JPH07181715A - Toner composition using pigment-containing composite particles and its production - Google Patents

Abstract

PURPOSE:To obtain a toner compsn. having low dependency on the environment and stable electrostatic chargeability and not causing imperfect cleaning or toner filming. CONSTITUTION:One or more kinds of hydrophobic monomers and one or more kinds of water-soluble monomers are subjected to deposition polymn. in an aq. system in the presence of a pigment to obtain pigment-contg. composite particles. A nonspherical toner is obtd. by associating and fusing the composite particles and the objective toner compsn. contg. the nonspherical toner and one or more kinds of fullerene or nanotube as an external additive is produced.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner composition used in electrophotography, electrostatic printing and magnetic recording.

[0002]

2. Description of the Related Art As a conventional electrophotographic method,
A large number of methods are known as described in U.S. Pat. No. 2,976,921 and Japanese Patent Publication No. 42-23910. In general, a latent image is formed on a photosensitive photoreceptor, then the latent image is developed with a toner, the toner image is transferred to a transfer material such as paper, and then fixed by heating, pressure or the like. Get a copy.
After the transfer is completed, a cleaning process is provided for removing the toner remaining on the photoconductor, and the process for obtaining the copy is repeated.

[0003]

However, the above-mentioned cleaning is carried out by various methods such as a blade method, a brush method and a web method. However, as the copying is repeated, the toner which cannot be removed by the current cleaning method is gradually removed from the surface of the photoreceptor. Accumulates on the surface and causes cleaning failure and toner filming. In order to improve such development, for example, Japanese Patent Publication No. 48
-8141, JP-A-50-120631, JP-A-52-84741 and the like propose methods of adding an external additive to a toner. Although these methods are useful for poor cleaning and toner filming, they are highly environmentally dependent,
This phenomenon is particularly noticeable in high temperature and high humidity, and the charge amount of the toner decreases as the copying is repeated, resulting in a decrease in image density, fog and toner scattering.

The present invention has been made based on the above circumstances, and an object of the present invention is to provide a toner composition having little environmental dependence, stable chargeability, and cleaning failure and toner filming. It is to provide things.

[0005]

The present inventors have used fullerenes and nanotubes as external additives in order to achieve the above-mentioned object. That is, since fullerenes and nanotubes can induce various groups such as conductivity, hydrophilicity, and hydrophobicity, it is possible to enhance the performance of the toner, such as fluidity, moisture resistance, and chargeability. Further, fullerene and NATNO-tube can be used as a charge additive by depositing on a surface of a known surface fluidity additive, for example, colloidal silica such as Aerosil R972 (trademark).

Based on such knowledge, at least one or more fullerenes or nanotubes as external additives, at least one or more hydrophobic monomers and at least one or more aqueous monomers are subjected to aqueous precipitation polymerization in the presence of a pigment. The above object was achieved by providing a toner composition containing a toner which is associated and fused with the pigment-containing composite particles.

[0007]

The present invention will be described in detail below.

The external additives used in the present invention include:
Fullerenes or nanotubes are used. The fullerene or nanotube is not particularly limited, and a conventionally known one can be used.

Specifically, as the fullerene, C ₆₀ Buckminster fullerene, C ₇₀ , C ₈₂ , and higher molecular weight fullerene can be used. Further, various groups such as an alkyl group having 1 to about 25 carbon atoms such as methyl, ethyl, propyl, butyl, etc., an aryl group having 6 to about 24 carbon atoms such as phenyl, naphthyl, etc., ethylenediamine, hydroxy, carboxy, Derivative fullerenes including carbonyl, amino, amide, osmilato, oxo, dioxo, keto, mercapto, alkoxy, imino, allyl, ethynyl, azo, nitroso, formyl, halo, cyano, carboxamide, alkoxycarbonyl, nitro, vinyl, peroxy, etc. Can be used.

Further, fullerenes and nanotubes in which a metal such as La, Y, Sc or the like is included in the internal space can also be used.

These fullerenes and nanotubes may be used alone or in combination of two or more kinds, or
It can be used in combination with conventionally known external additives.

The content ratio of fullerene or nanotube in the developer is 0.1 to 10 with respect to 100 parts by weight of the toner.
Parts by weight, preferably 1 to 8 parts by weight.

<Monomer component> As a monomer component for obtaining the pigment-containing polymer particles of the present invention, a hydrophobic monomer is an essential constituent component, and if necessary, a hydrophilic monomer and a crosslinkable monomer are used. Used.

