JP3262892B2 - Charge control agent composition and electrophotographic toner - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a charge control agent composition useful for a toner which is an electrophotographic developer and an electrophotographic toner containing the composition.

[0002]

2. Description of the Related Art In electrophotography, an electrostatic latent image is formed on a photoconductor layer composed of a photoconductive material and the like, developed with a powder developer, visualized, and fixed with heat or a solvent. The method of doing is general. Since the photoconductor layer can be positively or negatively charged, exposure under the original results in a positive or negative electrostatic latent image. When a negative electrostatic latent image is developed with a positively charged developing powder, a positive-positive image corresponding to the original is generated.

As such an electrophotographic developer, there is used a mixture of a fine particle powder comprising a resin called a toner and a colorant and a fine iron powder or a ferrite powder called a carrier.

In a powder toner, a binder resin, which is an essential component, is heated and melted, carbon as a coloring agent and a charge control agent are added thereto, dispersed by kneading, and after cooling, this is mechanically pulverized. Thereafter, a method of classifying and obtaining it is common.

[0005] Toner develops a latent image on a photoreceptor by a mechanism that causes charging by friction with a carrier (two-component developer) and friction with a sleeve (one-component developer). Since the toner is consumed by the development, it is always replenished. However, since the replenished toner has no charge, the toner is raised to a predetermined charge amount by stirring in the developing unit and friction on the sleeve. The charge amount of the toner is often set to about 10 to 30 μC / g.

[0006] Controlling the chargeability of the toner is the most important matter for the toner. The charging characteristics of the toner are governed by the resin which is the main component thereof, but usually, a desired frictional charging characteristic is obtained by adding a charge control agent. In recent years, demands for higher image quality, higher reliability, and higher speeds have necessitated more precise charging control than before. There is a strong need.

In order to perform good development, one of the characteristics required of the toner is how to start up the replenishment toner at a predetermined charge amount. If the toner rises poorly, low-charged toner will be generated and will not sufficiently transfer onto the photoreceptor, causing a decrease in density. The inside of the machine may be contaminated, or the deterioration of the developer may be accelerated.

In the case of a low-speed copying machine, the toner can be covered to some extent by stirring in the developing section. However, the higher the speed of the copying machine, the faster the replenished toner is transferred from the inside of the developing section to the photoreceptor, so that quick charging is achieved. Is required. In the case of a one-component toner, charging must be generated only by friction with the sleeve, not by friction with the carrier. Therefore, the rising property is more important than two-component toner.

Conventionally, it has been proposed to use a quaternary ammonium salt as a charge control agent (JP-A-62-53).
944, JP-A-62-71968 and JP-A-62-3259). However, the proposed charge control agent also has a compatibility with the resin, so that it does not readily mix uniformly with the resin during the production of the toner, leaving various problems in the properties of the toner.

In the case of toner, it is very important to uniformly disperse the charge control agent in the resin, and when the dispersibility is poor, the charge control agent is not uniformly mixed into the toner particles, and the quality of the toner is reduced. Non-uniformity occurs, and the rise of electrification tends to decrease and change with time tends to occur. The proposed toner using a quaternary ammonium salt or the like has a problem in that the charge is not stable at high temperature and high humidity, and remains unsatisfactory as a toner charge control agent. .

It is known that a hardly water-soluble inorganic salt is internally added to a toner for the purpose of preventing fusion of the toner to the surface of a metal sleeve or the surface of a photoreceptor, improving durability, and stabilizing charging. For example, JP-A-58-91462 discloses a toner internally containing barium sulfate, and JP-A-1-200377 discloses a toner internally containing tin oxide.

However, the former toner is liable to cause aggregation of barium sulfate, and is less effective in improving various properties of the toner. The latter toner, when used for a long time, causes a decrease in charge, resulting in a decrease in toner charge. There is a problem that scattering and image defects occur.

As an attempt to improve these drawbacks, there has been known a method of adding a small amount of fine powder of titanium oxide or an abrasive to the toner as an external additive (JP-A-4-153660, JP-A-63-163). 318569).

