JP2003122046A - Toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner which derive the potential of the toner having wax to the maximum and has excellent developability, transferability, fixability and durability. SOLUTION: The toner having toner particles containing a binder resin, a coloring agent and a wax and hydrophobic titanium oxide particulates are characterized in that the peak temperature of the maximum endothermic peak in the range of 30 to 150 deg.C at the endothermic curve in differential thermal analysis measurement ranges from 50 to 100 deg.C and the hydrophobic titanium oxide particulates are 5.0 to 12.0 in the ratio of the maximum strength to the minimum strength in the range of 2θ=20.0 to 40.0 deg is X-ray diffraction.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner that can be used for electrostatic charge development in an image forming method such as electrophotography, electrostatic recording, electrostatic printing, or image formation in a toner jet system, and to prevent high temperature offset. The present invention relates to a color toner that does not use the above-mentioned oil, or exhibits high definition even when using a fixing unit in which the amount of the used oil is reduced.

[0002]

2. Description of the Related Art Conventionally, as an image forming method, US Pat. No. 2,297,691 and JP-B-42-239 have been used.
No. 10 and Japanese Patent Publication No. 43-2474748, etc.
Many methods are known. Generally, a photoconductive substance is used to form an electrostatic charge image on a photoreceptor by various means,
Then, a toner image is formed by depositing toner on the electrostatic image. Then, if necessary, the toner image is transferred to the surface of an image support such as paper, and then fixed by heating, pressurizing, heating and pressurizing or solvent vapor to obtain a copy or print.

Regarding the method of developing an electrostatic image with toner, it is well known that an image is formed on the surface of a photoconductive material by electrostatic means and the image is developed with toner. For example, US Pat. 221,776, the powder cloud method, and 2,618,552, the cascade developing method, 2,874,0.
63, the magnetic brush method,
A method using a conductive magnetic toner described in Japanese Patent No. 909,258 is known.

When the method has a step of transferring a toner image, a cleaning step is usually provided to remove the residual toner on the photoconductor. Further, the toner image on the final image forming member such as paper is fixed on the support by heat, pressure, heat pressure or the like. Conventionally, this fixing step is often adopted by a heating and pressing means.

As the toner applied to these developing methods, generally, a thermoplastic resin and a colorant are melt-kneaded, then the kneaded product is cooled, and the cooled kneaded product is finely pulverized into colorant-containing resin particles. Particles are used. Polystyrene resin is the most common thermoplastic resin, but polyester resin, epoxy resin, and acrylic resin are also used. Carbon black is widely used as a non-magnetic colorant, and well-known pigments and dyes are widely known as colorants for color toners. In the case of magnetic toners, black mainly composed of iron oxide is used. Magnetic powder is used. In the case of a system using a two-component developer, the toner is usually used as a mixture with carrier particles such as iron powder and ferrite powder or resin-coated carrier particles thereof.

Regarding the formation of full-color images, in recent years,
In a copying machine or the like, the development from mono-color copying or mono-color printing to full-color copying or full-color printing is rapidly progressing, and two-color copying machines and full-color copying machines are being studied and put to practical use. For example, "Electrophotographic Society Journal" Vo1.22, No.1 (1983) and "Electrophotographic Society Journal" Vo1.25, No.1, P52 (1986) have been reported on color reproducibility and gradation reproducibility. . Color image formation by full-color electrophotography generally reproduces all colors using color toners of three primary colors of yellow, magenta, and cyan and, if necessary, black toner.

In the full-color copying method, light from the original is passed through a color separation light-transmitting filter having a complementary color relationship with the color of the toner to form an electrostatic image on the photoconductive layer, and then a development and transfer process is performed to form the color toner. Hold on a support. This step is sequentially performed a plurality of times, and while matching the registration, the color toners of the respective colors are superposed on the same support, and then the final full-color image is obtained by fixing once.

Generally, in the case of a developing system in which a developer is a two-component type developer consisting of a toner and a carrier, the developer causes the toner to be charged to a required charge amount and charge polarity by friction with the carrier, and electrostatically. The electrostatic force image is developed using a toner having a triboelectric charge by utilizing the attractive force. Therefore, in order to obtain a good visible image, the triboelectric chargeability of the toner must be good.

Further, from the viewpoint of forming an image having a good image quality in addition to the triboelectric chargeability, the color toner is required to satisfy the following characteristics. (1) The fixed toner is in a state of almost complete melting such that the shape of the toner particles cannot be discriminated so as to prevent diffused reflection of light and prevent color reproduction. (2) It has transparency for favorably performing subtractive color mixing of the above toner layer and the toner layers below which have different color tones. (3) Each color toner has a well-balanced hue and spectral reflection characteristics and sufficient saturation.

In order to solve the above problems, excellent charge-charging properties have been achieved in materials constituting toners, such as investigation of charge control agents and fluidity-imparting agents added to toners, and further improvement of binder as a base. Research is being done.

There is a method in which a charge control agent is added in advance together with the binder resin and the colorant when the toner is manufactured. However, it is not easy to uniformly disperse the charge control agent in the binder resin, and what substantially contributes to the charging property is in the vicinity of the toner particle surface and the charge control agent existing inside the toner particle. Since the agent does not contribute to the charging property, it is not easy to control the addition amount of the charge control agent or the amount present on the toner surface. For the reason that the charging auxiliary agent as described above is added, for example, a stirrer is used. Alternatively, a method of adhering the toner particles to the surface of the toner particles by an electrostatic force between the toner particles and the charging aid or a van der Waals force is generally used by using a mixer.

For example, Japanese Patent Publication No. 52-32256 and Japanese Unexamined Patent Publication No. 56-64352 disclose a technique of adding a charging auxiliary agent such as chargeable fine particles to a toner by adding a resin fine powder having a polarity opposite to that of the toner. A technique has been proposed, and Japanese Patent Application Laid-Open No. 61-160760 proposes a technique of adding a fluorine-containing compound to a developer to obtain stable triboelectric chargeability.

However, in this method, it is not easy to uniformly disperse the charging aid on the surface of the toner particles. The charging aids do not adhere to the toner particles and form agglomerates with each other, and the amount of the agglomerates released from the toner particles tends to increase. This tendency becomes more remarkable as the specific electric resistance of the charging aid increases and the particle size decreases. If there are many free aggregates, the performance of the toner is affected. For example, when many sheets are used, the triboelectric charge amount of the toner becomes unstable, the image density is not constant, and an image with a lot of fog is likely to be formed. Furthermore, when continuous copying is performed, the content of the charging aid changes, and it is difficult to maintain the initial image quality.

From the above viewpoints, various proposals have been made regarding the charging auxiliary agent added to the toner particles. As such a proposal, for example, titanium oxide fine particles are externally added to the toner particles to impart toner fluidity, It has been proposed to stabilize the charge.

In JP-A-60-112052, 2θ = 20.0 to 40.0d in X-ray diffraction described later.
Anatase type titanium oxide having a strength ratio (Ia / Ib) of the maximum strength Ia and the minimum strength Ib in the range of egg of greater than 12.0 and a low volume resistivity is known, but particularly in a high humidity environment. The frictional charge was leaked quickly, and there was a point to be particularly improved in terms of stabilization of charging.

Further, in Japanese Patent Laid-Open No. 5-72797 (corresponding EP-A-523654), the intensity ratio (Ia / Ib)
Is proposed for toners containing hydrophobic amorphous titanium oxide having a particle size of less than 5.0. Amorphous titanium oxide has a lower abrasivity than crystalline titanium oxide, and therefore there is a point to be improved in polishing the surface of the photoconductor and removing deposits on the surface of the photoconductor. Further, since amorphous titanium oxide has a large number of OH groups even after the hydrophobizing treatment, there is a point to be improved especially with respect to a decrease in chargeability due to water adsorption in a high humidity environment.

Further, Japanese Patent Laid-Open No. 6-332232 proposes to add a needle-shaped large-length titanium oxide having an intensity ratio (Ia / Ib) of over 12.0 to a toner. However, the needle-like shape and large and long particle diameters of titanium oxide have a great influence, and there is a point to be improved regarding the low fluidity of the toner.

Further, in JP-A-6-332233, titanium oxide particles having a strength ratio (Ia / Ib) of generally greater than 12.0 and represented by TiO _x (x = less than 2) are attached. Although proposed for toners, the titanium oxide particles are black or blue and are not suitable as an external additive for color toners such as yellow toners or magenta toners, and the particle size of titanium oxide is relatively large. However, there is a point to be improved in that the ability to impart fluidity to the toner is low and the surface of the photosensitive drum is easily damaged.

Further, JP-A-5-188633 proposes a toner containing a hydrophobized anatase type titanium oxide fine powder having an intensity ratio (Ia / Ib) of more than 12.0. Because of the complete anatase crystals, some titanium oxide particles agglomerate with each other, which damages the surface of the photosensitive drum, and when added externally to toner particles of small particle size, the fluidity of the toner is There is something to improve on the low.

In general, as titanium oxide, one having a rutile type crystal is also known, but since the BET specific surface area is small and the crystal growth is needle-like or columnar, the fluidity,
The level of imparting abrasiveness is low, which is not preferable.

Further, Japanese Patent Laid-Open No. 11-202543,
JP-A-11-237761 and JP-A-2001-66
In Japanese Patent Publication No. 820, there is proposed to use titanium fine particles obtained by subjecting metatitanic acid to a hydrophobic treatment to a toner, but oil for preventing high temperature offset as in the present invention is not used, or an amount of oil used is A toner used in combination with a fixing unit having a reduced amount of toner is not applicable and has a point to be improved.

Further, Japanese Patent Laid-Open No. 10-207117 proposes a toner in which the intensity ratio (Ia / Ib) between the maximum intensity Ia and the minimum intensity Ib in X-ray diffraction is specified. However, there is a problem to be solved as a toner which does not use oil for preventing high temperature offset as in the present invention or which is used in combination with a fixing unit in which the amount of oil used is reduced.