(1) Hydrophobic Monomer The hydrophobic monomer constituting the monomer component is not particularly limited, and conventionally known monomers can be used.

Specifically, radical polymerizable monomers such as vinyl aromatic type, (meth) acrylic acid ester type, vinyl ester type, vinyl ether type, monoolefin type, diolefin type, halogenated olefin type and polyvinyl type are used. It can be preferably used.

Examples of vinyl aromatic monomers include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, p-ethylstyrene. styrene,
pn-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene,
Examples thereof include styrene-based monomers such as 2,4-dimethylstyrene and 3,4-dichlorostyrene and derivatives thereof.

Examples of the (meth) acrylic acid ester-based monomer include methyl acrylate, ethyl acrylate,
Butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, β-hydroxyacrylate, γ -Propyl aminoacrylate, stearyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate and the like.

Examples of vinyl ester monomers include vinyl acetate, vinyl propionate, vinyl benzoate and the like.

Examples of vinyl ether type monomers include vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, vinyl phenyl ether and the like.

Examples of the mono-olefin type monomer include ethylene, propylene, isobutylene, 1-butene, 1-
Examples include pentene and 4-methyl-1-pentene.

Examples of the diolefin-based monomer include butadiene, isoprene and chloroprene.

These hydrophobic monomers can be used alone or in combination of two or more kinds.

(2) Hydrophilic Monomer The hydrophilic monomer which constitutes the monomer component is not particularly limited, but for example, a carboxyl group-containing monomer,
Sulfone group-containing monomer, phosphoric acid group-containing monomer, 1st
Monomers that can introduce a polar group into the side chain of the resulting polymer, such as secondary amines, secondary amines, tertiary amines, and quaternary ammonium salts, can be preferably used.

Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, cinnamic acid, maleic acid monobutyl ester and maleic acid monooctyl ester.

Examples of the sulfonic acid group-containing monomer include styrene sulfonic acid and 2-acrylamidopropyl sulfonic acid.

Examples of amine compounds include dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, 3-dimethylaminophenyl acrylate, 2-hydroxy-3-methacryloxypropyltrimethylammonium salt and the like. Can be mentioned.

These hydrophilic monomers can be used alone or in combination of two or more kinds.

By including the hydrophilic monomer as the monomer component, the polymerization rate at the time of aqueous precipitation polymerization is increased, and the molecular weight of the polymer can be easily controlled. Further, as a result of introducing a polar group into the polymer, when used as an electrophotographic toner, the chargeability can be controlled without adding a charge control agent or the like.

The proportion of the hydrophilic monomer in the monomer component is preferably 0.1 to 15% by weight, more preferably 0.5 to 12% by weight. If the proportion of the hydrophilic monomer is less than 0.1% by weight, the above effect cannot be sufficiently achieved, while this proportion is 15% by weight.
When it exceeds, the polymerization of only the hydrophilic monomer proceeds, and homopolymer formation occurs, which is not preferable.

(3) Crosslinkable Monomer Examples of the crosslinkable monomer include two or more unsaturated bonds such as divinylbenzene, divinylnaphthalene, divinyl ether, diethylene glycol methacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate and diallyl phthalate. The thing which has is mentioned.

By including the crosslinkable monomer as the monomer component, the resulting pigment-containing polymer particles can have improved properties such as strength.

(4) Chain Transfer Agent The control of the molecular weight and the molecular weight distribution of the polymer particles can be optionally achieved by adding a chain transfer agent to the polymerization reaction system. As the chain transfer agent, a thiol compound such as dodecanethiol is generally used, but it can be appropriately selected depending on the chain transfer constant for the monomer used.

<Pigment Particles> The pigment-containing polymer particles of the present invention are obtained by subjecting a monomer component to aqueous precipitation polymerization in an aqueous system in which pigment particles (organic pigment or inorganic pigment) are dispersed. is there.

The content ratio of the pigment in the pigment-containing polymer particles is 2 with respect to 100 parts by weight of the polymer component.
To 20 parts by weight, preferably 3 to 15 parts by weight.

(1) Organic Pigment Particles The organic pigment particles constituting the pigment-containing polymer particles are not particularly limited, and conventionally known particles of organic pigments can be used.