However, these external additives have an excessively strong polishing action, and may cause unnecessary wear of the photosensitive member when cleaning the toner. These external additives are sometimes transferred onto paper, and there is a problem that the image is contaminated.

[0015]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, has a good charging rise, is not affected by changes in temperature and humidity even after repeated development by continuous use, and is stable for a long time. It is an object of the present invention to provide a charge control agent composition having a high performance capable of reproducing a formed image and a toner containing the composition.

[0016]

As a result of various studies to solve these problems, the present inventors have prepared a specific quaternary ammonium salt as a charge control agent and a specific inorganic pigment, It has been found that the modified charge control agent composition has a characteristic that the dispersibility in the resin is extremely good, and the quaternary modified with the inorganic pigment prepared in this manner. The toner using the charge control agent composition comprising an ammonium salt solves the above-mentioned problems, that is, the problem of hastening the rise of charging, improving the stability of charging performance, and preventing the occurrence of toner scattering and image defects. The present inventors have determined that this is a solution and completed the present invention.

The present invention relates to a modified charge control agent composition prepared from a charge control agent comprising a quaternary ammonium salt and a specific inorganic pigment.

The present invention also relates to a toner as an electrophotographic developer containing a modified charge control agent composition prepared from a quaternary ammonium salt and a specific inorganic pigment.

Representative examples of the quaternary ammonium salt as a charge control agent usable in the charge control agent composition of the present invention include those represented by the following general formulas, oligomers having a quaternary ammonium salt, Polymers may be mentioned. In each of the general formulas, the anion X ⁻ is a halogen ion (Cl ⁻ , Br ⁻ , I ⁻ ), ClO ₄ ⁻ , B
F ₄ ⁻ , PF ₄ ⁻ , sulfate ion, nitrate ion, borate ion, phosphate ion, organic phosphate ion, carboxylate ion (anion such as acetic acid, benzoic acid, stearic acid, oleic acid), tetraphenyl borate , Cyanate,
Represents phenolate.

[0020]

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(Wherein R ₁ , R ₂ , R ₃ and R ₄ may be the same or different from each other, and each represents a substituted or unsubstituted aromatic carbocyclic group or a substituted or unsubstituted aromatic heterocyclic group. or represents a hydrocarbon group or an amide, ether, hydrocarbon group which may contain a thioether bond, a hydrogen atom or 1 to 22 carbon atoms, X ^-
Represents an anion. )

[0022]

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Wherein R ₁ and R ₂ are each independently hydrogen or a C ₁ -C ₂₂ hydrocarbon group;
₁ and R ₂ may be connected to each other to form an aromatic ring. R ₃ represents hydrogen or a C _{1 to} C ₂₂ hydrocarbon group;
R ₄ and R ₅ each independently represent a C ₁ -C ₈ alkylene group which may contain an amide, ether or thioether bond, and X ⁻ represents an anion. )

[0024]

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(Wherein R ₁ and R ₂ may be the same or different from each other, and each represents a substituted or unsubstituted aromatic carbocyclic group or a substituted or unsubstituted aromatic heterocyclic group, or
X represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, or a hydrocarbon group which may contain an amide, ether or thioether bond, and X ⁻ represents an anion. )

[0026]

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(Wherein R ₁ , R ₂ and R ₃ may be the same or different from each other, and each represents a substituted or unsubstituted aromatic carbocyclic group or substituted, unsubstituted aromatic heterocyclic group, or , A hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, or a hydrocarbon group which may contain an amide, ether or thioether bond, and Y is C, O,
S represents X and X ⁻ represents an anion. )

[0028]

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(In the formula, R ₁ , R ₂ and R ₃ may be the same or different from each other, and each represents a substituted or unsubstituted aromatic carbocyclic group or a substituted or unsubstituted aromatic heterocyclic group, hydrogen, It represents an atom or 1 to 22 amino hydrocarbon group having carbon atoms or an amide, ether, hydrocarbon group which may contain a thioether bond,, X ^- represents an anion).

