackness of the black toner according to the present invention is usually not more than 20, preferably not more than 19.8, more preferably not more than 19.5 when represented by L* value. When the blackness thereof is more than 20, the lightness of the black toner may be increased, resulting in insufficient blackness. The lower limit of the blackness of the black toner is usually about 15 when represented by L* value.
The volume resistivity of the black toner according to the present invention, is usually not less than 1.0 × 10¹³ Ω·cm, preferably not less than 3.0 x 10¹³ Ω·cm, more preferably not less than 5.0 x 10¹³ Ω·cm and less than 1.0 x 10¹⁷ Ω·cm. When the volume resistivity is less than 1.0 x 10¹³ Ω·cm, the charge amount of the black toner tends to vary depending upon environmental conditions in which the toner is used, resulting in unstable properties of the black toner.
The black toner according to the present invention may be produced by a known method of mixing and kneading a predetermined amount of a binder resin and a predetermined amount of the black non-magnetic composite particles together, and then pulverizing the mixed and kneaded material into particles. More specifically, the black non-magnetic composite particles and the binder resin are intimately mixed together with, if necessary, a mold release agent, a colorant, a charge-controlling agent or other additives by using a mixer. The obtained mixture is then melted and kneaded by a heating kneader, thereby dispersing the black non-magnetic composite particles in the binder resin. Successively, the molten mixture is cooled and solidified to obtain a resin mixture. The obtained resin mixture is then pulverized and classified, thereby producing a black toner having an aimed particle size.
As the mixers, there may be used a Henschel mixer, a ball mill or the like. As the heating kneaders, there may be used a roll mill, a kneader, a twin-screw extruder or the like. The pulverization of the resin mixture may be conducted by using pulverizers such as a cutter mill, a jet mill or the like. The classification of the pulverized particles may be conducted by known methods such as air classification, etc., as described in Japanese Patent No. 2683142 or the like.
As the other method of producing the black toner, there may be exemplified a suspension polymerization method or an emulsion polymerization method. In the suspension polymerization method, polymerizable monomers and the black non-magnetic composite particles are intimately mixed together with, if necessary, a colorant, a polymerization initiator, a cross-linking agent, a charge-controlling agent or the other additives and then the obtained mixture is dissolved and dispersed together so as to obtain a monomer composition. The obtained monomer composition is added to a water phase containing a suspension stabilizer while stirring, thereby granulating and polymerizing the composition to form black toner particles having an aimed particle size.
In the emulsion polymerization method, the monomers and the black non-magnetic composite particles are dispersed in water together with, if necessary, a colorant, a polymerization initiator or the like and then the obtained dispersion is polymerized while adding an emulsifier thereto, thereby producing black toner particles having an aimed particle size.
An important point of the present invention lies in that the black non-magnetic composite particles comprising the hematite particles or iron oxide hydroxide particles as the core particles, which have an average particle diameter of 0.055 to 0.95 µm and which may be coated with at least one compound selected from the group consisting of hydroxides of aluminum, oxides of aluminum, hydroxides of silicon and oxides of silicon; the organosilicon compounds coated on the surface of the hematite particle or iron oxide hydroxide particle; the carbon black fine particles having an average particle size of 0.002 to 0.05 µm, which are adhered on the surface of the coating composed of the organosilicon compounds, in which the total amount of the carbon black fine particles adhered to the coating composed of the organosilicon compounds is 1 to 25 parts by weight based on 100 parts by weight of the hematite particles or iron oxide hydroxide particles, can show not only excellent fluidity and blackness, but also an excellent dispersibility in a binder resin upon the production of a black toner due to less amount of carbon black fine particles desorbed (or fallen-off) from the surfaces of the particles.
The reason why the amount of the carbon black fine particles desorbed (or fallen-off) from the surfaces of the black non-magnetic composite particles according to the present invention, is small, is considered as follows. That is, the surfaces of the hematite particles or iron oxide hydroxide particles as the core particles and the organosilicon compounds are strongly bonded to each other, so that the carbon black fine particles bonded to the surfaces of the hematite particles or iron oxide hydroxide particles through the organosilicon compounds can be prevented from being desorbed from the hematite particles or iron oxide hydroxide particles.