Further, JP-A-5-232740, JP-A-11-38670 and JP-A-2000-2502.
No. 68 and Japanese Patent Laid-Open No. 2000-352838,
Although a toner containing wax and titanium oxide has been proposed, the low-temperature fixability is insufficient, and titanium oxide is outside the range of the strength ratio (Ia / Ib) of the present invention, and the potential of the toner containing wax is high. There is still room for consideration in eliciting.

From the above viewpoints, there is a demand for titanium oxide fine particles capable of improving sufficient fluidity, chargeability, abradability, environmental stability, and durability with respect to a toner containing wax.

Regarding the examination of charging properties for the purpose of further improving image quality, in recent years, demands for high definition and high image quality of copying machines or printers have been increasing in the market, and in the technical field concerned,
Attempts have been made to reduce the particle size of the toner to achieve high-quality color, but when the particle size of the toner particles becomes smaller, the surface area per unit weight increases, and the toner charge amount tends to increase. Image density is low and toner durability deterioration is likely to occur. In addition, since the toner has a large charge amount, the adhesive force between the toner particles is strong and the fluidity is lowered, so that problems may occur in stability of toner replenishment and tribo imparting to the replenished toner.

Regarding the examination of the fixing property for the purpose of improving the image quality, in the case of a normal color toner, an oil such as silicone oil or fluorine oil is added to the heating fixing roller without adding a releasing agent such as wax as much as possible. A technique is known in which coating is performed to improve high-temperature offset resistance and OHP transparency.

However, the fixed image thus obtained has extra oil attached to its surface. Therefore, the oil may adhere to the photoconductor to be contaminated, or the oil may swell the fixing roller to shorten the life of the fixing roller. Furthermore, since oil streaks are not generated on the fixed image, it is necessary to uniformly and quantitatively supply the oil onto the surface of the fixing roller, which tends to increase the size of the fixing device, which is not preferable.

Therefore, in the heating / pressurizing fixing means in which the oil for preventing the high temperature offset is not used or the amount of the oil used is reduced, the toner which can suppress the occurrence of the offset and further the fixed image can be formed. A toner having excellent transparency is desired.

From this point of view, polyester resins are often used as binder resins for color toners for full-color image formation, but toners having polyester resins as binder resins are generally affected by temperature and humidity. A color toner having a more stable charge amount even in a wide range of environments is desired, since it is easy to cause problems such as excessive charge amount under low humidity and insufficient charge amount under high humidity.

[0030]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner that solves the above problems, and more specifically, to maximize the potential of a wax-containing toner. Another object of the present invention is to provide a toner having excellent developing property, transfer property, fixing property and durability.

A further object of the present invention is to provide a toner capable of forming a clear image without fog, having a high image density, excellent reproducibility of fine lines, excellent gradation of highlight portions, and excellent durability stability. To provide.

A further object of the present invention is to provide a toner having excellent fluidity and excellent resolution and transferability.

A further object of the present invention is to polish or remove the deposits on the surface of the photoconductor generated by long-term use or to suppress the generation of the deposits and to obtain a stable image without image defects for a long period of time. It is to provide a toner that can.

A further object of the present invention is to provide a toner which is not easily affected by environment such as temperature and humidity and which has stable triboelectric charging characteristics.

A further object of the present invention is to provide a color toner suitable for forming a full-color image or a multi-color image.

A further object of the present invention is to provide a color toner having good transparency on OHP, excellent low-temperature fixing property, and high-temperature offset resistance.

A further object of the present invention is to provide a color toner having excellent storage stability, heat resistance and blocking resistance.

[0038]

The present invention has toner particles containing a binder resin, a colorant, and a wax, and hydrophobic titanium oxide fine particles, and has a temperature of 30 at an endothermic curve in a differential thermal analysis measurement. The maximum endothermic peak temperature in the range of ˜150 ° C. is in the range of 50 to 100 ° C., and the hydrophobic titanium oxide fine particles have a minimum intensity in the range of 2θ = 20.0 to 40.0 deg in X-ray diffraction. The toner has a maximum intensity ratio of 5.0 or more and 12.0 or less.

As a result of intensive studies, the inventors of the present invention have shown excellent low-temperature fixability and color mixture even in a heating / pressurizing fixing means in which oil for preventing high temperature offset is not used or the amount of oil used is reduced. Property, high temperature offset resistance, and excellent developability in all environments.
In order to achieve transferability, fixability, durability, and long-term storage stability in a high temperature environment, a color toner containing at least a binder resin, a colorant, a wax and hydrophobic titanium oxide fine particles is used. It has been found that having physical properties is extremely effective.

[0040]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to a toner in which a specific hydrophobic titanium oxide is applied to toner particles containing a wax having predetermined physical properties. In the present invention, the hydrophobic titanium oxide fine particles are analyzed by X-ray diffraction. 2θ = 20.0 to 40.0
The intensity ratio (Ia / Ib) of deg is related to the crystal form of the hydrophobic titanium oxide fine particles, the fluidity imparting ability to the toner, and the abrasivity imparting ability.

When Ia / Ib is less than 5.0, the hydrophobic titanium oxide fine particles do not have a clear peak derived from the crystal structure in X-ray diffraction, indicating that they are amorphous. Such hydrophobic titanium oxide fine particles have a lower ability to impart abrasiveness to the toner as compared with hydrophobic titanium oxide having a clear peak in X-ray diffraction. Therefore, the ability to polish the surface of the photoconductor and the ability to remove the deposits on the surface of the photoconductor are low. Therefore, the intensity ratio (Ia / Ib) is 5.0.
Hydrophobic titanium oxide fine particles of less than 1 are soft as particles because no crystal growth occurs, and even if the number average particle diameter to be described later is 1 to 100 nm,
It is considered that the ability to impart abrasiveness to the toner is lowered.

In particular, the toner containing wax as in the present invention has poor fluidity, and the wax easily comes out on the surface of the toner due to heat or mechanical shock, so that the adhesion to the surface of the photoreceptor is extremely strong. Therefore, when hydrophobic titanium oxide having Ia / Ib of less than 5.0 is used in combination with toner particles containing wax, the polishing ability of the photoreceptor surface and the ability to remove the deposits on the photoreceptor surface are reduced. Because it is low
Toner is apt to adhere to the surface of the photoreceptor due to durability, and image defects and cleaning defects tend to occur, which is not preferable.

From the above viewpoints, in order to maximize the potential of the toner having a wax having an excellent fixing performance and improve the durability performance, the polishing ability of the surface of the photoconductor and the photosensitivity as in the present invention are used. It is necessary to use it in combination with hydrophobic titanium oxide fine particles, which is excellent in the ability to remove deposits on the body surface.

When the intensity ratio (Ia / Ib) is larger than 12.0, coalescing particles are easily generated in the hydrophobic titanium oxide fine particles in the process of increasing the crystallinity, and the fluidity imparting ability to the toner is low. Filming on the surface of the photoconductor and damage to the surface of the photoconductor are likely to occur. In addition, when the hydrophobic treatment is performed, the coalesced particles become a factor that hinders the uniform reaction with the hydrophobizing agent, which is not preferable.

In particular, the toner containing the wax as in the present invention has poor fluidity due to the influence of the wax near the surface of the toner. Therefore, in order to maximize the potential of the toner having a wax having excellent fixing performance and to stably exhibit the toner performance in all environments, it is necessary to increase the external additive such as the hydrophobic titanium oxide fine particles. It is essential to provide liquidity.

Therefore, the intensity ratio (Ia / Ib) is 12.
When used in combination with a hydrophobic titanium oxide larger than 0, the fluidity of the toner is insufficient, so that the toner or wax component adheres to the surface of the photoconductor or the coalesced particles of the hydrophobic titanium oxide are exposed. It is likely to damage body parts such as the body surface and cleaning blade. These phenomena are not preferable because they cause image defects and poor cleaning.

X of the hydrophobic titanium oxide fine particles is preferable.
The maximum intensity Ia of 2θ = 20.0 to 40.0 deg in line diffraction is preferably 2θ = 24.0 to 26.0 deg, and the minimum intensity Ib is preferably 2θ = 28.0 to 33.0 deg.

This is because the hydrophobic titanium oxide fine particles are in the process of crystal growth from amorphous to anatase type.
Alternatively, it indicates that an amorphous part and an anatase type crystal part are mixed.

In the present invention, surface treatment with a hydrophobizing agent can be utilized as a general means for imparting hydrophobicity to titanium oxide. The hydrophobic titanium oxide used in the present invention may be prepared by adding titanium oxide particles to a dispersion system to hydrophobize them by a hydrophobizing agent, or producing titanium oxide particles in the dispersion system, and then producing the titanium oxide particles or the process thereof. The intermediate in 1 may be hydrophobized with a hydrophobizing agent.

The raw material and the manufacturing method of the hydrophobic titanium oxide fine particles are not particularly limited, but as a result of diligent studies on imparting fluidity, charging characteristics and charging stability of the hydrophobic titanium oxide fine particles, the reaction with the hydrophobizing agent was carried out. The point is to contain a proper amount of OH group, hydrophobic titanium oxide fine particles in the middle stage of transition of the crystalline form from amorphous to anatase type, or a mixture of amorphous part and anatase type crystal part, It has been found that it is effective to use the hydrophobic titanium oxide fine particles with less aggregate.
Therefore, in order to obtain the hydrophobic titanium oxide of the present invention, it is preferable to add a seed having an anatase type crystal structure. By adding the seed, excessive crystal growth is suppressed, so that the number of coarse particles is reduced, and it is possible to suppress the occurrence of drum scratches in durability.

In the method for producing hydrophobic titanium oxide used in the present invention, the seed having the anatase type crystal structure can be obtained by various methods. Specifically, it is obtained by thermally hydrolyzing an aqueous titanyl sulfate solution. Anatase-type titania sol obtained by neutralizing the hydrous hydrophobic titanium oxide slurry with ammonia water, filtering and washing the hydrophobic titanium oxide cake with water to deflocculate it with hydrochloric acid is suitable.

An example of producing the hydrophobic titanium oxide used in the present invention will be shown.