[0030]

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(Wherein R ₁ and R ₂ may be the same or different from each other, and each represents a substituted or unsubstituted aromatic carbocyclic group or a substituted or unsubstituted aromatic heterocyclic group, or
X represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, or a hydrocarbon group which may contain an amide, ether or thioether bond, and X ⁻ represents an anion. )

[0032]

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(Wherein R ₁ is a substituted or unsubstituted aromatic carbocyclic group or a substituted or unsubstituted aromatic heterocyclic group, or a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, or it represents an amide, an ether, a hydrocarbon group which may contain a thioether bond, X ^- represents an anion).

The anion component of the quaternary ammonium salts of the present invention, halogen ions (Cl ^-, Br ^-,
I ⁻ ), ClO ₄ ⁻ , BF ₄ ⁻ , PF ₄ ⁻ , sulfate ion, nitrate ion, borate ion, phosphate ion, organic phosphate ion, carboxylate ion (acetic acid, benzoic acid, stearic acid, oleic acid, etc.) Anion), tetraphenylborate, cyanate, and phenolate.

The inorganic pigment used in the present invention includes barium sulfate, magnesium hydroxide, aluminum hydroxide, calcium carbonate, dimagnesium phosphate, magnesium carbonate, barium carbonate, calcium sulfate, zinc silicate, calcium silicate, and silicate. Magnesium and aluminum silicate. Further, an inorganic pigment coated with an organic compound, an organic polymer, a hydrophobizing agent, a titanate coupling agent or the like can be used.

As the above-mentioned inorganic pigment, any of synthetic products and natural products can be used. Further, an inorganic pigment reaction liquid generated by the reaction can also be used. For example, a mixture of barium sulfate and aluminum hydroxide obtained by the reaction of barium chloride with aluminum sulfate and alkali, or a mixture of zinc carbonate and sodium sulfate obtained by the reaction of zoda carbonate and zinc sulfate, or a mixture of sodium carbonate and calcium chloride Calcium carbonate obtained by the reaction with
Or, calcium sulfate or the like obtained by a reaction between sodium sulfate and calcium chloride.

The charge control agent composition of the present invention is prepared from the above-mentioned quaternary ammonium salt and an inorganic pigment. As a method for preparing the charge control agent composition from the quaternary ammonium salt and the inorganic pigment, any method can be adopted as long as a method of obtaining a homogeneous composition of both can be obtained. In producing a quaternary ammonium salt, an inorganic pigment is added at any stage of the production process to obtain a homogeneous composition of a quaternary ammonium salt as a reaction product and the inorganic pigment as a final product. Is preferred.

It is particularly preferred that the inorganic pigment is added by being present together with the reaction raw material compound in the reaction system for producing the quaternary ammonium salt. Further, it may be added to the reaction mixture transferred from the quaternary ammonium salt formation reaction step to the purification step, or may be added by mixing with a wet cake-like filtration product obtained from the purification step. A method in which a quaternary ammonium salt produced by the reaction is filtered off in a purification step, dried, and then an inorganic pigment is immediately added, pulverized and mixed to prepare a homogeneous composition may be used.

A charge controlling agent composition having the same performance by wet-homogeneously mixing a dried quaternary ammonium salt and an inorganic pigment in an appropriate solvent, for example, water, a mixture of water and an organic solvent, or an organic solvent alone, in a wet manner. It is possible to get things.

The charge control agent composition obtained by the above method can be used for the production of a toner as it is after drying, and if necessary, may be further pulverized and classified before use. The content of the inorganic pigment in the charge control agent composition obtained in the present invention is such that the charge control agent composition does not deteriorate the properties as a charge control agent.

The charge control agent composition of the present invention described above has a good dispersibility in a resin, and a toner using the charge control agent composition has a good charge rise and has a low temperature, low humidity and high temperature and high humidity. Under the above environment, even if used for a long time, the toner instability and scattering of the toner, which had problems in the past, can be solved.
As a result, a clear developed image is obtained.