Specific examples of organic pigments include C.I.
I. Pigment Red 2, C.I. I. Pigment Red 3, C.I. I. Pigment Red 5, C.I. I. Pigment Red 6, C.I. I. Pigment Red 7, C.I. I. Pigment Red 15, C.I. I. Pigment Red 16, C.I.
I. Pigment Red 48: 1, C.I. I. Pigment Red 53: 1, C.I. I. Pigment Red 57: 1, C.I. I.
Pigment Red 122, C.I. I. Pigment Red 123,
C. I. Pigment Red 139, C.I. I. Pigment Red 144, C.I. I. Pigment Red 149, C.I. I. Pigment Red 166, C.I. I. Pigment Red 177, C.I.
I. Pigment Red 178, C.I. I. Pigment Red 2
Pigments for magenta or red such as 22; C.I. I.
Pigment Orange 31, C.I. I. Pigment Orange 43
Pigments for oranges such as C.I. I. Pigment Yellow 12,
C. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14, C.I. I. Pigment Yellow 15, C.I. I. Pigment Yellow 17, C.I. I. Pigment Yellow 93,
C. I. Pigment Yellow 94, C.I. I. Pigment Yellow 138 and other yellow pigments; C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 2, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 16,
C. I. Pigment Blue 60 and other cyan pigments; C.I.
I. Pigment Green 7 and other green pigments can be used, and these can be used alone or in combination of two or more kinds.

(2) Inorganic Pigment Particles The inorganic pigment particles forming the pigment-containing polymer particles are not particularly limited, and particles composed of conventionally known inorganic pigments can be used.

Specific examples of preferred inorganic pigments include carbon black such as furnace black, channel black, acetylene black, thermal black and lamp black, and magnetic powder such as ferrite and magnetite. Can be used alone or in combination of two or more.

(3) Surface Modification of Inorganic Pigment Particles The inorganic pigment particles constituting the pigment-containing polymer particles are preferably surface-treated with a surface modifier.

As such a surface modifier, conventionally known ones can be used, and particularly, a silane compound, a titanium compound, an aluminum compound and the like can be preferably used.

Examples of the silane compound include alkoxysilanes such as methyltrimethoxysilane, phenyltrimethoxysilane, methylphenyldimethoxysilane and diphenyldimethoxysilane, silizane such as hexamethyldisilazane, γ-chloropropyltrimethoxysilane, and the like.
Vinyltrichlorosilane, vinyltrimethoxysilane,
Examples include vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-ureidopropyltriethoxysilane. To be

Examples of the titanium compound include "Planeact TTS", "Planeact 9S", and "Planeact 38".
"S""Plennact41B""Plennact46B""Plennact55""Plennact138S""Plennact 238
S "[above, manufactured by Ajinomoto Co., Inc.]," A-1 "," B- "
1 ”,“ TOT ”,“ TST ”,“ TAA ”,“ TA ”
"T", "TLA", "TOG", "TBSTA", "A"
-10 "," TBT "," B-2 "," B-4 "," B- "
7 "," B-10 "," TBSTA-400 "," TT
"S", "TOA-30", "TSDMA", "TTA"
"B", "TTOP" [above, manufactured by Nippon Soda Co., Ltd.] and the like.

Examples of the aluminum compound include "Planeact AL-M" (manufactured by Ajinomoto Co., Inc.) and the like.

The amount of these surface modifiers used is 0.1 to 20% by weight, preferably 1 to 15% by weight based on the inorganic pigment particles.
Weight%

<Production Method of Pigment-Containing Polymer Particles> The production method of the present invention is carried out while controlling the concentration of the surfactant existing in the aqueous system during the dispersion of the pigment and the aqueous precipitation polymerization reaction.

Specifically, the pigment-containing polymer particles of the present invention can be suitably produced by the pigment dispersion step, dilution step and polymerization step described below.

(1) Pigment Dispersion Step Pigment particles are dispersed in an aqueous system in the presence of a surfactant having a critical micelle formation concentration (CMC) or higher to prepare a pigment dispersion liquid.

The surfactant is appropriately selected from anionic surfactants, cationic surfactants and the like.
For example, sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, dodecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride and the like can be mentioned. Preferred is sodium dodecyl sulfate.

Examples of the dispersing method include mechanical stirring treatment using a sand grinder or the like, sonication treatment using ultrasonic waves or the like, and pressure dispersing treatment using manton gorin or the like.

Since it is difficult to disperse the pigment particles to the level of the primary particles, the pigment particles are usually dispersed in the aqueous system in the state of agglomerated particles formed by agglomeration of the primary particles.