(A) In order to obtain hydrophobic titanium oxide fine particles having less uniform aggregates and a uniform particle size distribution in a dispersion liquid obtained by decomposing ilmenite as a starting material with sulfuric acid, anatase type A titania sol having a crystal structure is added as a seed and then hydrolyzed to produce a slurry metatitanic acid. After adjusting the pH of this metatitanic acid slurry, sufficiently stir it so that coalescence of metatitanic acid particles does not occur in the slurry,
While being dispersed in the solution, a hydrophobizing agent is added dropwise and mixed to react. By subjecting this to filtration, drying and crushing treatment, hydrophobic titanium oxide fine particles are produced.

(B) Titanium tetraisopropoxide was used as a raw material, and the raw material was sent to a glass wool of a vaporizer heated to about 200 ° C. using a chemical pump as a carrier gas and nitrogen gas as a carrier gas. After evaporating and instantly heating and decomposing at about 300 ° C. in the reactor, rapid cooling is performed to collect the product. This is further baked at about 300 ° C. for about 2 hours, and the strength ratio (Ia /
Ib) is adjusted and subjected to a hydrophobization treatment to produce hydrophobic titanium oxide fine particles.

Further, BET of hydrophobic titanium oxide fine particles
The specific surface area is preferably in the range of 100 to 350 m ² / g.

When the BET specific surface area of the hydrophobic titanium oxide fine particles is smaller than 100 m ² / g, it is shown that the hydrophobic titanium oxide fine particles have a large particle size and that there are aggregates or coarse particles of the hydrophobic titanium oxide. However, problems such as deterioration of fluidity of the toner, damage to the surface of the photoconductor, and deformation or damage of cleaning means such as a cleaning blade are likely to occur. Further, when the particle size of the hydrophobic titanium oxide fine particles is large, they are easily separated from the toner particles, and the ability to impart stable fluidity to the toner containing the wax as in the present invention is insufficient, so that it is stable for a long period of time. However, it is difficult to maintain high toner performance. Further, the liberated hydrophobic titanium oxide fine particles remain in the developing machine in a large amount and adhere to various devices in the main body of the image forming apparatus to adversely affect them, which is not preferable.

When the BET specific surface area of the hydrophobic titanium oxide fine particles is larger than 350 m ² / g, the amount of water adsorbed on the hydrophobic titanium oxide fine particles increases, which may adversely affect the charging characteristics of the toner. Particularly, in a high humidity environment, the triboelectric charge amount of the toner is reduced, and image quality deterioration such as toner scattering, fog, and increase in image density is likely to occur.

The number average particle diameter of the hydrophobic titanium oxide fine particles is from 1 to 100 from the viewpoint of imparting fluidity to the toner and polishing property.
It is preferably nm. When the number average particle diameter of the hydrophobic titanium oxide fine particles is smaller than 1 nm, the toner particles are likely to be embedded on the surface of the toner particles, so that the toner deterioration is likely to occur early and the durability is lowered, and the hydrophobic titanium oxide fine particles have a sharpening property. It tends to be low.

On the other hand, when the average particle diameter of the hydrophobic titanium oxide fine particles is larger than 100 nm, the fluidity of the toner is lowered and the charging is apt to become non-uniform, resulting in deterioration of image quality, toner scattering and fog. It is easy to occur. In addition, the surface of the photoconductor is likely to be seriously scratched, image defects are likely to occur, and a cleaning member such as a cleaning blade is likely to be deformed or damaged.

Regarding the polishing and removal of the surface of the photoconductor and its deposits, the toner temporarily stays at the pressure contact part of the cleaning member such as the photoconductor surface and the cleaning blade when being cleaned from the photoconductor surface. Hydrophobic titanium oxide fine particles existing on the surface of the toner particles that have stayed have a function of polishing and removing the surface of the photoconductor and its deposits.

However, the hydrophobic titanium oxide fine particles are not embedded in the toner particle surface, but are dispersed in the toner in a state close to the primary particle diameter without agglomerates and uniformly exist on the toner particle surface. preferable. In order for the hydrophobic titanium oxide fine particles to have a suitable polishing property, the number average particle diameter is 1 to 100 nm, and the intensity ratio between the maximum intensity and the minimum intensity in X-ray diffraction of the hydrophobic titanium oxide fine particles has a specific value. The hydrophobic titanium oxide fine particles exhibiting the above are very effective.

In the present invention, the hydrophobic degree of the hydrophobic titanium oxide fine particles is preferably in the range of 40 to 90%.

When the degree of hydrophobicity is less than 40%, the triboelectric charge amount of the toner tends to decrease, and especially in a high humidity environment, the charge amount decreases, and toner scattering, fog, and image quality deterioration are likely to occur. The hydrophobic titanium oxide fine particles have a hydrophobicity of 9
When it is more than 0%, it becomes difficult to control the charge of the hydrophobic titanium oxide fine particles themselves, and the toner is likely to be charged up especially in a low humidity environment.

Examples of the hydrophobizing agent include silane coupling agents, titanate coupling agents, aluminum coupling agents, and zircoaluminate coupling agents.

Specifically, for example, as the silane coupling agent, those represented by the following general formula are preferable.

Embedded image R _m SiY _n [wherein, R represents an alkoxy group, m represents an integer of 1 to 3, Y represents an alkyl group, a vinyl group, a phenyl group, a methacryl group, an amino group, an epoxy group, A mercapto group or a derivative thereof, and n represents an integer of 1 to 3]

Examples of such silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, isobutyltrimethoxysilane and dimethyldimethoxy. Examples thereof include silane, dimethyldiethoxysilane, trimethylmethoxysilane, hydroxypropyltrimethoxysilane, phenyltrimethoxysilane, n-hexadecyltrimethoxysilane, and n-octadecyltrimethoxysilane.

The treatment amount is as follows:
The amount is preferably 1 to 60 parts by weight, more preferably 3 to 50 parts by weight, based on 00 parts by weight. If the treatment amount is too small, the titanium oxide may not be sufficiently hydrophobized. If the treatment amount is too large, the uniform hydrophobic treatment may be hindered.

In the present invention, the alkylalkoxysilane coupling agent represented by the following general formula is particularly suitable.

[Chemical 4] [In the formula, n represents an integer of 4 to 12 and m represents an integer of 1 to 3]

In the alkylalkoxysilane coupling agent, when n is smaller than 4, the treatment is easy but the degree of hydrophobicity is low, which is not preferable. When n is greater than 12, the hydrophobicity is sufficient, but the particles of the hydrophobic titanium oxide fine particles are often coalesced with each other, so that the fluidity-imparting ability is likely to decrease. m
When is larger than 3, the reactivity of the alkylalkoxysilane coupling agent is lowered and it becomes difficult to favorably make the hydrophobic. More preferably, the alkylalkoxysilane coupling agent has n of 4 to 8 and m of 1 to 2.

The treatment amount of the alkylalkoxysilane coupling agent is also preferably 1 to 60 parts by weight, more preferably 3 to 100 parts by weight with respect to 100 parts by weight of the hydrophobic titanium oxide fine particles.
50 parts by weight is good. If the treatment amount is too small, the titanium oxide may not be sufficiently hydrophobized. If the treatment amount is too large, the uniform hydrophobic treatment may be hindered.

The hydrophobizing treatment may be carried out by using one kind of hydrophobizing agent alone, or by using two or more kinds of hydrophobizing agents.
For example, one type of coupling agent may be used alone for hydrophobic treatment, or two types of coupling agents may be used simultaneously or after performing a hydrophobic treatment with a coupling agent, and then another coupling agent for further hydrophobic treatment. You may perform a conversion process.

In the present invention, there are the following methods for carrying out the hydrophobic treatment of the hydrophobic titanium oxide fine particles with a hydrophobizing agent, but the present invention is not particularly limited to these methods.

(A) As the hydrophobic treatment by the wet method,
While sufficiently mechanically mixing and stirring in a dispersion liquid of a predetermined amount of hydrophobic titanium oxide fine particles or metatitanic acid fine particles, a predetermined amount of a hydrophobizing agent or a diluent thereof or a mixed liquid thereof is added,
Mixing and stirring are further performed so that the particles do not coalesce. After thoroughly mixing and stirring, dry and crush.

(B) As an example of the hydrophobizing treatment method by the dry method, first, a predetermined amount of hydrophobic titanium oxide fine particles is stirred by an apparatus such as a blender, and a predetermined amount of the hydrophobizing agent or its diluted solution or its mixed solution is added. Add by dropping or spraying and mix thoroughly. After that, a predetermined amount of the hydrophobizing agent, the diluting liquid, or the mixed liquid thereof is added, and the mixture is sufficiently mixed and stirred. The resulting mixture is then heated and dried. Then, it is crushed by stirring with a device such as a blender.

In particular, by adding an alkylalkoxysilane coupling agent to a solution in which fine particles of metatitanic acid are dispersed in a slurry, the fine particles of metatitanic acid are made hydrophobic, and then the heat treatment is performed to obtain a strength ratio (Ia / Ib). The method of producing hydrophobic titanium oxide fine particles of 5.0 to 12.0 is preferable because the hydrophobic treatment is uniformly carried out in the state of primary particles and coarse aggregates of the hydrophobic titanium oxide fine particles are hard to be produced. Is.

The hydrophobic titanium oxide fine particles used in the present invention preferably have a volume resistivity value of 10 ⁸ Ω · cm or more. If the volume resistivity is less than 10 ⁶ Ω · cm, the toner may be insufficiently charged. The volume resistivity value can be arbitrarily adjusted by surface treatment with a hydrophobizing agent, dispersion of a conductive substance, etc., and is measured when a current is applied in a disk-shaped state under a predetermined load. It can be measured by the so-called tablet method in which the volume specific resistance is obtained from the voltage.

The hydrophobic titanium oxide fine particles are toner particles 10
0.1 to 5 parts by weight is suitable for 0 parts by weight. When the content is less than 0.1 parts by weight, the effect of addition is small and the fluidity of the toner tends to be low. 5% by weight
If it exceeds, the fluidity of the toner is too high, and on the contrary, uniform charging is likely to be hindered.

As the binder resin used for the toner particles,
Conventionally, various material resins known as toner binding resins are used.