The toner of the present invention is characterized by containing the charge control agent composition of the present invention. In the general method of manufacturing powder toner, the temperature at which the resin is heated and melted is
Although it depends on the type of resin, the temperature is generally 150 ° C. or lower.
The charge control agent is dispersed therein by kneading. As the characteristics of the charge control agent, it is required that the melting point is equal to or higher than the kneading temperature and the solubility in the resin is extremely low. It is known that the charge control agent dispersed in the resin is dispersed in the form of small particles in individual toner particles obtained by pulverization and classification. Therefore, when manufacturing a charge control agent, it is important to design the charge control agent to maximize its characteristics.

The amount of the charge control agent composition is suitably from 0.1 to 15% by weight, particularly preferably from 0.5 to 10% by weight, based on the weight of the toner.

The toner of the present invention further contains a binder and a colorant in addition to the charge control agent composition. Examples of the binder that can be preferably used in the toner of the present invention include polystyrene, styrene such as polyvinyltoluene and its substituted monomers, styrene-substituted styrene copolymers, styrene-acrylate copolymers, and styrene- Methacrylic acid copolymer, styrene-acrylonitrile copolymer,
Examples include polyvinyl chloride, polyethylene / silicone resin, polyester, polyurethane, polyamide, epoxy resin, modified rosin, and phenol resin. However, other materials that have been used as a binder material for a toner are also applicable.

As the coloring substance, for example, C.I. I. Pigment Yellow 12, C.I. I. Solvent Yellow 1
8, C.I. I. Disperse Yellow 33, C.I. I. Pigment Red-122, C.I. I. Solvent Red-1
9, C.I. I. Pigment Blue 15, C.I. I. Pigment Black-1, C.I. I. Solvent Black-3,
C. I. Solvent Black-22 and carbon black. However, other materials conventionally used as toner colorants are also applicable.

In the present invention, the toner powder of the present invention is prepared by melting and solidifying the charge control agent composition in a weight ratio of 0.1 to 50% with respect to the synthetic resin, and then solidifying the resultant. Coarsely pulverized, further pulverized by a jet mill pulverizer, and then classified by an airflow classifier, or prepared by adding a polymerization initiator to a synthetic resin monomer, and then adding the charge control agent composition to the monomer. 0.1 to 50 by weight
%, And the mixture is polymerized while being suspended in water. At this time, other coloring agents or carbon black may be added as a dye.

The toner thus produced gives a charge amount suitable for the development of an electrostatic image due to friction with the carrier, and is not affected by changes in temperature and humidity even when development is repeated for a long time. The charge amount is kept constant, and the charge distribution is uniform and kept constant.

Examples of the carrier include iron powder, a magnetic core coated with a styrene-methyl methacrylate copolymer, a silicone resin, a mixed resin of a styrene-methyl methacrylate copolymer and a silicone resin, and a carrier coated with a styrene tetrafluoride polymer. Can be used. Further, the charge control agent composition according to the present invention provides excellent charging characteristics even when used in a so-called one-component toner containing a magnetic substance. It can also be used for capsule toner and polymerized toner.

The magnetic material used as the magnetic material includes fine powders of metals such as iron, nickel, and cobalt;
Alloys of metals such as cobalt, copper, aluminum, nickel, and zinc; metal oxides such as aluminum oxide, iron oxide, and titanium oxide; ferrites such as iron, manganese, nickel, cobalt, and zinc; vanadium nitride; Nitrides such as chromium, carbides such as tungsten carbide and silicon carbide, and mixtures thereof can be used.

As the magnetic material, iron oxides such as magnetite, hematite, and ferrite are preferable.

[0051]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples of the production of the composition and examples of use as a toner, but the present invention is not limited to these Examples. In addition, the amount and part of each component described in an Example show a weight part unless there is particular notice.