The particle size of the dispersed pigment particles is as follows:
In the case of organic pigment particles, the primary particle diameter is preferably 10 times or less, more preferably 8 times or less. In the case of inorganic pigment particles, the primary particle diameter is preferably 20 times or less, more preferably 15 times or less.

When the particle size of the pigment particles is too large, it becomes impossible to produce the intended pigment-containing polymer particles having a small particle size, and the pigment particles having a large particle size move out of the reaction system. As a result, the composite of the pigment and the polymer cannot be sufficiently achieved.

In the pigment dispersion step, the concentration of the surfactant present in the water system needs to be equal to or higher than the critical micelle formation concentration (CMC).

Only when the concentration of the surfactant is equal to or higher than the critical micelle forming concentration (CMC) is 0.05 to 1 μm.
Dispersion of pigment particles of about m is preferably performed.

(2) Diluting Step The pigment dispersion prepared in the pigment dispersing step is diluted until the concentration of the surfactant becomes less than the critical micelle forming concentration (CMC) to prepare a diluted dispersion.

(3) Polymerization Step A monomer component and a polymerization initiator are added to the diluted dispersion prepared in the dilution step to carry out aqueous precipitation polymerization.

As the polymerization initiator used for initiating the aqueous precipitation polymerization reaction, a water-soluble radical polymerization initiator, for example, a persulfate such as potassium persulfate or ammonium persulfate; 4,4′-azobis-4-cyanokyl Herbic acid and its salts, 2,
Azo compounds such as 2'-azobis (2-aminodipropane) salt; peroxide compounds and the like can be preferably used. In addition, a combination of the above polymerization initiator and a reducing agent,
You may use it as a redox type polymerization initiator with large polymerization activity. By using a redox type polymerization initiator, the polymerization reaction can be performed at a low temperature, and further reduction of the polymerization time can be expected.

Regarding the concentration of the polymerization initiator in the reaction system of the aqueous precipitation polymerization, the preferable range differs depending on whether organic pigment particles are used or inorganic pigment particles are used.

When using organic pigment particles When using organic pigment particles, the concentration of the polymerization initiator is preferably 0.001 to 0.03 mol / l, and more preferably 0.003 to 0.025 mol / l. .

The concentration of the polymerization initiator is a (mol /
l), when the concentration of the monomer component is b (mol / l),
The value of "a / b" is preferably in the range of 0.004 to 0.10. When the concentration of the polymerization initiator is too low, the amount of radicals generated is small, and therefore the polymerization reaction is not completed and the monomer remains. On the other hand, when the concentration of the polymerization initiator is too high, soap-free polymerization occurs, a polymer containing no pigment is produced, and phase separation between the polymer and the organic pigment occurs, which is not preferable.

When Using Inorganic Pigment Particles When using inorganic pigment particles, the concentration of the polymerization initiator is preferably 0.002 to 0.02 mol / l, and more preferably 0.005 to 0.015 mol / l. . Further, the concentration of the polymerization initiator is c (mol / l) and the concentration of the monomer component is d.
(Mol / l), the value of "c / d" is 0.005 to 0.1
It is preferably in the range of 0. When the concentration of the polymerization initiator is too low, the amount of radicals generated is small, and therefore the polymerization reaction is not completed and the monomer remains. On the other hand, when the concentration of the polymerization initiator is excessively high, soap-free polymerization occurs, a polymer containing no pigment is produced, and phase separation between the polymer and the inorganic pigment occurs, which is not preferable.

As the polymerization reaction temperature, any temperature may be selected as long as it is at least the minimum radical generation temperature of the polymerization initiator, but it is usually in the range of 50 to 80 ° C. It is also possible to carry out the polymerization reaction at room temperature by using a polymerization initiator started at room temperature, for example, a polymerization initiator formed by combining hydrogen peroxide and a reducing agent such as ascorbic acid.

As described above, the present invention is characterized in that the aqueous precipitation polymerization reaction is carried out under the condition that the concentration of the surfactant is less than the critical micelle forming concentration (CMC).

When the aqueous precipitation polymerization reaction is carried out in a state of being above the critical micelle forming concentration (CMC), the emulsion polymerization of the monomer component is carried out in the micelles existing in the aqueous system, and the polymer particles containing no pigment. Will be generated.

(4) Association Fusing Step The pigment-containing composite particles produced in the polymerization step are used for association and fusion to produce a non-spherical toner.