In particular, in the case of the alkoxysilane compounds (1) and the fluoroalkylsilane compounds (3), metallosiloxane bonds (≡Si-O-M wherein M represents a metal atom contained in the hematite particles or iron oxide hydroxide particles as the core particles, such as Si, Al, Fe or the like) are formed between the surfaces of the hematite particles or iron oxide hydroxide particles and alkoxy groups contained in the organosilicon compounds onto which the carbon black fine particles are adhered, thereby forming a stronger bond between the organosilicon compounds on which the carbon black fine particles are adhered, and the surfaces of the hematite particles or iron oxide hydroxide particles.
The reason why the amount of the carbon black fine particles desorbed (or fallen-off) from the surfaces of the black non-magnetic composite particles according to the present invention, is small, is considered as follows. That is, the surfaces of the hematite particles or iron oxide hydroxide particles and the organosilicon compounds are strongly bonded to each other, so that the carbon black fine particles bonded to the surfaces of the hematite particles or iron oxide hydroxide particles through the organosilicon compounds can be prevented from being desorbed from the hematite particles or iron oxide hydroxide particles.
The reason why the black non-magnetic composite particles according to the present invention can show an excellent dispersibility in a binder resin upon the production of black toner, is considered such that since only a small amount of the carbon black fine particles are desorbed (or fallen-off) from the surfaces of the black non-magnetic composite particles, the black non-magnetic composite particles is free from deterioration in dispersibility due to the desorbed (or fallen-off) carbon black fine particles, and further since the carbon black fine particles are adhered onto the surfaces of the black non-magnetic composite particles and, therefore, irregularities are formed on the surfaces of the black non-magnetic composite particles, the contact between the particles can be suppressed.
The reason why the black non-magnetic composite particles according to the present invention can show an excellent fluidity, is considered as follows. That is, the carbon black fine particles which are ordinarily agglomerated together due to fineness thereof, are allowed to be uniformly and densely adhered on the surfaces of the hematite particles or iron oxide hydroxide particles as the core particles and, therefore, can be dispersed nearly in the form of primary particles, so that many fine irregularities are formed on the surfaces of the hematite particles or iron oxide hydroxide particles.
The reason why the black non-magnetic composite particles according to the present invention can show an excellent blackness, is considered such that since the carbon black fine particles are uniformly and densely adhered on the surfaces of the hematite particles or iron oxide hydroxide particles as the core particles, the color tone of the core particles is hidden behind the carbon black fine particles, so that an inherent color tone of carbon black can be exhibited.
Therefore, the black toner produced by using the above black non-magnetic composite particles, can show excellent fluidity and blackness.
The reason why the black toner according to the present invention can show an excellent fluidity, is considered as follows. That is, the black non-magnetic composite particles on which a large amount of the carbon black fine particles are uniformly adhered, are blended in the black toner, so that many fine irregularities are formed on the surface of the black toner.
The reason why the black toner according to the present invention can show an excellent blackness, is considered such that the black non-magnetic composite particles having an excellent blackness is blended in the black toner.
As described above, since the black non-magnetic composite particles according to the present invention, are excellent not only in fluidity and blackness, but also in dispersibility in a binder resin due to less amount of the carbon black fine particles desorbed or (fallen-off) from the surfaces thereof, the black non-magnetic composite particles according to the present invention, are suitable as black non-magnetic composite particles for black toner capable of attaining a high image quality and a high copying speed.
In addition, since the black non-magnetic composite particles according to the present invention, are excellent in dispersibility in a binder resin, the particles can show excellent handling property and workability and, therefore, are preferable from an industrial viewpoint.
Further, the black toner produced from the above black non-magnetic composite particles which are excellent in fluidity and blackness, can also show excellent fluidity and blackness. Accordingly, the black toner is suitable as black toner capable of attaining a high image quality and a high copying speed.
Furthermore, in the black toner according to the present invention, since the black non-magnetic composite particles contained therein are excellent in dispersibility, it is possible to expose the black non-magnetic composite particles to the surface of the black toner independently and separately. As a result, the black toner can be free from being deteriorated in electric resistance due to the existence of the carbon black fine particles. Accordingly, the black toner according to the present invention is suitable as a high-resistance or insulated black toner.