Example 1 Quaternary ammonium salt:

[0053]

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20.0 parts of N, N-dimethyl-N, N-ditetradecylammonium chloride was added to methanol 10
Dissolved in 0 parts. Aluminum hydroxide (2μ)
After adding 8.2 parts of m), a solution consisting of 14.4 parts of sodium tetraphenylborate and 100 parts of methanol was poured. After stirring at 30 ° C., the precipitated white precipitate was separated by filtration and sufficiently washed with water. After drying, a composition 1 having a quaternary ammonium salt and aluminum hydroxide composition ratio of 80:20 was obtained.

Next, 88 parts of a styrene-n-butyl methacrylate copolymer resin [Himer SBM-73F manufactured by Sanyo Chemical Co., Ltd.], 5 parts of low molecular weight polypropylene [Viscol 550-P manufactured by Sanyo Chemical Co., Ltd.], 5 parts of carbon Black [# 44 manufactured by Mitsubishi Kasei Corporation] 5 parts, composition 1 2
After the partial premixing, the mixture was melt-kneaded and further pulverized and classified to obtain a toner having a particle size of 5 to 25 μm.

To 3 parts of this toner, an iron powder carrier (TEFV 200/300, manufactured by Powder Tech) 9
Seven parts were mixed to prepare a developer. After stirring the developer, the triboelectric charge was measured by a blow-off charge measuring device (manufactured by Toshiba Chemical). Stirring time is 30 seconds, 1 minute,
The triboelectric charge (μC / g) after 3 minutes, 5 minutes, 10 minutes, 30 minutes and 2 hours was 2.5, 4.0, respectively.
6.1, 8.8, 9.0, 9.2, and 9.3. 5
The value after minutes was 94.6% of the value after 2 hours, and the rise of charging was good.

Further, when this toner was put into a developing device, continuous copying was performed and an image test was performed. As a result, a good image was obtained at the start, and the image quality remained unchanged after 50,000 sheets. There was no outbreak. Furthermore, high temperature and high humidity of 35 ° C., 85% RH and 10 ° C., 30%
Even under a low-temperature and low-humidity environment of% RH, image quality equivalent to that of copying under a normal temperature and normal humidity environment was obtained. Also, neither toner scattering nor offset occurred.

Example 2 20.0 parts of N, N-dimethyl-N, N-ditetradecylammonium chloride were dissolved in 100 parts of methanol. In it, sodium tetraphenylborate 1
A solution consisting of 4.4 parts and 100 parts of methanol was poured. After stirring at 30 ° C., the quaternary ammonium salt (Compound 1) was filtered off.

After the wet cake was stirred and dispersed in 100 minutes of water at room temperature, 8.2 parts of the same aluminum hydroxide (2 μm) as in Example 1 was added, and the mixture was stirred overnight, filtered off, and sufficiently filtered. The resultant was washed with water and dried to obtain a composition 2 having a quaternary ammonium salt (compound 1) and aluminum hydroxide in a composition ratio of 80:20.

Next, a toner was prepared in the same manner as in Example 1 except that the composition 1 was changed to the composition 2, and the triboelectric charge of the toner was measured. As a result, the triboelectric charge (μC / g) at 30 seconds, 1 minute, 3 minutes, 5 minutes, 10 minutes, 30 minutes, and 2 hours of stirring with the iron carrier was 2.3 and 4.0, respectively. , 5.4, 8.6, 8.9,
9.0 and 9.3. The triboelectric charge after stirring for 5 minutes was 92.5% of the value after 2 hours, and a toner having a good rise in a short time was obtained.

The toner was put into the developing device, continuous copying was performed, and an image test was performed.
A good image was obtained, the image quality remained unchanged after 50,000 sheets, and toner scattering and offset did not occur. Furthermore, good image quality was obtained without being affected by high-temperature and high-humidity and low-temperature and low-humidity environments.

Example 3 A quaternary ammonium salt (compound 1) synthesized in the same manner as in Example 2 was filtered off and dried. Immediately after drying, the same aluminum hydroxide (2 μm) as in Example 1 was added and mixed, and the mixture was pulverized with a pulverizer to obtain a composition 3 having a quaternary ammonium salt and aluminum hydroxide composition ratio of 80:20.