For example, styrene copolymers such as polystyrene, styrene-butadiene copolymer and styrene-acrylic copolymer; ethylene polymers such as polyethylene, ethylene-vinyl acetate copolymer and ethylene-vinyl alcohol copolymer. Copolymer: Phenolic resin, epoxy resin, acrylic phthalate resin, polyamide resin, polyester resin, maleic acid resin, and the like. These resins may be used alone, or two or more kinds of resins may be mixed and used.

Among these resins, (a) a polyester resin having a particularly high negative charging ability, (b) a hybrid resin component having a polyester unit and a vinyl-based copolymer unit, or (c) a polyester resin. The effect of the present invention is enhanced when a mixture of a vinyl copolymer and a vinyl copolymer is used.

These resins, in particular, when combined with a wax, can effectively function as a wax at the time of fixing, and therefore have very excellent fixability, color mixing property, heat resistance,
Although it has good blocking resistance and is suitable for color toners, it has a strong negative charging ability and is apt to become excessively charged, but by using the hydrophobic titanium oxide fine particles used in the present invention, adverse effects are improved and excellent. Toner is obtained.

When a polyester resin is used as the binder resin, alcohol and carboxylic acid, carboxylic acid anhydride, carboxylic acid ester or the like can be used as a raw material monomer. Specifically, for example, as the dihydric alcohol component, polyoxypropylene (2.2) -2,2-
Bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.0)-
2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl)
Propylene, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane and other bisphenol A alkylene oxide adducts, ethylene glycol, diethylene glycol, triethylene glycol,
1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4- Examples thereof include cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A, hydrogenated bisphenol A and the like.

Examples of trihydric or higher alcohol components include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,
2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3.
5-trihydroxymethylbenzene etc. are mentioned.

As acidic components, aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or their anhydrides; alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or their anhydrides;
Examples thereof include succinic acid substituted with an alkyl group having 6 to 12 carbon atoms or an anhydride thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid or an anhydride thereof.

Among them, a bisphenol derivative represented by the following general formula (1) is particularly used as a diol component,
Carboxylic acid component consisting of divalent or higher carboxylic acid or its acid anhydride or its lower alkyl ester (eg fumaric acid, maleic acid, maleic anhydride, phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc.) Polyester resins obtained by polycondensing these as acid components are preferable because they have good charging characteristics as color toners.

[0086]

[Chemical 5]

In the binder resin contained in the toner of the present invention, the "hybrid resin component" means a resin in which a vinyl polymer unit and a polyester unit are chemically bonded. Specifically, a polyester unit and a vinyl polymer unit obtained by polymerizing a monomer having a carboxylic acid ester group such as (meth) acrylic acid ester are formed by a transesterification reaction,
It is preferable to form a graft copolymer (or block copolymer) using a vinyl polymer as a trunk polymer and a polyester unit as a branch polymer.

Examples of the vinyl-based monomer for producing the vinyl-based resin include the following. Styrene: o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert- Butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-chlorostyrene, 3, Styrene and its derivatives such as 4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene and p-nitrostyrene; styrene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated such as butadiene and isoprene Polyenes; vinyl chloride, vinylden chloride,
Vinyl halides such as vinyl bromide and vinyl fluoride;
Vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-methacrylic acid
Α-methylene aliphatic monocarboxylic acids such as butyl, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate. Esters; methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate,
Dodecyl acrylate, 2-ethylhexyl acrylate,
Stearyl acrylate, 2-chloroethyl acrylate,
Acrylic esters such as phenyl acrylate; Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone; N-vinyl pyrrole, N
-N-vinyl compounds such as vinylcarbazole, N-vinylindole and N-vinylpyrrolidone; vinylnaphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide.

Further, unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenylsuccinic acid, fumaric acid and mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, alkenylsuccinic anhydride Unsaturated dibasic acid anhydrides such as: maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl ester Half ester of unsaturated dibasic acid such as half ester, alkenyl succinic acid methyl half ester, fumaric acid methyl half ester, mesaconic acid methyl half ester; unsaturated dibasic acid ester such as dimethyl maleic acid, dimethyl fumaric acid; Le acid, methacrylic acid, crotonic acid,
Α, β-unsaturated acids such as cinnamic acid; crotonic anhydride,
Α, β-unsaturated acid anhydrides such as cinnamic acid anhydride,
An anhydride of β-unsaturated acid and lower fatty acid; alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid,
Examples thereof include monomers having a carboxyl group such as acid anhydrides and monoesters thereof.

Further, acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1- Mention may be made of monomers having a hydroxy group such as hydroxy-1-methylhexyl) styrene.

In the toner of the present invention, the vinyl polymer unit of the binder resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups, but the crosslinking used in this case. Examples of the agent include aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; examples of diacrylate compounds linked by an alkyl chain include ethylene glycol diacrylate, 1,
3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate and acrylate of the above compounds were replaced with methacrylate. Examples of the diacrylate compound linked by an alkyl chain containing an ether bond include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, and the like.
Examples thereof include polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and those obtained by replacing the acrylate of the above compounds with methacrylate; examples of the diacrylate compounds linked by a chain containing an aromatic group and an ether bond include Oxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,
2-bis (4-hydroxyphenyl) propane diacrylate and the compounds obtained by replacing the acrylates of the above compounds with methacrylates can be mentioned.

As the polyfunctional cross-linking agent, pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate and the above compounds in which acrylate is replaced with methacrylate; Triallyl cyanurate, triallyl trimellitate and the like can be mentioned.

In the present invention, it is preferable that at least one of the vinyl copolymer component and the polyester resin component contains a monomer component capable of reacting with both resin components. Among the monomers that constitute the polyester resin component, examples of monomers that can react with the vinyl copolymer include unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof.
Among the monomers constituting the vinyl-based copolymer component, those capable of reacting with the polyester resin component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.

As a method for obtaining a reaction product of a vinyl resin and a polyester resin, either one of the above-mentioned polymers containing a monomer component capable of reacting with each of the vinyl resin and the polyester resin is present. Alternatively, a method of obtaining by polymerizing both resins is preferable.

The polymerization initiator used when producing the vinyl copolymer of the present invention is, for example, 2,2′-
Azobisisobutyronitrile, 2,2'-azobis (4
-Methoxy-2,4-dimethylvaleronitrile), 2,
2'-azobis (-2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), dimethyl-2,2'-azobisisobutyrate,
1,1′-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) isobutyronitrile,
2,2'-azobis (2,4,4-trimethylpentane), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2'-azobis (2-methyl-propane), methyl ethyl ketone peroxide , Acetylacetone peroxide, ketone peroxides such as cyclohexanone peroxide, 2,2-bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide,
1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α,
α′-bis (t-butylperoxyisopropyl) benzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m- Trioyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, dimethoxyisopropyl peroxydicarbonate, di ( 3-
Methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, t-butylperoxyacetate, t-butylperoxyisobutyrate, t-butylperoxy neodecanoate, t-butylperoxy-2. -Ethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, t-butylperoxyisopropyl carbonate, di-t-butylperoxyisophthalate, t-butylperoxyallylcarbonate,
Examples thereof include t-amylperoxy-2-ethylhexanoate, di-t-butylperoxyhexahydroterephthalate, and di-t-butylperoxyazelate.

Examples of the production method capable of preparing the hybrid resin used in the toner of the present invention include the production methods shown in the following (1) to (6).

(1) A method in which vinyl resin, polyester resin and hybrid resin components are blended after production, and the blend is produced by dissolving and swelling in an organic solvent (eg xylene) and then distilling off the organic solvent. It Incidentally, the hybrid resin component, after separately producing a vinyl polymer and a polyester resin, dissolved and swollen in a small amount of an organic solvent, added with an esterification catalyst and alcohol,
An ester compound synthesized by performing transesterification by heating can be used.

(2) After the production of the vinyl polymer unit,
It is a method of producing a polyester unit and a hybrid resin component in the presence of this. The hybrid resin component is produced by reacting a vinyl polymer unit (a vinyl monomer can be added if necessary) with a polyester monomer (alcohol, carboxylic acid) and / or polyester. Also in this case, an organic solvent can be appropriately used.

(3) A method of producing a vinyl polymer unit and a hybrid resin component in the presence of the polyester unit after the production. The hybrid resin component is produced by reacting a polyester unit (a polyester monomer can be added if necessary) with a vinyl-based monomer and / or a vinyl-based polymer unit.

(4) After the vinyl polymer unit and the polyester unit are produced, the vinyl resin and / or the polyester monomer (alcohol, carboxylic acid) are added in the presence of these polymer units to produce the hybrid resin component. It Also in this case, an organic solvent can be appropriately used.

(5) After the production of the hybrid resin component, a vinyl-based monomer and / or a polyester monomer (alcohol, carboxylic acid) is added to carry out addition polymerization and / or polycondensation reaction to give a vinyl-based polymer unit and A polyester unit is manufactured. In this case, as the hybrid resin component, those manufactured by the above-mentioned manufacturing methods (2) to (4) can be used, and those manufactured by a known manufacturing method can be used as necessary. Furthermore, an organic solvent can be appropriately used.

(6) A vinyl polymer unit, a polyester unit and a hybrid resin component are produced by mixing a vinyl monomer and a polyester monomer (alcohol, carboxylic acid, etc.) and continuously performing addition polymerization and polycondensation reaction. To be done. Furthermore, an organic solvent can be appropriately used.

In the above production methods (2) to (6), the vinyl polymer unit and / or the polyester unit may be a plurality of polymer units having different molecular weights and crosslinking degrees.

The binder resin contained in the toner of the present invention is (a) a hybrid resin having a polyester unit and a vinyl copolymer unit, or (b) a mixture of a hybrid resin and a polyester resin. , (C) a mixture of a hybrid resin and a vinyl-based copolymer, (d) a polyester resin, and (e) a mixture of a polyester-based resin and a vinyl-based copolymer can be used. From the viewpoint that sufficient high temperature offset resistance, heat resistance, and blocking resistance can be obtained, a hybrid resin having a polyester unit and a vinyl copolymer unit, or a mixture of a polyester resin and a vinyl copolymer is used. It is preferable to use.