Various methods of associative fusion bonding include, for example, JP-A-60-220358 and JP-A-4-284461. However, it is quite difficult to control the desired particle size and particle size distribution by these methods. Therefore, the inventors of the present invention, the method of Japanese Patent Application No. 5-115572, that is, non-spherical particles by the method of adding an organic solvent infinitely soluble in water and coagulant of the critical aggregation concentration of the polymer fine particle dispersion or more Was generated.

[0067]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited thereto.

The particle size of the pigment particles dispersed in the pigment dispersion liquid, and the particle size of the obtained pigment-containing polymer particles are determined by the electrophoretic light scattering photometer "ELS-800" [Otsuka Electronics Co., Ltd.].
Manufactured]. The molecular weight of the pigment-containing polymer particles was measured using GPC "HLC-8020" (manufactured by Tosoh Corporation).

Example-1 (1) Preparation of pigment dispersion 1.62 g of pigment was added to an aqueous solution prepared by dissolving 0.346 g of sodium dodecyl sulfate in 50 ml of ion-exchanged water, and an ultrasonic homogenizer Model US-150T (Nippon Seiki Co., Ltd.) was used. (Manufactured by Seisakusho) to prepare a pigment dispersion liquid. Table 1 shows the pigment dispersion particle diameters of the pigment dispersion liquids (D-1 to 4) in which the pigments are changed and dispersed by using the above method.

[0070]

[Table 1]

(2) Synthesis of Pigment-Containing Polymer Particles The dispersions (D-1 to 4) were mixed with a 500 ml cooling tube, a thermometer,
Put in a four-headed flask equipped with a stirrer and a nitrogen introduction tube, and degassed deionized water 150 ml, styrene monomer 25 g, n
-Butyl acrylate monomer 4.9g and methacrylic acid monomer 1.6g were added, and the internal temperature was raised to 70 ° C while stirring at a stirring speed of 500 rpm under a nitrogen stream. An aqueous solution of a polymerization initiator in which 1.125 g of potassium persulfate was dissolved in 50 ml of degassed deionized water at 70 ° C was added, and after polymerization for 7 hours, the internal temperature was lowered to room temperature and filtration was performed with a No. 3 glass filter. It was Table 2 shows the average particle size, molecular weight and molecular weight distribution of the produced pigment-containing polymer particles (P-1 to 4).

[0072]

[Table 2]

(3) Synthesis of non-spherical toner The pigment-containing polymer particles P-1 to P-4 were used, and these were mixed with 1N-
An aqueous sodium hydroxide solution was used and adjusted so that the methyl methacrylate component in the polymer particles would be a certain amount of sodium salt using an electric conductivity measuring device. The degree of dissociation at this time
75%. The critical concentration of potassium chloride at this time was measured to find that P-1 was 0.07 mol / l and P-2 to 4
Was 0.09 mol / l. Thereafter, 100 ml of each pigment-containing polymer particle dispersion liquid was placed in a four-headed flask equipped with a stirrer, a cooling tube, and a thermometer, and 6.04 g of potassium chloride was dissolved in 50 ml of water while stirring at a speed of 250 rpm at room temperature. Add a salt solution, add 50 ml of iso-propanol, and add 250 ml of water.
After adding, the non-spherical toner (P
R-1 to 4) were obtained. The average particle size (d
₅₀ ), particle size distribution (CV) and degree of non-sphericity. The results are shown in Table 3 below.

[0074]

[Table 3]

(4) Manufacture of developer 3 parts by weight of fullerene C _{60 was} added to 100 parts by weight of each of the above-mentioned non-spherical toners PR-1 to PR 4, and 5 parts by weight of this externally added toner and methyl methacrylate were added. / 95 parts by weight of ferrite particles (carrier, average particle size 60 µm) surface-coated with / styrene copolymer (MAA / St = 7/3 weight ratio) were mixed to prepare developers-1 to 4.

For comparison, the non-spherical toner PR-1 is used.
2 parts by weight of silica fine particles "R-972" and 1 part by weight of titanium oxide fine particles "T-805" to 100 parts by weight of
A comparative developer mixed with the carrier was prepared.

Example-2 Using Pigment Dispersion D-1 and polymerizing in the same manner as in Example-1 except that 0.2 g of t-dodecyl mercaptan, which is a chain transfer agent, was added at the time of polymerization to control the molecular weight. Polymer particles (P-5) were obtained. P-5 average particle size, molecular weight (M
W) and MW / MN are also shown in Table 2.