Next, a toner was prepared in the same manner as in Example 1 except that the composition 1 was replaced with the composition 3, and the triboelectric charge was measured. As a result, the stirring time with the iron carrier was 30 seconds, 1 minute, 3 minutes, 5 minutes, 10 minutes, and 30 minutes.
The amount of triboelectric charge (μC / g) per minute and 2 hours is 2.4, 4.1, 5.6, 8.4, 8.8, 9.0, respectively.
9.2. The measured amount of stirring for 5 minutes was 91.3% as compared with the value after 2 hours, and a toner having a good rise in a short time was obtained.

The toner was put into a developing device, continuous copying was performed, and an image test was performed.
A good image was obtained, the image quality remained unchanged after 50,000 sheets, and toner scattering and offset did not occur. Furthermore, high temperature and high humidity of 35 ° C., 85% RH and 10 ° C., 30%
Even under a low-temperature and low-humidity environment of% RH, image quality equivalent to that of copying under a normal temperature and normal humidity environment was obtained. Also, neither toner scattering nor offset occurred.

Comparative Example 1 A toner was prepared in the same manner as in Example 1 except that 1.0 part of a quaternary ammonium salt (compound 1) synthesized and dried was used in the same manner as in Example 1, but without using aluminum hydroxide. Then, the triboelectric charge was measured. The stirring time of the developer is 30 seconds, 1
Minutes, 3 minutes, 5 minutes, 10 minutes, 30 minutes, and 2 hours, the triboelectric charge amount (μC / g) is 1.8, 3.0, and 4.0.
4, 6.0, 7.6, 8.6 and 9.4. The triboelectric charge after stirring for 5 minutes was 63.8% of the triboelectric charge after 2 hours, and the charging rise was extremely low.

Further, an image test was conducted in the same manner as in Example 1. As a result, a clear image without fog was obtained as an initial image, but an unclear image with fog was obtained from about 1,000 sheets.

Comparative Example 2 A toner was synthesized in the same manner as in Example 2 and a dried quaternary ammonium salt (Compound 1) was used, and the raw materials used in the preparation of the toner were made to have the following composition to obtain a toner in the same manner as in Example 1. .

Styrene-n-butyl methacrylate copolymer resin 88 parts [Himer SBM-73F manufactured by Sanyo Chemical Co., Ltd.] Low molecular weight polypropylene 5 parts [Viscol 550-P manufactured by Sanyo Chemical Co., Ltd.] Carbon black [# 44 Mitsubishi Chemical Co., Ltd.] 5 parts Quaternary ammonium salt (Compound 1) 1 part Aluminum hydroxide (2 μm) 1 part

Using this toner, the developer was adjusted in the same manner as in Example 1, and the stirring time with the iron carrier was 30 seconds.
The triboelectric charges for 1 minute, 3 minutes, 5 minutes, 10 minutes, 30 minutes, and 2 hours were 1.9, 3.1, 4.8,
6.5, 7.8, 8.7 and 9.5. The triboelectric charge amount after stirring for 5 minutes was 68.4% of the value after 2 hours, and the charge rise was poor. Further, an image test was performed in the same manner as in Example 1. As a result, the initial image was a clear image without fog, but became an unclear image with fog from around 1,000 sheets.

As shown by the above results, it can be seen that the toner using the charge control agent composition of the present invention has a very excellent rise in charge.

Further, it is important that the toner and the carrier are uniformly dispersed in a short period of time in the characteristic that charging rises quickly. Therefore, the toner of Examples 1 to 3 and Comparative Examples 1 and 2 is stirred for 30 seconds. Was visually observed and compared. A developer was prepared by mixing 3 parts of a toner with 97 parts of a carrier (manufactured by Powder Tech, iron powder carrier TEFV 200/300), and an image was taken with a copying machine.

In the toners of Examples 1 to 3 using the charge control agent composition of the present invention, the dispersion state of the toner and the carrier was almost uniform, whereas the toners of Comparative Examples 1 and 2 were in the dispersion state. However, it was uneven and uneven. In the toners of Examples 1 to 3, the dispersion of the toner and the carrier was achieved in a short time, and as a result, the rise of charging was excellent. In addition, the toners of Examples 1 to 3 provided good images with good image quality and little background fog. This is considered to be due to the charging characteristics due to the difference in the dispersion state of the quaternary ammonium salt and the inorganic pigment.