EXAMPLES

The present invention is described in more detail by Examples and Comparative Examples, but the Examples are only illustrative and, therefore, not intended to limit the scope of the present invention.
Various properties were measured by the following methods.
(1) The average particle diameter, the average major axial diameter and average minor axial diameter of hematite particles or iron oxide hydroxide particles, black non-magnetic composite particles and carbon black fine particles were respectively expressed by the average of values (measured in a predetermined direction) of about 350 particles which were sampled from a micrograph obtained by magnifying an original electron micrograph (x 20,000) by four times in each of the longitudinal and transverse directions.
(2) The aspect ratio of the particles was expressed by the ratio of average major axial diameter to average minor axial diameter thereof.
(3) The geometrical standard deviation of particle diameter was expressed by values obtained by the following method. That is, the particle diameters (or major axial diameters) were measured from the above magnified electron micrograph. The actual particle diameters (or major axial diameters) and the number of the particles were calculated from the measured values. On a logarithmic normal probability paper, the particle diameters (or major axial diameters) were plotted at regular intervals on the abscissa-axis and the accumulative number (under integration sieve) of particles belonging to each interval of the particle diameters (or major axial diameters) were plotted by percentage on the ordinate-axis by a statistical technique. The particle diameters (or major axial diameters) corresponding to the number of particles of 50 % and 84.13 %, respectively, were read from the graph, and the geometrical standard deviation was calculated from the following formula: Geometrical standard deviation = {particle diameters (or major axial diameters) corresponding to 84.13 % under integration sieve}/{particle diameters (or major axial diameters) (geometrical average diameter) corresponding to 50 % under integration sieve}The closer to 1 the geometrical standard deviation value, the more excellent the particle diameter distribution.
(4) The specific surface area was expressed by the value measured by a BET method.
(5) The amount of Mn which was present within hematite particles or iron oxide hydroxide particles or on surfaces thereof, the amounts of Al and Si which were present within black non-magnetic composite particles or on surfaces thereof, and the amount of Si contained in the organosilicon compounds, were measured by a fluorescent X-ray spectroscopy device 3063 (manufactured by Rigaku Denki Kogyo Co., Ltd.) according to JIS K0119 "General rule of fluorescent X-ray analysis".
(6) The amount of carbon adhered on the black non-magnetic composite particles was measured by "Horiba Metal, Carbon and Sulfur Analyzer EMIA-2200 Model" (manufactured by Horiba Seisakusho Co., Ltd.).
(7) The fluidity of hematite particles or iron oxide hydroxide particles, black non-magnetic composite particles and black toner was expressed by a fluidity index which was a sum of indices obtained by converting on the basis of the same reference measured values of an angle of repose, a degree of compaction (%), an angle of spatula and a degree of agglomeration as particle characteristics which were measured by a powder tester (tradename, produced by Hosokawa Micron Co., Ltd.). The closer to 100 the fluidity index, the more excellent the fluidity of the particles.
(8) The blackness of hematite particles or iron oxide hydroxide particles, black non-magnetic composite particles and black toner was measured by the following method. That is, 0.5 g of sample particles and 1.5 cc of castor oil were intimately kneaded together by a Hoover's muller to form a paste. 4.5 g of clear lacquer was added to the obtained paste and was intimately kneaded to form a paint. The obtained paint was applied on a cast-coated paper by using a 6-mil applicator to produce a coating film piece (having a film thickness of about 30 µm). The thus obtained coating film piece was measured according to JIS Z 8729 by a multi-light source spectrographic colorimeter MSC-IS-2D (manufactured by Suga Testing Machines Manufacturing Co., Ltd.) to determine an L* value of colorimetric indices thereof. The blackness was expressed by the L* value measured. Here, the L* value represents a lightness, and the smaller the L* value, the more excellent the blackness.
(9) The desorption percentage of carbon black fine particles adhered on the black non-magnetic composite particles was measured by the following method. The closer to zero the desorption percentage, the smaller the amount of carbon black fine particles desorbed from the surfaces of the black non-magnetic composite particles. That is, 3 g of the black non-magnetic composite particles and 40 ml of ethanol were placed in a 50-ml precipitation pipe and then was subjected to ultrasonic dispersion for 20 minutes. Thereafter, the obtained dispersion was allowed to stand for 120 minutes, and the carbon black fine particles desorbed were separated from the black non-magnetic composite particles on the basis of the difference in specific gravity between both the particles. Next, the black non-magnetic composite particles from which the desorbed carbon black fine particles were separated, were mixed again with 40 ml of ethanol, and the obtained mixture was further subjected to ultrasonic dispersion for 20 minutes. Thereafter, the obtained dispersion was allowed to stand for 120 minutes, thereby separating the black non-magnetic composite particles and the carbon black fine particles desorbed from each other. The thus obtained black non-magnetic composite particles were dried at 100°C for one hour, and then the carbon content thereof was measured by the "Horiba Metal, Carbon and Sulfur Analyzer EMIA-2200 Model" (manufactured by Horiba Seisakusho Co., Ltd.). The desorption percentage of the carbon black fine particles was calculated according to the following formula: Desorption percentage of carbon black fine particles = {(Wa - We)/Wa} × 100 wherein Wa represents an amount of carbon black fine particles initially adhered on the black non-magnetic composite particles; and We represents an amount of carbon black fine particles still adhered on the black non-magnetic composite particles after desorption test.
(10) The dispersibility in a binder resin of the black non-magnetic composite particles was evaluated by counting the number of undispersed agglomerated particles on a micrograph (x 200 times) obtained by photographing a sectional area of the obtained black toner particle using an optical microscope (BH-2, manufactured by Olympus Kogaku Kogyo Co., Ltd.), and classifying the results into the following five ranks. The 5th rank represents the most excellent dispersing condition.

Rank 1:

not less than 50 undispersed agglomerated particles per 0.25 mm² were recognized;

Rank 2:

10 to 49 undispersed agglomerated particles per 0.25 mm² were recognized;

Rank 3:

5 to 9 undispersed agglomerated particles per 0.25 mm² were recognized;

Rank 4:

1 to 4 undispersed agglomerated particles per 0.25 mm² were recognized;

Rank 5:

No undispersed agglomerated particles were recognized.
(11) The average particle diameter of the black toner was measured by a laser diffraction-type particle diameter distribution-measuring apparatus (Model HELOSLA/KA, manufactured by Sympatec Corp.).
(12) The volume resistivity of the black toner was measured by the following method.
That is, first, 0.5 g of a sample particles to be measured was weighted, and press-molded at 140 Kg/cm² using a KBr tablet machine (manufactured by Simazu Seisakusho Co., Ltd.), thereby forming a cylindrical test piece.
Next, the thus obtained cylindrical test piece was exposed to an atmosphere maintained at a temperature of 25°C and a relative humidity of 60 % for 12 hours. Thereafter, the cylindrical test piece was set between stainless steel electrodes, and a voltage of 15V was applied between the electrodes using a Wheatstone bridge (TYPE2768, manufactured by Yokogawa-Hokushin Denki Co., Ltd.) to measure a resistance value R (Ω).
The cylindrical test piece was measured with respect to an upper surface area A (cm²) and a thickness t₀ (cm) thereof. The measured values were inserted into the following formula, thereby obtaining a volume resistivity X (Ω·cm). X (Ω·cm) = R x (A/t0)

Example 1:

20 kg of granular-shaped Mn-containing hematite particles shown in the electron micrograph (x 20,000) of Fig. 1 (average particle size: 0.30 µm; geometrical standard deviation value: 1.46; BET specific surface area value: 3.6 m²/g; Mn content: 13.3 % by weight (calculated as Mn) based on the weight of the particle; blackness (L* value): 22.6; fluidity index: 36), were deagglomerated in 150 liters of pure water using a stirrer, and further passed through a "TK pipeline homomixer" (tradename, manufactured by Tokushu Kika Kogyo Co., Ltd.) three times, thereby obtaining a slurry containing the granular-shaped Mn-containing hematite particles.
Successively, the obtained slurry containing the granular-shaped Mn-containing hematite particles was passed through a transverse-type sand grinder (tradename "MIGHTY MILL MHG-1.5L", manufactured by Inoue Seisakusho Co., Ltd.) five times at an axis-rotating speed of 2,000 rpm, thereby obtaining a slurry in which the granular-shaped Mn-containing hematite particles were dispersed.
The particles in the obtained slurry which remained on a sieve of 325 meshes (mesh size: 44 µm) was 0 %. The slurry was filtered and washed with water, thereby obtaining a filter cake containing the granular-shaped Mn-containing hematite particles. After the obtained filter cake containing the granular-shaped Mn-containing hematite particles was dried at 120°C, 11.0 kg of the dried particles were then charged into an edge runner "MPUV-2 Model" (tradename, manufactured by Matsumoto Chuzo Tekkosho Co., Ltd.), and mixed and stirred at 30 Kg/cm for 30 minutes, thereby lightly deagglomerating the particles.
110 g of methyl triethoxysilane was mixed and diluted with 200 ml of ethanol to obtain a methyl triethoxysilane solution. The methyl triethoxysilane solution was added to the deagglomerated granular-shaped Mn-containing hematite particles under the operation of the edge runner. The granular-shaped Mn-containing hematite particles were continuously mixed and stirred at a linear load of 60 Kg/cm for 60 minutes.
Next, 990 g of carbon black fine particles shown in the electron micrograph (x 20,000) of Fig. 2 (particle shape: granular shape; average particle size: 0.022 µm; geometrical standard deviation value: 1.68; BET specific surface area value: 134 m²/g; and blackness (L* value): 16.6) were added to the granular-shaped Mn-containing hematite particles coated with methyl triethoxysilane for 10 minutes while operating the edge runner. Further, the mixed particles were continuously stirred at a linear load of 60 Kg/cm for 60 minutes to adhere the carbon black fine particles on the coating composed of methyl triethoxysilane, thereby obtaining black non-magnetic composite particles.
The obtained black non-magnetic composite particles were aged at 105°C for 60 minutes by using a drier to evaporate water, ethanol or the like which were remained on surfaces of the black non-magnetic composite particles. As shown in the electron micrograph (x 20,000) of Fig. 3, the resultant black non-magnetic composite particles had an average particle diameter of 0.31 µm. In addition, the black non-magnetic composite particles showed a geometrical standard deviation value of 1.46, a BET specific surface area value of 9.1 m²/g, a fluidity index of 48 and a blackness (L* value) of 17.6. The desorption percentage of the carbon black fine particles from the black non-magnetic composite particles was 6.6 %. The coating amount of an organosilane compound produced from methyl triethoxysilane was 0.16 % by weight, calculated as Si. Since no independent carbon black fine particles were observed on the electron micrograph of Fig. 3, it was determined that a whole amount of the carbon black fine particles were adhered on the coating composed of the organosilane compound produced from methyl triethoxysilane.

Example 2:

400 g of the black non-magnetic composite particles obtained in Example 1, 540 g of styrene-butyl acrylate-methyl methacrylate copolymer resin (molecular weight = 130,000, styrene/butyl acrylate/methyl methacrylate = 82.0/16.5/1.5), 60 g of polypropylene wax (molecular weight: 3,000) and 15 g of a charge-controlling agent were charged into a Henschel mixer, and mixed and stirred therein at 60°C for 15 minutes. The obtained mixed particles were melt-kneaded at 140°C using a continuous-type twin-screw kneader (T-1), and the obtained kneaded material was cooled, coarsely pulverized and finely pulverized in air. The obtained particles were subjected to classification, thereby producing a black toner.
The obtained black toner had an average particle diameter of 10.1 pm, a dispersibility of 5th rank, a fluidity index of 75, a blackness (L* value) of 18.6, a volume resistivity of 1.2 x 10¹⁴ Ω·cm.

Example 3:

20 kg of granular-shaped Mn-containing hematite particles shown in the electron micrograph (x 20,000) of Fig. 1 (average particle diameter: 0.30 µm; geometrical standard deviation value: 1.46; BET specific surface area value: 3.6 m²/g; Mn content: 13.3 % by weight (calculated as Mn) based on the weight of the particle; blackness (L* value): 22.6; fluidity index: 36), were deagglomerated in 150 liters of pure water using a stirrer, and further passed through a "TK pipeline homomixer" (tradename, manufactured by Tokushu Kika Kogyo Co., Ltd.) three times, thereby obtaining a slurry containing the granular-shaped Mn-containing hematite particles.
Successively, the obtained slurry containing the granular-shaped Mn-containing hematite particles was passed through a transverse-type sand grinder (tradename "MIGHTY MILL MHG-1.5L", manufactured by Inoue Seisakusho Co., Ltd.) five times at an axis-rotating speed of 2,000 rpm, thereby obtaining a slurry in which the granular-shaped Mn-containing hematite particles were dispersed.
The particles in the obtained slurry which remained on a sieve of 325 meshes (mesh size: 44 µm) was 0 %. The slurry was filtered and washed with water, thereby obtaining a filter cake containing the granular-shaped Mn-containing hematite particles. After the obtained filter cake containing the granular-shaped Mn-containing hematite particles was dried at 120°C, 11.0 kg of the dried particles were then charged into an edge runner "MPUV-2 Model" (tradename, manufactured by Matsumoto Chuzo Tekkosho Co., Ltd.), and mixed and stirred at 30 Kg/cm for 30 minutes, thereby lightly deagglomerating the particles.
110 g of methyl hydrogen polysiloxane (tradename: "TSF484", produced by Toshiba Silicone Co., Ltd.) were added to the deagglomerated granular-shaped Mn-containing hematite particles under the operation of the edge runner. The granular-shaped Mn-containing hematite particles were continuously mixed and stirred at a linear load of 60 Kg/cm for 60 minutes.
Next, 990 g of carbon black fine particles shown in the electron micrograph (× 20,000) of Fig. 2 (particle shape: granular shape; average particle diameter: 0.022 µm; geometrical standard deviation value: 1.68; BET specific surface area value: 134 m²/g; and blackness (L* value): 16.6) were added to the granular-shaped Mn-containing hematite particles coated with methyl hydrogen polysiloxane for 10 minutes while operating the edge runner. Further, the mixed particles were continuously stirred at a linear load of 60 Kg/cm for 60 minutes to adhere the carbon black fine particles on the coating composed of methyl hydrogen polysiloxane, thereby obtaining black non-magnetic composite particles.
The obtained black non-magnetic composite particles were dried at 105°C for 60 minutes by using a drier to evaporate water or the like which were remained on surfaces of the black non-magnetic composite particles. The obtained black non-magnetic composite particles had an average particle diameter of 0.31 µm. In addition, the black non-magnetic composite particles had a geometrical standard deviation value of 1.46, a BET specific surface area value of 8.9 m²/g, a fluidity index of 46 and a blackness (L* value) of 18.2. The desorption percentage of the carbon black fine particles from the black non-magnetic composite particles was 6.4 %. The coating amount of methyl hydrogen polysiloxane was 0.41 % by weight, calculated as Si. Since no independent carbon black fine particles were observed on the electron micrograph, it was determined that a whole amount of the carbon black fine particles were adhered on the coating composed of methyl hydrogen polysiloxane.

Example 4:

400 g of the black non-magnetic composite particles obtained in Example 3, 540 g of styrene-butyl acrylate-methyl methacrylate copolymer resin (molecular weight = 130,000, styrene/butyl acrylate/methyl methacrylate = 82.0/16.5/1.5), 60 g of polypropylene wax (molecular weight: 3,000) and 15 g of a charge-controlling agent were charged into a Henschel mixer, and mixed and stirred therein at 60°C for 15 minutes. The obtained mixed particles were melt-kneaded at 140°C using a continuous-type twin-screw kneader (T-1), and the obtained kneaded material was cooled, coarsely pulverized and finely pulverized in air. The obtained particles were subjected to classification, thereby producing a black toner.
The obtained black toner had an average particle diameter of 10.1 µm, a dispersibility of 5th rank, a fluidity index of 73, a blackness (L* value) of 19.7, a volume resistivity of 9.6 x 10¹⁴ Ω·cm.

Example 5:

20 kg of granular-shaped Mn-containing hematite particles shown in the electron micrograph (× 20,000) of Fig. 1 (average particle diameter: 0.30 pm; geometrical standard deviation value: 1.46; BET specific surface area value: 3.6 m²/g; Mn content: 13.3 % by weight (calculated as Mn) based on the weight of the particle; blackness (L* value): 21.6; fluidity index: 36), were deagglomerated in 150 liters of pure water using a stirrer, and further passed through a "TK pipeline homomixer" (tradename, manufactured by Tokushu Kika Kogyo Co., Ltd.) three times, thereby obtaining a slurry containing the granular-shaped Mn-containing hematite particles.
Successively, the obtained slurry containing the granular-shaped Mn-containing hematite particles was passed through a transverse-type sand grinder (tradename "MIGHTY MILL MHG-1.5L", manufactured by Inoue Seisakusho Co., Ltd.) five times at an axis-rotating speed of 2,000 rpm, thereby obtaining a slurry in which the granular-shaped Mn-containing hematite particles were dispersed.
The particles in the obtained slurry which remained on a sieve of 325 meshes (mesh size: 44 µm) was 0 %. The slurry was filtered and washed with water, thereby obtaining a filter cake containing the granular-shaped Mn-containing hematite particles. After the obtained filter cake containing the granular-shaped Mn-containing hematite particles was dried at 120°C, 11.0 kg of the dried particles were then charged into an edge runner "MPUV-2 Model" (tradename, manufactured by Matsumoto Chuzo Tekkosho Co., Ltd.), and mixed and stirred at 30 Kg/cm for 30 minutes, thereby lightly deagglomerating the particles.
165 g of tridecafluorooctyl trimethoxysilane (tradename "TSL8257", produced by Toshiba Silicone Co., Ltd.) were added to the deagglomerated granular-shaped Mn-containing hematite particles under the operation of the edge runner. The granular-shaped Mn-containing hematite particles were continuously mixed and stirred at a linear load of 60 Kg/cm for 60 minutes.
Next, 550 g of carbon black fine particles shown in the electron micrograph (× 20,000) of Fig. 2 (particle shape: granular shape; average particle diameter: 0.022 µm; geometrical standard deviation value: 1.68; BET specific surface area value: 134 m²/g; and blackness (L* value): 16.6) were added to the granular-shaped Mn-containing hematite particles coated with tridecafluorooctyl trimethoxysilane for 10 minutes while operating the edge runner. Further, the mixed particles were continuously stirred at a linear load of 60 Kg/cm for 60 minutes to adhere the carbon black fine particles on the coating composed of tridecafluorooctyl trimethoxysilane, thereby obtaining black non-magnetic composite particles.
The obtained black non-magnetic composite particles were aged at 105°C for 60 minutes by using a drier to evaporate water or the like which were remained on surfaces of the black non-magnetic composite particles. The obtained black non-magnetic composite particles had an average particle diameter of 0.31 µm. In addition, the black non-magnetic composite particles showed a geometrical standard deviation value of 1.45, a BET specific surface area value of 5.0 m²/g, a fluidity index of 49 and a blackness (L* value) of 17.8. The desorption percentage of the carbon black fine particles from the black non-magnetic composite particles was 6.5 %. The coating amount of a fluoroalkyl organosilane compound produced from tridecafluorooctyl trimethoxysilane was 0.10 % by weight, calculated as Si. Since no independent carbon black fine particles were observed on the electron micrograph, it was determined that a whole amount of the carbon black fine particles were adhered on the coating composed of the fluoroalkyl organosilane compound produced from tridecafluorooctyl trimethoxysilane.