Using the pigment-containing polymer particles (P-5), a non-spherical toner (PR-5) was obtained in the same manner as in Example-1. The average particle size, CV value, and non-sphericity of PR-5 are also shown in Table 3.

Using this non-spherical toner (PR-5),
A developer (Developer-5) was prepared in the same manner as in Example-1.

Using the electrophotographic copying machine "U-BIX-3028" equipped with a heat roller fixing device and a cleaning blade, the developers 1 to 5 and the comparative developer were used to obtain the charge amount, the cleaning property, and the fog at low temperature and low humidity ( LL, 10 ° C, relative humidity 20%) Normal temperature and humidity (NN, 20 ° C, relative temperature 55%) High temperature and high humidity (HH,
It was evaluated under the environment of 30 ° C and relative humidity of 85%).

The evaluation method is as follows.

(1) Charge amount The charge amount at the initial stage and after 50,000 copies were measured by the blow-off method.

(2) Fog The reflection densities of the respective colors of the white background portion of the copy images formed continuously were measured by "Sakura densitometer PDA-60" (manufactured by Konica Corporation), and the reflection density was 0.02. Fog was judged by the number of copies at the time when it exceeded.

(3) Cleaning Property The surface of the photoconductor was visually observed and evaluated by the number of copies when the cleaning failure occurred.

The results are shown in Table 4 below. From the results shown in Table 4, it is understood that the developers-1 to 5 of the present invention have excellent various properties.

Example 3 Non-spherical toner PR-1 was added and mixed with 3 parts by weight of nanotubes per 100 parts by weight, and further mixed with the carrier to prepare a developer-6, and the same evaluation as above was carried out. The results are shown in Table 4.
Shown in. From these results, it is understood that the developer-6 of the invention has various properties.

Example 4 Non-spherical toner PR-1 was added and mixed with 100 parts by weight of fullerene C _{60 (} 2 parts by weight) and nanotubes (1 part by weight), and further mixed with the carrier to prepare a developer-7. Table 4 shows the results of evaluations similar to the above. From these results, it is understood that the developer-7 of the present invention has excellent properties.

Example-5 100 parts by weight of non-spherical toner PR-1 and 1 part by weight of silica fine particles "R-972", and titanium oxide fine particles "T-80".
1 part by weight of "5", 1 part by weight of fullerene C ₆₀ , and mixed,
Further, the results of performing the same evaluation as above by mixing the carrier and adjusting the developer-8 are shown in Table 4. From this result,
It can be seen that the developer-8 of the present invention has excellent properties.

Example-6 1 part by weight of silica fine particles "R-972" and 100 parts by weight of non-spherical toner PR-1 and titanium oxide fine particles "T-80" were used.
1 part by weight of 5 "and 1 part by weight of nanotubes were added and mixed, and further mixed with the above carrier to prepare a developer-9, and the same evaluation as above was performed. From these results, it is found that the developer-9 of the invention has various properties.

[0090]

[Table 4]

[0091]

INDUSTRIAL APPLICABILITY The toner composition of the present invention can be improved in fluidity, moisture resistance, chargeability and the like by inducing various groups such as conductivity, hydrophilicity and hydrophobicity as external additives. Since fullerenes and nanotubes are used, it is possible to provide a toner composition having little environmental dependence, stable chargeability, and no cleaning failure or toner filming.

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Claims (3)

[Claims] 1. A pigment-containing composite particle obtained by subjecting at least one or more hydrophobic monomers and at least one or more water-soluble monomers to aqueous precipitation polymerization in the presence of a pigment to associate,
A toner composition using pigment-containing composite particles containing a fused non-spherical toner and at least one or more fullerenes or nanotubes as external additives. 2. The non-spherical particles are produced by a method of adding an aggregating agent having a concentration not lower than the critical aggregation concentration of the polymer fine particle dispersion and an organic solvent infinitely soluble in water in the associating and fusing step. A toner composition using the pigment-containing composite particles according to claim 1. 3. A pigment-containing composite particle formed by aqueous precipitation polymerization in the presence of a pigment, using acrylic acid ester or methacrylic acid ester as at least a hydrophobic monomer, and acrylic acid or methacrylic acid as at least a water-soluble monomer. A method for producing a toner composition using a non-spherical toner that is associated and fused and a pigment-containing composite particle that contains at least one or more fullerenes or nanotubes as an external additive.