In the present invention, the acid value of the resin is 1 to
40 mgKOH / g is preferable because excellent charging stability can be obtained in each environment. The binder resin has an acid value of 1
If it is less than mgKOH / g, the toner tends to be charged up, and the image density tends to be low particularly in a low humidity environment. Also, the acid value of the binder resin is 40 mgKOH / g
When it is larger, the stability of the toner charge amount with time decreases, and the charge amount is likely to decrease with durability. Especially, in a high humidity environment, image defects such as toner scattering and fog are likely to occur.

Further, in the toner of the present invention, the glass transition temperature of the binder resin is from 50 to 50 in consideration of the storage stability and fixing property of the toner and the color mixing property with other color toners.
The temperature is preferably 80 ° C, more preferably 55 to 75 ° C.

When the glass transition temperature of the binder resin is lower than 50 ° C., the fixing property is excellent, but the offset resistance is lowered, and the fixing roller is contaminated and the winding around the fixing roller occurs, which is not preferable. Furthermore, the gloss of the image surface after fixing becomes too high, and the image quality deteriorates, which is not preferable.

The glass transition temperature of the binder resin is 80 ° C.
If it is larger than the above range, the fixing property is deteriorated and the set fixing temperature of the main body of the copying machine is unavoidably increased, the obtained image generally has low gloss, and the color mixing property is deteriorated as a full-color toner, which is not preferable.

The resin component of the toner of the present invention has a main peak in the molecular weight range of 3,500 to 20,000 in the molecular weight distribution measured by gel permeation chromatography (GPC), which is preferable. Exists in a region having a molecular weight of 4,000 to 15,000, and Mw / Mn is preferably 300 or more, more preferably 500 or more.

When the main peak is in the region where the molecular weight is less than 3,500, the hot offset resistance of the toner is insufficient. On the other hand, the main peak has a molecular weight of 20,000.
When it is in the super range, no sufficient low-temperature fixability of the toner can be obtained in combination with a fixing unit that does not use oil or uses a small amount of oil.
It is not preferable because the transparency of OHP becomes insufficient. Further, when Mw / Mn is less than 300, it becomes impossible to obtain good offset resistance.

The toner of the present invention contains one or more waxes. Examples of waxes used in the present invention include low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, aliphatic hydrocarbon waxes such as paraffin wax, and oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax, Or block copolymers thereof; waxes containing a fatty acid ester such as carnauba wax, sazol wax, montanic acid ester wax as a main component, and fatty acid esters such as deoxidized carnauba wax partially or wholly deoxidized Things are included.

Further, as the wax used in the present invention, saturated linear fatty acids such as palmitic acid, stearic acid and montanic acid; blancic acid, eleostearic acid,
Unsaturated fatty acids such as valinaric acid; saturated alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubayl alcohol, ceryl alcohol and melysyl alcohol; polyhydric alcohols such as sorbitol; linoleic acid amide, oleic acid amide, Fatty acid amides such as lauric acid amide; saturated fatty acid bisamides such as methylenebisstearic acid amide, ethylenebiscapric acid amide, ethylenebislauric acid amide, hexamethylenebisstearic acid amide;
Unsaturated fatty acid amides such as ethylene bis oleic acid amide, hexamethylene bis oleic acid amide, N, N 'dioleoyl adipamic acid amide, N, N' dioleoyl sebacic acid amide; m-xylene bis stearic acid amide, N, Aromatic bisamides such as N'distearyl isophthalic acid amide; Aliphatic metal salts such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate (generally called metallic soap); aliphatic hydrocarbons Waxes obtained by grafting wax onto vinyl monomers such as styrene and acrylic acid; partial esterification products of fatty acids such as behenic acid monoglyceride and polyhydric alcohols; having hydroxyl groups obtained by hydrogenation of vegetable oils and fats Methyl ester compound Etc., and the like.

As the wax particularly preferably used in the present invention, an aliphatic hydrocarbon wax can be mentioned. For example, a low molecular weight alkylene polymer obtained by radically polymerizing alkylene under a high pressure or a Ziegler catalyst under a low pressure; an alkylene polymer obtained by thermally decomposing a high molecular weight alkylene polymer; an Arge process from a synthesis gas containing carbon monoxide and hydrogen The synthetic hydrocarbon wax obtained from the distillation residue of the hydrocarbon obtained by or by hydrogenating these is preferable. Further, the one in which the hydrocarbon wax is fractionated by the use of press sweating method, solvent method, vacuum distillation or fractional crystallization method is more preferably used.

The hydrocarbon as a base is synthesized by a reaction of carbon monoxide and hydrogen using a metal oxide catalyst (often two or more kinds of multi-component system) [eg, gintol method, hydrocoal method (fluidization method). Hydrocarbon compounds synthesized by using a catalyst bed]; hydrocarbons having up to several hundred carbon atoms obtained by the Arge method (using a fixed catalyst bed) in which a lot of waxy hydrocarbons are obtained; alkylene such as ethylene Hydrocarbons polymerized by the Ziegler catalyst are preferred because they are linear hydrocarbons having a small number of branches, small size, and long saturation. A wax synthesized by a method that does not rely on the polymerization of alkylene is particularly preferable because of its molecular weight distribution.

Regarding the molecular weight distribution of the wax, it is preferable that the main peak is in the region of molecular weight of 400 to 2400.
More preferably, it is in the region of 430 to 2000. By having such a molecular weight distribution, preferable thermal characteristics can be imparted to the toner.

Further, the melting point of the above wax is preferably from 60 to 100 ° C., more preferably from 65 to 90 ° C., so that the wax functions more effectively during fixing of the toner.

The wax is used in an amount of 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass, per 100 parts by mass of the binder resin.

The method of adding the wax is not particularly limited, but it is usually added to the toner by a method of dissolving the resin in a solvent, raising the temperature of the resin solution and adding and mixing while stirring, or a method of mixing at the time of kneading.

In the present invention, the toner may contain an organometallic compound. The organometallic compound used in the present invention is preferably a compound of an aromatic carboxylic acid and a divalent or higher metal. Examples of the aromatic carboxylic acid include three kinds of compounds represented by the following formulas.

[0120]

[Chemical 6] [In the formula, R ₁ to R ₇ are the same or different groups, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon _{atoms, -OH, -NH 2, -NH (} CH 3 ), -N
_{(CH 3) 2, -OCH 3} , -O (C 2 H 5), - COOH
Or show a -CONH _2. ]

Preferred R ₁ is a hydroxyl group,
An amino group and a methoxy group are mentioned, and a hydroxyl group is preferable among them. As the aromatic carboxylic acid, a dialkyl salicylic acid such as di-tert-butyl salicylic acid is particularly preferable.

As the metal forming the organometallic compound,
A divalent or higher valent metal atom is preferred. Mg as a divalent metal
²⁺ , Ca ²⁺ , Sr ²⁺ , Pb ²⁺ , Fe ²⁺ , Co ²⁺ , N
^Examples thereof include i ²⁺ , Zn ²⁺ and Cu ²⁺ . As the divalent metal, Zn ²⁺ , Ca ²⁺ , Mg ²⁺ and Sr ²⁺ are preferable. Examples of trivalent or higher metals include Al ³⁺ , Cr ³⁺ , Fe ³⁺ and Ni ³⁺ . Of these metals, preferred is Al ³⁺ ,
Fe ³⁺ , Cr ³⁺ and Zn ²⁺ are particularly preferable Al.
³⁺ .

In the present invention, the organometallic compound is preferably an aluminum compound of di-tert-butylsalicylic acid or a zinc compound of di-tert-butylsalicylic acid.

The metal compound of the aromatic carboxylic acid is obtained by, for example, dissolving the aromatic carboxylic acid in an aqueous solution of sodium hydroxide, dropping an aqueous solution in which metal atoms having a valence of 2 or more are melted into the aqueous solution of sodium hydroxide, and stirring with heating. Then, the pH of the aqueous solution is adjusted, cooled to room temperature, and then filtered and washed with water to synthesize a metal compound of an aromatic carboxylic acid.
However, the synthesis method is not limited to the above.

The organometallic compound is 0.1 to 10 parts by mass (more preferably 0.5 to 100 parts by mass) per 100 parts by mass of the binder resin.
It is preferable to use 9 parts by mass from the viewpoint of adjusting the viscoelastic property and triboelectric charging property of the toner.

In the toner of the present invention, a compound other than the above-mentioned organometallic compounds can be used as a charge control agent, if necessary, in order to further stabilize its chargeability. Examples of the charge control agent include nigrosine and imidazole compounds. The charge control agent is used in an amount of 0.1 to 10 parts by mass, preferably 0.1 to 7 parts by mass, per 100 parts by mass of the binder resin.

When the toner is positively charged in the present invention, nigrosine, a triphenylmethane compound, a rhodamine dye, polyvinyl pyridine or the like may be added as a charge control agent having a positive charge property. preferable.

In the case of producing a color toner, it is preferable to use a colorless or pale color positive charge control agent that does not affect the color tone of the toner. Next, the particle size distribution of the toner will be described.

Regarding the image formed with the toner of the present invention,
Image density, highlight reproducibility (halftone reproducibility),
As a result of diligent studies on fine line reproducibility, the toner to which the hydrophobic titanium oxide fine particles are externally added has a weight average particle diameter of 3 to
It is preferably 9 μm. Further, the amount of toner particles of 4 μm or less greatly contributes particularly to the improvement of highlight reproducibility.

When the weight average particle diameter of the toner is larger than 9 μm, there are basically few toner particles that can contribute to high image quality, and it is difficult to faithfully adhere to the fine electrostatic charge image on the photosensitive drum, and the highlight Poor reproducibility, low resolution, too much toner on the electrostatic image,
It tends to cause an increase in toner consumption.

On the contrary, when the weight average particle diameter of the toner is smaller than 3 μm, the charge amount per unit weight of the toner is apt to be high, and the density is low, particularly the image density is low at low temperature and low humidity. In particular, it is not suitable for developing an image having a high image area ratio such as a graphic image.