Example 6:

400 g of the black non-magnetic composite particles obtained in Example 5, 540 g of styrene-butyl acrylate-methyl methacrylate copolymer resin (molecular weight = 130,000, styrene/butyl acrylate/methyl methacrylate = 82.0/16.5/1.5), 60 g of polypropylene wax (molecular weight: 3,000) and 15 g of a charge-controlling agent were charged into a Henschel mixer, and mixed and stirred therein at 60°C for 15 minutes. The obtained mixed particles were melt-kneaded at 140°C using a continuous-type twin-screw kneader (T-1), and the obtained kneaded material was cooled, coarsely pulverized and finely pulverized in air. The obtained particles were subjected to classification, thereby producing a black toner.
The obtained black toner had an average particle diameter of 10.0 µm, a dispersibility of 5th rank, a fluidity index of 76, a blackness (L* value) of 19.2, a volume resistivity of 2.8 × 10¹⁴ Ω·cm.

Core particles 1 to 4:

Various hematite particles or iron oxide hydroxide particles, were prepared by known methods. The same procedure as defined in Example 1 was conducted by using the thus prepared particles, thereby obtaining deagglomerated hematite particles or iron oxide hydroxide particles as core particles.
Various properties of the thus obtained hematite particles or iron oxide hydroxide particles are shown in Table 1.

Core particles 5:

The same procedure as defined in Example 1 was conducted by using 20 kg of the deagglomerated granular-shaped Mn-containing hematite particles (core particles 1) and 150 liters of water, thereby obtaining a slurry containing the granular-shaped Mn-containing hematite particles. The pH value of the obtained re-dispersed slurry containing the granular-shaped Mn-containing hematite particles was adjusted to 10.5 by adding an aqueous sodium solution, and then the concentration of the slurry was adjusted to 98 g/liter by adding water thereto. After 150 liters of the slurry was heated to 60°C, 5444 ml of a 1.0 mol/liter sodium alminate solution (equivalent to 1.0 % by weight (calculated as Al) based on the weight of the granular-shaped Mn-containing hematite particles) was added to the slurry. After allowing the slurry to stand for 30 minutes, the pH value of the slurry was adjusted to 7.5 by adding an acetic acid solution. After allowing the slurry to stand for 30 minutes, the slurry was subjected to filtration, washing with water, drying and pulverization, thereby obtaining the granular-shaped Mn-containing hematite particles coated with hydroxides of aluminum.
Main production conditions are shown in Table 2, and various properties of the obtained granular-shaped Mn-containing hematite particles are shown in Table 3.

Core particles 6 to 8:

The same procedure as defined in the production of the core particles 5 above, was conducted except that kind of core particles, and kind and amount of additives used in the surface treatment were varied, thereby obtaining surface-treated hematite particles or iron oxide hydroxide particles.
Main production conditions are shown in Table 2, and. various properties of the obtained surface-treated hematite particles or iron oxide hydroxide particles are shown in Table 3.

Examples 7 to 14 and comparative Examples 1 to 5:

The same procedure as defined in Example 1 was conducted except that kind of hematite particles or iron oxide hydroxide particles to be treated, addition or non-addition of an alkoxysilane compound in the coating treatment with alkoxysilane compound, kind and amount of the alkoxysilane compound added, treating conditions of edge runner in the coating treatment, kind and amount of carbon black fine particles adhered, and treating conditions of edge runner used in the adhering process of the carbon black fine particles, were varied, thereby obtaining black non-magnetic composite particles. The black non-magnetic composite particles obtained in Examples 7 to 14 were observed by an electron microscope. As a result, almost no independent carbon black fine particles were recognized. Therefore, it was confirmed that a substantially whole amount of the carbon black fine particles were adhered on the coating composed of organosilane compound produced from the alkoxysilane compound.
Various properties of the carbon black fine particles A to C are shown in Table 4.
Main production conditions are shown in Table 5, and various properties of the obtained black non-magnetic composite particles are shown in Table 6.
Meanwhile, in Comparative Example 1, the granular-shaped Mn-containing hematite particles uncoated with the alkoxysilane compound and the carbon black fine particles were mixed and stirred together by an edge runner in the same manner as described above, thereby obtaining treated particles. An electron micrograph (x 20,000) of the thus treated particles is shown in Fig. 4. As shown in Fig. 4, it was confirmed that the carbon black fine particles were not adhered on the surfaces of the granular-shaped Mn-containing hematite particles, and both the particles were present independently.