Example 4 As in Example 1, except that aluminum hydroxide (2 μm) was used.
m) was replaced with aluminum hydroxide (30 μm) to prepare composition 4. Further, a toner was prepared using Composition 4 instead of Composition 1, and the triboelectric charge of the toner was measured. As a result, the mixing time of the toner and the iron carrier was 3
The triboelectric charges (μC / g) in 0 second, 1 minute, 3 minutes, 5 minutes, 10 minutes, 30 minutes, and 2 hours are 2.6, 4.3, 6.3, 8.9, and 9.9, respectively. 0, 9.3,
9.3. The value after stirring for 5 minutes was 95.7% of the value after 2 hours, indicating a good charge rise.

The toner was put into a developing device, continuous copying was performed, and an image test was performed. As a result, a good image was obtained at the start, and the image quality was unchanged after 50,000 sheets. There was no outbreak. Further 35
Image quality equivalent to copying under normal temperature and normal humidity was obtained even in a high temperature and high humidity environment of 90 ° C. and 85% RH and in a low temperature and low humidity environment of 10 ° C. and 30% RH. Also, neither toner scattering nor offset occurred.

Embodiment 5

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12.5 parts of N, N-dimethyl-N-tetradecylamine and 20.0 parts of tetradecyl bromide were dissolved in 100 parts of methanol. After adding 18.0 parts of calcium carbonate (1.5 μm), the mixture was stirred at 50 ° C. The precipitated white precipitate was separated by filtration. After drying, the composition ratio of quaternary ammonium salt and calcium carbonate is 50:50.
The composition 5 was obtained.

Next, a toner was prepared in the same manner as in Example 1 except that the composition 1 was changed to the composition 5, and the triboelectric charge of the toner was measured. The triboelectric charge (μC / g) after stirring for 30 seconds, 1 minute, 3 minutes, 5 minutes, 10 minutes, 30 minutes and 2 hours was 3.3, 5.3, and 7, respectively.
2, 9.9, 10.1, 10.3, and 10.4.
The value after stirring for 5 minutes was 95.2% of the value after 2 hours, and the rise of charging was good.

Further, when this toner was put into the developing device, continuous copying was performed and an image test was performed. As a result, a good image was obtained at the start, and the image quality remained unchanged after 50,000 sheets. There was no outbreak. Furthermore, high temperature and high humidity of 35 ° C., 85% RH and 10 ° C., 30%
Even under a low-temperature and low-humidity environment of% RH, image quality equivalent to that of copying under a normal temperature and normal humidity environment was obtained. Also, neither toner scattering nor offset occurred.

Example 6 12.5 parts of N, N-dimethyl-N-tetradecylamine and 20.0 parts of tetradecyl bromide were dissolved in methanol 10
Dissolved in 0 parts. After stirring at 50 ° C., the quaternary ammonium (compound 2) was filtered off.

After the wet cake was stirred and dispersed in 60 parts of water at 10 ° C., the same calcium carbonate as in Example 5 (1.
5 μm), 18 parts were added, and the mixture was stirred overnight, and then filtered.
The resultant was washed with water and dried to obtain a composition 6 having a composition ratio of quaternary ammonium salt (compound 2) and calcium carbonate of 50:50.

Next, a toner was prepared in the same manner as in Example 1 except that the composition 1 was changed to the composition 6, and the triboelectric charge of the toner was measured. As a result, the triboelectric charge (μC / g) in the stirring time with the iron content carrier for 30 seconds, 1 minute, 3 minutes, 5 minutes, 10 minutes, 30 minutes, and 2 hours was 3.0 and 5.0, respectively. , 7.1, 9.5, 9.9,
10.2 and 10.3. The triboelectric charge after stirring for 5 minutes was 92.2% of the value after 2 hours, and a toner having a good rise in a short time was obtained.