Further, when the weight average particle diameter of the toner is smaller than 3 μm, the specific surface area of the toner becomes large,
Since the amount of wax in the vicinity of the toner surface is extremely large, the contact charging with the carrier is not smoothly performed, the amount of toner that cannot be sufficiently charged increases, and the toner scatters on the non-image portion and the fog becomes conspicuous. In order to deal with this, it is conceivable to reduce the diameter of the carrier in order to increase the specific surface area of the carrier,
With a toner having a weight average diameter of less than 3 μm, self-aggregation of the toner easily occurs, uniform mixing with the carrier is not achieved in a short time, and fog tends to occur in continuous replenishment durability of the toner.

The toner of the present invention comprises toner particles having a particle diameter of 4 μm or less, which is 8 to 70% by number of the total number of particles, preferably 10 to
It is preferable to have 60% by number. If the number of toner particles having a particle diameter of 4 μm or less is less than 8% by number, the number of fine toner particles required for high image quality is small, and in particular, the toner is continuously consumed by continuing copying or printing. The effective toner particle component in the developing device decreases, the balance of the toner particle size distribution deteriorates, and the image quality gradually deteriorates.

When the toner particles having a particle diameter of 4 μm or less exceed 70% by number, the toner particles are likely to aggregate with each other,
The toner often behaves as a toner lump, resulting in a rough image, a decrease in resolution, or a large density difference between the edge portion and the inside of the electrostatic charge image, resulting in a slightly hollow image. Easy and not preferable.

Particularly in the present invention, the content of the toner particles of 10.08 μm or more is preferably 2 to 25% by volume, and more preferably 3.0 to 20.0% by volume. If it is more than 25% by volume, the image quality is deteriorated, and more than necessary development (that is, excessive toner overload) occurs, resulting in an increase in toner consumption.
On the other hand, if the content is less than 2% by volume, the fluidity of the toner may be deteriorated and the image quality may be degraded.

Further, in order to further improve the effect of the present invention, for the purpose of improving the chargeability and fluidity of the toner,
10% to 90% by number of particles of 5.04 μm or less,
It is preferably 15% to 80% by number.

In order to make full use of such fine toner particles containing wax, it is important to greatly improve the fluidity and stabilize the charge, and a good image can be formed even if either of them is lacking. Is difficult.

Therefore, the potential of the fine particle toner containing the wax as described above is maximized and high resolution,
In order to achieve high gradation, the fluidity imparting ability as described above,
It is necessary to externally add and use specific hydrophobic titanium oxide fine particles having excellent charging characteristics, and the best image can be obtained by combining both.

Generally, when the toner is made into fine particles, the toner tends to be easily scattered from the developing device, but the hydrophobic titanium oxide fine particles used in the present invention have a high charge imparting ability.
Both improvement of fluidity and stabilization of charging can be achieved. The weight average particle diameter of the toner and the above number% can be adjusted by the manufacturing conditions of the classified product, the mixing of the classified product, and the like.

Further, in the present invention, the cohesion degree of the toner is preferably 2 to 35% (preferably 2 to 30%, more preferably 2 to 25%).

If the degree of cohesion exceeds 35%, the stability of the amount of toner conveyed from the toner hopper to the developing device may be reduced, the toner and the carrier may not be mixed properly, and the toner may not be sufficiently charged. easy. Therefore, even if the toner is made into fine particles and the coloring power of the toner is optimized, it is difficult to stably obtain a high-quality image. On the other hand, if the toner cohesion is less than 2%, the toner is likely to be scattered from the developing device, which is not preferable. The cohesion degree can be adjusted by using a pulverizer, pulverizing conditions, mixing conditions of external additives, and the like.

As the colorant for the toner of the present invention, known dyes or pigments may be used alone or in combination of two or more. In the present invention, the pigment may be used alone, but it is more preferable from the viewpoint of the image quality of a full-color image to improve the sharpness by using the dye and the pigment together.

As the coloring pigment for magenta toner, C.I.
I. Pigment Red 1, 2, 3, 4, 5, 6, 7,
8, 9, 10, 11, 12, 13, 14, 15, 16,
17, 18, 19, 21, 22, 23, 30, 31, 3
2, 37, 38, 39, 40, 41, 48, 49, 5
0, 51, 52, 53, 54, 55, 57, 58, 6
0, 63, 64, 68, 81, 83, 87, 88, 8
9, 90, 112, 114, 122, 123, 163,
202, 206, 207.209; C.I. I. Pigment Violet 19; C.I. I. Bat red 1, 2, 1
0, 13, 15, 23, 29, 35 and the like.

Examples of the magenta toner dye include C.I. I Solvent Red 1, 3, 8, 23, 24, 25, 27,
30, 49, 81, 82, 83, 84, 100, 10
9, 121; C.I. I. Disperse Red 9; C.I. I.
Solvent Violet 8, 13, 14, 21, 27;
C. I. Oil soluble dyes such as Disper Violet 1,
C. I. Basic Red 1, 2, 9, 12, 13, 1
4, 15, 17, 18, 22, 23, 24, 27, 2
9, 32, 34, 35, 36, 37, 38, 39, 4
0; C.I. I. Basic Violet 1, 3, 7, 1
Basic dyes such as 0, 14, 15, 21, 25, 26, 27 and 28 can be mentioned.

Examples of color pigments for cyan toner include C.I.
I. Pigment Blue 2, 3, 15, 16, 17; C.I.
I. Bat Blue 6; C.I. I. Acid Blue 45, or a copper phthalocyanine pigment having a structure represented by the following formula, in which 1 to 5 phthalimidomethyl groups are substituted in the phthalocyanine skeleton, and the like can be given.

[0146]

[Chemical 7] [In formula, n shows the integer of 1-5. ]

As the coloring pigment for yellow, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 1
1, 12, 13, 14, 15, 16, 17, 23, 6
5, 73, 74, 83, 97, 155, 180; C.I.
I. Butt Yellow 1, 3, 20, and the like.

In addition, C.I. I. Direct green 6,
C. I. Basic Green 4, C.I. I. Dyes such as Basic Green 6 and Solvent Yellow 162 can also be used.

As the black colorant used in the present invention, carbon black, a magnetic substance, and a color tone adjusted to black using the above-mentioned yellow / magenta / cyan colorant can be used.

The amount of the colorant used is preferably 0.1 to 15 parts by mass, more preferably 0.5 to 12 parts by mass, and most preferably 2 to 10 parts by mass with respect to 100 parts by mass of the binder resin. .

As a method for producing toner particles, a method in which the constituent materials are well kneaded by a heat kneader such as a hot roll, a kneader or an extruder, mechanically pulverized, and pulverized powder is classified to obtain toner particles; A method of obtaining toner particles by dispersing a material such as a colorant in a binder resin solution and then spray-drying; mixing a polymerizable monomer to constitute the binder resin with a predetermined material to form a monomer composition. A toner production method by suspension polymerization can be applied in which a toner is obtained and a toner particle is obtained by polymerizing an emulsion suspension of this composition.

The use form of the toner of the present invention is not particularly limited. For example, it may be used as a one-component developer, may be mixed with a carrier and used as a two-component developer, or a magnetic material may be used in toner particles. It may be mixed and used as a magnetic toner, or may be used as a non-magnetic toner formed by mixing a non-magnetic material. When the color toner of the present invention is used in a two-component developer, examples of carriers used in combination include surface-oxidized or non-oxidized iron, nickel, copper, zinc, cobalt, manganese, chromium, rare earth metals and the like. Alloys or oxides and ferrites can be used.

Particularly, magnetic ferrite particles of three elements of Mn-Mg-Fe formed mainly of manganese, magnesium and iron components are preferable in that good charging characteristics can be obtained. Furthermore, Mn-Mg-Fe The three-element magnetic ferrite particles contain 0.001 to 1% by mass of silicon element.
(More preferably 0.005 to 0.5% by mass) is particularly preferable when a silicone resin is used as a coating resin for magnetic ferrite particles.

The magnetic carrier particles are preferably coated with a resin, and the resin is preferably a silicone resin. In particular, a nitrogen-containing silicone resin or a modified silicone resin produced by reacting a nitrogen-containing silane coupling agent with a silicone resin is used in the color toner of the present invention to impart a negative triboelectric charge, environmental stability, and carrier. It is preferable in terms of suppressing the contamination of the surface of the.

The magnetic carrier has an average particle size of 15 to 60.
μm (more preferably 25 to 50 μm) is preferable in relation to the weight average particle diameter of the color toner.

The average particle size and particle size distribution of the magnetic carrier are
Laser diffraction type particle size distribution analyzer HELOS (made by JEOL) is used in combination with dry dispersion unit RODOS (made by JEOL), lens focal length 200 mm, dispersion pressure 3.0 bar (0.3 MPa), measurement time 1 to 2 seconds. Under the measurement conditions of the above, the range of the particle size of 0.5 μm to 350.0 μm is divided into 31 channels as shown in Table 1 below and measured, and 50% particle size (median size) of the volume distribution is obtained as the average particle size. The volume% of particles in each particle size range is determined from the volume-based frequency distribution.

[0157]

[Table 1]

The laser diffraction type particle size distribution measuring device HELOS used for measuring the particle size distribution is a device for performing measurement using the Franhofer diffraction principle. Briefly explaining this measurement principle, when a laser beam is irradiated from a laser light source to a measurement particle, a diffraction image is formed on the focal plane of the lens on the opposite side of the laser light source, and the diffraction image is detected by a detector. The particle size distribution of the measurement particles is calculated by performing arithmetic processing.

As a method for preparing the magnetic particles so as to have the above-mentioned average particle size and specific particle size distribution, for example, classification can be carried out by using a sieve. In particular, in order to carry out classification with high accuracy, it is preferable to perform sieving by repeating a plurality of times using a sieve having an appropriate opening. It is also an effective means to use a mesh whose opening shape is controlled by plating or the like.

In order to obtain stable charging characteristics in any environment, it is preferable to coat the surface of the carrier particles with a resin. As a method of coating the surface of the carrier particles with a resin, a conventionally known method such as a method of dissolving or suspending a resin in a solvent and applying the resin and attaching it to the carrier particles, or a method of simply mixing with a powder can be applied.