Examples 15 to 22 and Comparative Examples 6 to 17:

The same procedure as defined in Example 2 was conducted by using the black non-magnetic composite particles obtained in Examples 7 to 14, the core particles 1 to 4, the carbon black fine particles A to C, the mixed particles composed of the granular-shaped Mn-containing hematite particles and the carbon black fine particles used in Comparative Example 1, and the black non-magnetic particles obtained in Comparative Examples 2 to 5, thereby obtaining black toners.
Main production conditions and various properties of the obtained black toners are shown in Table 7.

Examples 23 to 46 and Comparative Examples 18 to 26:

The same procedure as defined in Example 3 was conducted except that kind of hematite particles or iron oxide hydroxide particles to be treated, addition or non-addition of a polysiloxane or modified polysiloxane, kind and amount of the polysiloxane or modified polysiloxane, treating conditions of edge runner in the coating treatment, kind and amount of carbon black fine particles adhered, and treating conditions of edge runner used in the adhering process of the carbon black fine particles, were varied, thereby obtaining black non-magnetic composite particles. The black non-magnetic composite particles obtained in Examples 23 to 46 were observed by an electron microscope. As a result, almost no independent carbon black fine particles were recognized. Therefore, it was confirmed that a substantially whole amount of the carbon black fine particles were adhered on the coating composed of polysiloxane or modified polysiloxane.
Main production conditions are shown in Tables 8, 10 and 12, and various properties of the obtained black non-magnetic composite particles are shown in Tables 9, 11 and 13.

Examples 47 to 70 and Comparative Examples 27 to 35:

The same procedure as defined in Example 4 was conducted by using the black non-magnetic particles obtained in Examples 47 to 70, and the black non-magnetic composite particles obtained in Comparative Examples 18 to 26, thereby obtaining black toners.
Main production conditions and various properties of the obtained black toners are shown in Tables 14 to 16.

Examples 71 to 78 and Comparative Examples 36 to 38:

The same procedure as defined in Example 5 was conducted except that kind of hematite particles or iron oxide hydroxide particles to be treated, addition or non-addition of a fluoroalkyl organosilane compound, kind and amount of the fluoroalkyl organosilane compound added, treating conditions of edge runner in the coating treatment, kind and amount of carbon black fine particles adhered, and treating conditions of edge runner used in the adhering process of the carbon black fine particles, were varied, thereby obtaining black non-magnetic composite particles. The black non-magnetic composite particles obtained in Examples 71 to 78 were observed by an electron microscope. As a result, almost no independent carbon black fine particles were recognized. Therefore, it was confirmed that a substantially whole amount of the carbon black fine particles were adhered on the coating composed of a fluoroalkyl organosilane compound produced from the fluoroalkylsilane compound.
Main production conditions are shown in Table 17, and various properties of the obtained black non-magnetic composite particles are shown in Table 18.

Examples 79 to 86 and Comparative Examples 39 to 41:

The same procedure as defined in Example 6 was conducted by using the black non-magnetic particles obtained in Examples 71 to 78, and the black non-magnetic composite particles obtained in Comparative Examples 36 to 38, thereby obtaining black toners.
Main production conditions and various properties of the obtained black toners are shown in Table 19.

Claims

Black non-magnetic composite particles for a black toner composite, comprising:

(a) hematite and/or iron oxide hydroxide particles having an average particle diameter of from 0.055 to 0.95 µm;

(b) a coating on the surface of said hematite and/or iron oxide hydroxide particles, comprising at least one organosilicon compound selected from:

(1) organosilane compounds obtainable by drying or heat-treating alkoxysilane compounds,

(2) polysiloxanes or modified polysiloxanes, and

(3) fluoroalkyl organosilane. compounds obtainable by drying or heat-treating fluoroalkylsilane compounds; and

(c) carbon black fine particles adhered on said coating wherein said adhered carbon black is obtainable by mixing and stirring from 1 to 25 parts by weight, per 100 parts by weight of said hematite and/or iron oxide hydroxide particles, of carbon black fine particles having an average particle size of 0.002 to 0.05 µm with said hematite and/or iron oxide hydroxide particles having a surface coating of a said alkoxysilane compound, a said polysiloxane or modified polysiloxane and/or a said fluoroalkylsilane compound.
Particles according to claim 1, wherein said hematite and/or iron oxide hydroxide particles have a coat on at least a part of the surface thereof, which comprises at least one hydroxide or oxide selected from hydroxides or oxides of either aluminum or silicon in an amount of from 0.01 to 50 % by weight, calculated as Al and/or SiO₂, based on the total weight of the hematite and/or iron oxide hydroxide particles.
Particles according to claim 1 or 2, wherein said alkoxysilane compound is represented by the general formula (I): R¹ _aSiX_4-a wherein R¹ is C₆H₅-, (CH₃)₂CHCH₂- or n-C_bH_2b+1- (wherein b is an integer of from 1 to 18); X is CH₃O- or C₂H₅O-; and a is an integer of from 0 to 3.
Particles according to claim 3, wherein said alkoxysilane compound is methyl triethoxysilane, dimethyl diethoxysilane, tetraethoxysilane, phenyl triethoxysilane, diphenyl diethoxysilane, methyl trimethoxysilane, dimethyl dimethoxysilane, tetramethoxysilane, phenyl trimethoxysilane, diphenyl dimethoxysilane, isobutyl trimethoxysilane or decyl trimethoxysilane.
Particles according to any one of the preceding claims, wherein said polysiloxanes are represented by the general formula (II):
wherein R² is H- or CH₃-, and d is an integer of 15 to 450.
Particles according to claim 5, wherein said polysiloxanes have methyl hydrogen siloxane units.
Particles according to any one of the preceding claims, wherein said modified polysiloxanes are selected from:

(A) polysiloxanes modified with at least one polyether and/or polyester and/or epoxy compound, and

(B) polysiloxanes whose molecular terminal is modified with at least one group selected from carboxylic acid, alcohol and hydroxyl groups.
Particles according to claim 7, wherein said polysiloxanes modified with at least one polyether and/or polyester and/or epoxy compound are represented by the general formula (III), (IV) or (V):
wherein R³ is -(-CH₂-)_h-; R⁴ is -(-CH₂-)_i-CH₃; R⁵ is -OH, -COOH, -CH=CH₂, -C(CH₃)=CH₂ or -(-CH₂-)_j-CH₃; R⁶ is -(-CH₂-)_k-CH₃; g and h are integers of from 1 to 15; i, j and k are integers of from 0 to 15; e is an integer of from 1 to 50; and f is an integer of from 1 to 300;
wherein R⁷, R⁸ and R⁹ are -(-CH₂-)_q- and may be the same or different; R¹⁰ is -OH, -COOH, -CH=CH₂, -C(CH₃)=CH₂ or -(-CH₂-)_r-CH₃; R¹¹ is -(-CH₂-)_s-CH₃; n and q are integers of from 1 to 15; r and s are integers of from 0 to 15; e' is an integer of from 1 to 50; and f' is an integer of from 1 to 300; or
wherein R¹² is -(-CH₂-)_v-; v is an integer of from 1 to 15; t is an integer of from 1 to 50; and u is an integer of from 1 to 300.
Particles according to claim 7 or 8, wherein said polysiloxanes whose molecular terminal is modified with at least one group selected from carboxylic acid, alcohol and hydroxyl groups are represented by the general formula (VI):
wherein R¹³ and R¹⁴ are -OH, R¹⁶OH or R¹⁷COOH and may be the same of different; R¹⁵ is -CH₃ or -C₆H₅; R¹⁶ and R¹⁷ are -(-CH₂-)_y-; y is an integer of from 1 to 15; w is an integer of from 1 to 200; and x is an integer of from 0 to 100.
Particles according to any one of the preceding claims, wherein said fluoroalkylsilane compounds are represented by the general formula (VII): CF₃(CF₂)_zCH₂CH₂(R¹⁸)_a'SiX_4-a' wherein R¹⁸ is CH₃-, C₂H₅-, CH₃O- or C₂H₅O-; X is CH₃O- or C₂H₅O-; and z is an integer of from 0 to 15; and a' is an integer of from 0 to 3.
Particles according to any one of the preceding claims, wherein the amount of said coating organosilicon compound(s) is from 0.02 to 5.0 % by weight, calculated as Si, based on the total weight of the organosilicon compound(s) and said hematite and/or iron oxide hydroxide particles.
Particles according to any one of the preceding claims, which have an average particle diameter of from 0.06 to 1.0 µm.
Particles according to any one of the preceding claims, which have a geometrical standard deviation of particle diameters of from 1.01 to 2.0.
Particles according to any one of the preceding claims, which have a BET specific surface area value of from 1 to 200 m²/g.
Particles according to any one of the preceding claims, which have a flowability index of from 45 to 80.
Particles according to any one of the preceding claims, which have a blackness (L* value) of from 15 to 20.
A process for producing black non-magnetic composite particles as claimed in claim 1, which process comprises:

(a) mixing and stirring said hematite and/or iron oxide hydroxide particles together with at least one silicon-containing compound selected from:

(1) alkoxysilane compounds,

(2) polysiloxanes or modified polysiloxanes, and

(3) fluoroalkylsilane compounds,

thereby coating the surface of said hematite ahd/or iron oxide hydroxide particles with said compound;

(b) adding carbon black fine particles having an average particle size of 0.002 to 0.05 µm in an amount of 1 to 25 parts by weight based on 100 parts by weight of said hematite and/or iron oxide hydroxide particles, thereby obtaining mixed particles;

(c) mixing and stirring said mixed particles; and

(d) drying or heat-treating, thereby adhering said carbon black on the surface of the coating comprising the organosilicon compound.
Black toner composition comprising:

a binder resin and black non-magnetic composite particles according to any one of claims 1 to 16.
Toner according to claim 18, which comprises from 50 to 3500 parts by weight of binder- resin per 100 parts by weight of said black non-magnetic composite particles.
Toner according to claim 18 or 19, which has an average particle diameter of from 3 to 25 µm.
Toner according to any one of claims 18 to 20, which has a flowability index of from 70 to 100.
Toner according to any one of claims 18 to 21, which has a blackness (L* value) of from 15 to 20.
Toner according to any one of claims 18 to 22, which has a volume resistivity of not less than 1.0 x 10¹³ Ω· cm.
A method for production of a black toner, which method comprises mixing black non-magnetic composite particles according to any one of claims 1 to 16 with a binder resin and processing the resulting mixture thereby to form the toner.