Further, the toner was put into a developing device, continuous copying was performed, and an image test was performed.
A good image was obtained, the image quality remained unchanged after 50,000 sheets, and toner scattering and offset did not occur. Further, good image quality was obtained without being affected by high temperature / high humidity and low temperature / low humidity.

Comparative Example 3 A toner was prepared in the same manner as in Example 1 except that 1.0 part of a quaternary ammonium salt (compound 2) synthesized and dried was used in the same manner as in Example 1, but without using aluminum hydroxide. Then, the triboelectric charge was measured. The stirring time of the developer is 30 seconds, 1
Minutes, 3 minutes, 5 minutes, 10 minutes, 30 minutes, and 2 hours, the triboelectric charge amount (μC / g) is 1.8, 3.0, and 4.0.
2, 5.3, 6.0, 6.8 and 7.3. The triboelectric charge after stirring for 5 minutes was 72.6% of the triboelectric charge after 2 hours, and the charging rise was extremely low.

Further, an image test was conducted in the same manner as in Example 1. As a result, a clear image without fog was obtained as an initial image, but an unclear image with fog was obtained from about 1,000 sheets.

Compositions 7 to 19 containing the quaternary ammonium salts shown in Tables 1 and 2 were prepared in the same manner as in Example 1, and used in Examples 7 to 16 and Comparative Examples Comparative Example 4 to Comparative Example 13 were used in the same manner as in Example 2. The results are shown in Tables 3 and 4. In Tables 3 and 4, the resin used, the method of measuring the charge amount, and the criteria for each evaluation item are as follows.

Resin A: Styrene-acrylic acid copolymer [Hymer SBM-
73 Sanyo Chemical Co., Ltd.] B: Styrene-acrylic acid copolymer [Hymer TB-1
000 manufactured by Sanyo Chemical Co., Ltd.] C: Polyester [HP-313 Nippon Synthetic Chemical Co., Ltd.]
D) Polyester [HP-320 Nippon Synthetic Chemical Co., Ltd.
E: Polystyrene [Average molecular weight 1500]

Charge amount: Measured value after stirring for 2 hours Judgment: ○: no practical problem ×: practical problem

[0088]

[Table 1]

[0089]

[Table 2]

[0090]

[Table 3]

[0091]

[Table 4]

[0092]

According to each of the examples and comparative examples, when the charge controlling agent comprising the quaternary ammonium salt and the inorganic pigment is used, the dispersion of the quaternary ammonium salt having the effect of the charge controlling agent itself into the resin is extremely high. It can be seen that the toner particles have good charging characteristics, that is, have a uniform charging level and excellent charge retention. Along with this, the dispersion of the toner particles and the carrier was made possible in a short time, the rise of charging was quickened, and the copy speed was made faster. At the same time, the toner has a longer life and is less affected by environmental changes such as low temperature, low humidity, and high temperature and high humidity.

Continuation of the front page (56) References JP-A-61-194452 (JP, A) JP-A-4-125655 (JP, A) JP-A-59-200252 (JP, A) JP-A-6-11882 (JP) , A) (58) Field surveyed (Int. Cl. ⁷ , DB name) G03G 9/097

Claims (2)

(57) [Claims] 1. An anionic component comprising a halogen ion and C
10 ₄ ⁻ , BF ₄ ⁻ , PF ₄ ⁻ , sulfate ion, nitrate ion, borate ion, phosphate ion, organic phosphate ion,
Quaternary ammonium salt having carboxylate ion, tetraphenylborate, cyanate, phenolate, calcium carbonate, magnesium carbonate, barium carbonate, barium sulfate, calcium sulfate, magnesium hydroxide, aluminum hydroxide, calcium silicate, silicic acid A charge control agent composition prepared from one or more inorganic pigments selected from the group consisting of aluminum, zinc silicate, magnesium silicate, and dimagnesium phosphate. 2. An electrophotographic toner comprising the charge control agent composition of claim 1 and a binder substance and a coloring substance as main components.