The substance adhered to the surface of the carrier particles varies depending on the toner, but for example, polytetrafluoroethylene, monochlorotrifluoroethylene polymer, polyvinylidene fluoride, silicone resin, polyester resin, styrene resin, acrylic resin, polyamide, It is suitable to use polyvinyl butyral, amino acrylate resin or the like alone or in combination. Silicone resin is particularly preferable.

The coating resin is preferably 0.1 to 30% by weight (preferably 0.5 to 20% by weight) based on the carrier.

The average particle size of the carrier is 10 to 100 μm,
It is preferably 20 to 70 μm.

When a two-component developer is prepared by mixing with the toner of the present invention, the mixing ratio is 2 to 15% by weight, preferably 3 to 13% by weight, more preferably the toner concentration in the developer. Good results are usually obtained when the amount is 4 to 10% by weight. When the toner concentration is less than 2% by weight, the image density tends to be low, and when the toner containing the wax as in the present invention is used, the developer is likely to deteriorate, which is not preferable. If it exceeds 15% by weight, the distribution of the charge amount of the toner is widened to cause fog and scattering in the machine, which is not preferable.

The method of measuring each characteristic value relating to the toner of the present invention will be described below.

<Hydrophobic Titanium Oxide Fine Particles Ia and Ib
Method of measuring> hydrophobic titanium oxide fine particles Ia and Ib
Is determined by an X-ray diffraction spectrum using a characteristic X-ray Ka line of Cu as a radiation source, and 2θ = 2.0 to 40.0.
The maximum intensity in the range of deg is Ia (Kcps), and the minimum intensity is Ib (Kcps). As a measuring machine, for example, a powerful full-automatic X-ray diffractometer MXP18 (manufactured by Mac Science Co.) can be used.

<Method of measuring number average particle diameter of hydrophobic titanium oxide fine particles> The primary particle diameter is determined by observing the hydrophobic titanium oxide fine particles with a transmission electron microscope and measuring the major axis of 100 particles. Ask for. The particle size on the toner particles is observed with a scanning electron microscope, and the major axis of 100 particles is measured to obtain the number average particle size. Magnification at the time of measurement is 40,000-6
The target is particles of 0.5 nm or more.

<Method for measuring BET specific surface area of hydrophobic titanium oxide fine particles> For the BET specific surface area of hydrophobic titanium oxide fine particles, for example, a fully automatic gas adsorption amount measuring device (Autosoap 1) manufactured by Yuasa Ionics Co., Ltd. is used. Then, it is determined by the BET multipoint method using nitrogen as the adsorption gas. As a pretreatment of the sample, deaeration is performed at 50 ° C. for 10 hours.

<Measurement Method of Hydrophobicity> The hydrophobicity of the hydrophobic titanium oxide fine particles can be determined by a methanol titration test. The methanol titration test is an experimental test for confirming the degree of hydrophobicity of an inorganic fine powder having a hydrophobized surface.

The hydrophobicity measurement using methanol for evaluating the hydrophobicity of the hydrophobic titanium oxide fine particles is performed as follows. 0.2 g of the hydrophobic titanium oxide fine particles to be tested is added to 50 ml of water in an Erlenmeyer flask. Titrate the methanol from the burette. At this time, the solution in the flask is constantly stirred with a magnetic stirrer. The completion of the sedimentation of the hydrophobic titanium oxide fine particles is confirmed by suspending the whole amount in the liquid, and the degree of hydrophobicity is as follows:
Expressed as a percentage of methanol in a liquid mixture of methanol and water.

<Measurement of Particle Size Distribution of Toner> The weight average particle size of the toner and the number% of particles having a predetermined particle size can be obtained by measuring the particle size distribution of the toner. As a measuring device, Coulter Counter TA-II or Coulter Multisizer II (manufactured by Coulter) is used. As the electrolytic solution, about 1% NaCl aqueous solution is prepared using first-grade sodium chloride. For example, ISOTON-II (manufactured by Coulter Scientific Japan Co.) can be used.

As the measuring method, the above-mentioned electrolytic aqueous solution 100 was used.
0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) as a dispersant in 150 ml.
In addition, 2 to 20 mg of the measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes.
Using a 0 μm aperture, the volume and number of toner particles are measured for each channel, and the volume distribution and number distribution of toner are calculated. Then, the weight-based toner weight average particle diameter (D
4) (The central value of each channel is used as a representative value for each channel).

The channels are 2.00 to 2.52.
μm; 2.52 to 3.17 μm; 3.17 to 4.00 μm
m; 4.00 to 5.04 μm; 5.04 to 6.35 μ
m; 6.35 to 8.00 μm; 8.00 to 10.08 μm
m; 10.08-12.70 μm; 12.70-16.
00 μm; 16.0-20.20 μm; 20.20
25.40 μm; 25.40-32.00 μm; 32.
13 channels of 00-40.30 μm are used.

<Aggregation Degree Measuring Method> The aggregation degree is used as one means for measuring the flow characteristics of a sample (a toner having an external additive, etc.). The larger the value of this aggregation degree, the poorer the fluidity of the sample. To judge. As the measuring device, a powder tester (manufactured by Hosokawa Micron Co.) having a digital vibrometer (DigiVibro MODEL 1332) is used.

As the measuring method, 200 mesh, 100 mesh, and 60 mesh sieves were placed on the vibrating table in the order of narrow openings, that is, in order of the 200 mesh, 100 mesh, and 60 mesh sieves so that the 60 mesh sieve was at the top. Set on top of each other.

5 g of an accurately weighed sample was added onto the set 60-mesh sieve, the input voltage to the vibrating table was adjusted so that the displacement value of the digital vibrometer was 0.500 mm, and vibration was applied for 15 seconds. . Then, the weight of the sample remaining on each sieve is measured to obtain the cohesion degree according to the following formula. The sample used was left at 23 ° C. and 60% RH for about 12 hours, and the measurement environment was 23 ° C. and 60% RH.

[0177]

[Equation 1]

<Differential thermal analysis measurement> The above-mentioned endothermic peak of the wax was measured by a differential scanning calorimeter (DSC measuring device), DSC-
7 (manufactured by Perkin Elmer) using ASTM D34
Measure according to 18-82.

The measurement sample is 2 to 10 mg, preferably 5 m
Weigh g accurately. Put this in an aluminum pan, use an empty aluminum pan as a reference, and measure temperature range 3
The measurement is performed at a temperature rising rate of 10 ° C./min between 0 and 200 ° C. under normal temperature and normal humidity. During this temperature raising process and temperature lowering process, the temperature 3
The endothermic and exothermic peaks of the main peak of the DSC curve in the range of 0 to 200 ° C are obtained.

<Molecular Weight Distribution by GPC Measurement> The average molecular weight ratio of the resin component of the toner is measured under the following conditions by a chromatogram by gel permeation chromatography (GPC).

The column was stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (THF) as a solvent was passed through the column at this temperature at a flow rate of 1 ml / min to adjust the sample concentration to 0.05 to 0.6 mass%. About 50 to 200 μl of a THF sample solution of the resin is injected and measured. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value and the number of counts (retention time) of a calibration curve prepared from several kinds of monodisperse polystyrene standard samples.

As a standard polystyrene sample for preparing a calibration curve, for example, manufactured by Tosoh Corporation or Pressure Ch
electrical Co. Made molecular weight 6 × 10 ² , 2.1
× 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 1
0 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8.6 × 10 ⁵ ,
It is suitable to use 2 × 10 ⁶ , 4.48 × 10 ⁶ and use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.

As the column, a plurality of commercially available polystyrene gel columns are preferably combined in order to accurately measure the molecular weight region of 10 ³ to 2 × 10 ⁶ , for example, Shodex GPC KF-801 manufactured by Showa Denko KK, 80
2, 803, 804, 805, 806, 807 combinations and Waters μ-styragel 50
A combination of 0, 10 ³ , 10 ⁴ and 10 ⁵ can be mentioned.

<Method of Measuring Acid Value> In the present invention, the acid value of the binder resin can be measured by a conventional method. For example, 2 to 10 g of a sample is weighed in a 200 to 300 mL Erlenmeyer flask, and methanol: toluene is added. Dissolve the resin by adding about 50 mL of a mixed solvent of 30:70. If the solubility seems to be poor, a small amount of acetone may be added. 0.1%
Using a mixed indicator of bromthymol blue and phenol red, the titration was carried out with a previously standardized N / 10 potassium hydroxide-alcohol solution, and the acid value was calculated from the following formula from the consumption amount of the potassium hydroxide-alcohol solution.

[Equation 2] Acid value = KOH (mL) × N × 56.1 / Sample weight (g) (However, N is a factor of N / 10KOH)

<Measurement Method of Glass Transition Temperature> In the present invention, the glass transition temperature of the binder resin may be measured using a differential thermal analysis measuring device (DSC measuring device) or DSC-7 (manufactured by Perkin Elmer Co.). it can. For example, 5 to 20 mg, preferably 10 mg of the measurement sample is precisely weighed.
This is placed in an aluminum pan, an empty aluminum pan is used as a reference, the measurement temperature range is 30 ° C. to 200 ° C., and the temperature rising rate is 10 ° C./min. In this temperature rising process, an endothermic peak of the main peak in the temperature range of 40 to 100 ° C. is obtained. At this time, the intersection point between the line at the midpoint of the baseline and the differential heat curve before and after the endothermic peak appears is defined as the glass transition temperature Tg.

Next, an example of a developing device for developing a non-magnetic one-component toner using the toner of the present invention will be described. The developing mode using the toner of the present invention is not necessarily limited to this.

FIG. 2 shows an apparatus for developing an electrostatic charge image formed on the electrostatic charge image carrier. In the electrostatic charge image carrier 61, electrostatic charge image formation is performed by electrophotographic process means or electrostatic recording means (not shown). Toner carrier 62
Is made of aluminum or stainless steel, and is made of a non-magnetic sleeve rotatable in the direction of arrow a in the figure. The non-magnetic one-component color toner is stored in the hopper 63 and is supplied onto the toner carrier 62 by the supply roller 64. The supply roller 64 is the toner carrier 62 after development.
The toner on the top is also stripped. Toner carrier 62
The toner supplied above is uniformly and thinly applied by the toner applying blade 65.

Toner coating blade 65 and toner carrier 6
The contact pressure with 2 is 3 as the linear pressure in the sleeve generatrix direction.
〜250 g / cm, preferably 10 to 120 g / cm is effective. When the contact pressure is less than 3 g / cm, it becomes difficult to apply the toner uniformly, and the charge amount distribution of the toner becomes broad, which easily causes fog and scattering. If the contact pressure exceeds 250 g / cm, a large pressure is applied to the toner, so that the toner particles tend to agglomerate or are crushed, which is not preferable. By adjusting the contact pressure to 3 to 250 g / cm, it becomes possible to satisfactorily loosen the agglomeration of the toner having a small particle diameter, and it is possible to instantly increase the triboelectric charge amount of the toner. For the toner application blade 65, it is preferable to use a triboelectric charging series material suitable for charging the toner to a desired polarity.

The toner coating blade 65 is preferably made of silicone rubber, urethane rubber or styrene-butadiene rubber. The use of conductive rubber is preferable because it can prevent the toner from being triboelectrically charged excessively. Further, the surface of the toner coating blade 65 may be coated if necessary. In particular, when used as a negative toner, it is preferable to coat a positively chargeable resin such as polyamide resin.

In a system in which the toner coating blade 65 applies a thin layer of toner onto the toner carrier 62, the thickness of the toner layer on the toner carrier 62 is set to the same as that of the toner carrier 62 in order to obtain a sufficient image density. It is preferable that the length is smaller than the facing gap length with respect to the electrostatic charge image carrier 61, and an alternating electric field is applied to this gap. A bias power source 66 shown in FIG. 2 applies an alternating electric field or a developing bias in which a direct current electric field is superimposed on the alternating electric field between the toner carrier 62 and the electrostatic image carrier 61, whereby electrostatic charge is applied from the toner carrier 62. It is possible to facilitate the movement of the toner on the image carrier 61 and obtain a higher quality image.

An image forming apparatus capable of favorably carrying out the full-color image forming method using the toner of the present invention will be described with reference to FIG.

FIG. 3 is a schematic block diagram showing an example of an image forming apparatus for forming a full-color image by electrophotography. The image forming apparatus shown in FIG. 3 is used as a full-color copying machine or a full-color printer. In the case of a full-color copying machine, as shown in FIG. 3, it has a digital color image reader section in the upper part and a digital color image printer section in the lower part.

In the image reader section, the original 30 is placed on the original table glass 31 and exposed and scanned by the exposure lamp 32, so that the reflected light image from the original 30 is condensed on the full color sensor 34 by the lens 33, and the color color is obtained. Obtain a decomposed image signal. The color-separated image signal is processed by a video processing unit (not shown) via an amplifier circuit (not shown) and sent to a digital image printer section.

In the image printer section, the photosensitive drum 1, which is an image carrier, has a photosensitive layer having, for example, an organic photoconductor, and is rotatably carried in the arrow direction. Around the photosensitive drum 1, a pre-exposure lamp 11, a corona charger 2,
Laser exposure optical system 3, potential sensor 12, four developing devices 4Y, 4C, 4M for accommodating four color toners of different colors.
B, the on-drum light amount detecting means 13, the transfer device 5, and the cleaning device 6 are arranged.

In the laser exposure optical system, the image signal from the reader section is converted into an optical signal for image scan exposure by a laser output section (not shown), and the converted laser light is reflected by the polygon mirror 3a. It is projected onto the surface of the photosensitive drum 1 via the lens 3b and the mirror 3c.

The printer section uses the photosensitive drum 1 when forming an image.
Is rotated in the direction of the arrow, and the photosensitive drum 1 is uniformly negatively charged by the corona charger 2 after the charge is removed by the pre-exposure lamp 11, and the light image E is emitted for each separated color, and the photosensitive drum 1 is statically charged. Form a charge image.

Next, a predetermined developing device is operated to develop the electrostatic charge image on the photosensitive drum 1, and a toner image is formed on the photosensitive drum 1 with toner. Developing devices 4Y, 4C, 4M,
4B includes eccentric cams 24Y, 24C, 24M,
By the operation of 24B, the photosensitive drum 1 is selectively approached in accordance with each separated color, and the development is performed.

The transfer device includes a transfer drum 5a, a transfer charger 5b, an attraction charger 5c for electrostatically attracting a transfer material as a recording material, an attraction roller 5g facing the attraction charger 5c, an inner charger 5d and an outer charger. It has a container 5e and a separation charger 5h. The transfer drum 5a is rotatably rotatably supported, and a transfer sheet 5f, which is a transfer material carrier that carries a transfer material, is integrally adjusted on a cylinder in an opening area of its peripheral surface. A resin film such as a polycarbonate film is used for the transfer sheet 5f.

The transfer material is conveyed from the cassette 7a, 7b or 7c to the transfer drum 5a through the transfer sheet conveying system.
It is carried on the transfer drum 5a. The transfer material carried on the transfer drum 5a is repeatedly conveyed to the transfer position facing the photosensitive drum 1 as the transfer drum 5a rotates, and by the action of the transfer charger 5b during the process of passing the transfer position,
The toner image on the photosensitive drum 1 is transferred onto the transfer material.

The toner image may be directly transferred from the photoconductor to the transfer material, or the toner image on the photoconductor may be transferred to the intermediate transfer material, and the toner image may be transferred from the intermediate transfer material to the transfer material. good.

The above-mentioned image forming process is carried out by using yellow (Y),
By repeating the processes for magenta (M), cyan (C) and black (B), a color image in which four color toner images are overlaid on the transfer material on the transfer drum 5a is obtained.

The transfer material on which the four color toner images have been transferred in this manner is separated from the transfer drum 5a by the action of the separation claw 8a, the separation push-up roller 8b and the separation charger 5h, and the heating and pressure fixing device 9 is attached. The toner is mixed under heat and fixed there by fixing the toner to the transfer material, thereby forming a full-color fixed image.
The sheet is discharged to 0, and the formation of the full-color image is completed.

At this time, the fixing operation speed in the heating and pressure fixing device 9 is the process speed of the main body (for example, 160 mm /
sec) is performed later (for example, 90 mm / sec). This is because when the unfixed image in which two to four layers of toner are laminated is melt-mixed, it is necessary to give a sufficient heating amount to the toner. The amount is increasing.

Next, an example of fixing means applied in image formation using the toner of the present invention will be described.

In FIG. 4, a fixing roller 39, which is a fixing means, is a 2 mm thick RTV silicone rubber layer (room temperature vulcanizing type, J
IS-A hardness 20) 42, and a polytetrafluoroethylene (PTFE) layer 43 having a thickness of 50 μm is provided on the outside thereof.

On the other hand, the pressure roller 40 which is a pressure means.
Is 2 mm thick on a 5 mm thick aluminum cored bar 44, for example.
mm RTV silicone rubber layer (rubber hardness JIS-A hardness 40) 45, with a thickness of 150 μm PTFE on the outside
Have layers.

In FIG. 4, both the fixing roller and the pressure roller have an outer diameter of 60 mm. However, since the pressure roller has a higher hardness, in the paper discharge test with a blank sheet, the discharge direction is the contact point of both rollers. It goes to the pressure roller side from the perpendicular to the line connecting the center lines of both rollers. It is extremely important to set the paper discharge direction to the pressure roller side in order to prevent the fixing support from winding around the fixing support when fixing a copy image having a large image area. As a means for making the paper discharge direction on the pressure roller side, a method of making the hardness difference described above, a method of making the diameter of the pressure roller smaller than that of the fixing roller, or a setting temperature of the pressure roller side more than that of the fixing roller is used. There is a method in which a small amount of paper dust is used by elevating the water content on the back surface of the fixing paper, that is, the paper surface on the pressure roller side, to a higher temperature.

Further, the fixing roller 39 is provided with a halogen heater 46 as a heat generating means, and the pressure roller 4
At 0, a halogen heater 47 is also provided in the core bar,
The transfer material is heated from both sides. The thermistor 48 in contact with the fixing roller 39 and the pressure roller 40
The temperatures of the fixing roller 39 and the pressure roller are detected by a and 48b, and the controller 49 is based on the detected temperatures.
The halogen heaters 46 and 47 are controlled by a and 49b, respectively, and the temperature of the fixing roller 39 and the temperature of the pressure roller 40 are both constant (for example, 160 ° C. ± 1).
It is controlled so that the temperature is maintained at 0 ° C. The fixing roller 39 and the pressure roller 40 have a total pressure of 3 by a pressure mechanism (not shown).
It is pressurized at 90 N (40 kgf).

In FIG. 4, C is a fixing roller cleaning device using an oil-impregnated paper web, and C1 is a cleaning blade for removing oil and dirt adhering to the pressure roller. Oil for paper web impregnation
The use of 50 to 3000 cSt of silicone oil (silicone oils such as dimethyl silicone oil and diphenyl silicone oil) makes it easy to supply a small amount of oil and to provide a fixed image quality (especially uniform). It has high gloss and oil marks).
When the oil is not applied, it is preferable to remove the cleaning device of C, use paper or cloth web not impregnated with oil, use a cleaning blade, a cleaning pad, or a cleaning roller.

The fixing roller cleaning device C cleans the nonwoven fabric web 56 made of Nomex (trade name of DuPont) by pressing the fixing roller 45 against the fixing roller 39. The web 56 is appropriately taken up by a take-up device (for example, a roller on the one end side of C in the figure) so that toner or the like is prevented from accumulating on the contact portion with the fixing roller 39.

Since the toner of the present invention is excellent in low-temperature fixability and high-temperature offset resistance, it is possible to reduce the coating amount of the release agent, and the amount of dirt on the cleaning device is also small.

The toner image of the toner of the present invention is preferably subjected to heat pressure fixing under the temperature condition of the fixing roller surface temperature of 150 ° C. ± 30 ° C., and the fixing member is fixed at the time of fixing the toner image on the recording material. The coating amount of silicone oil supplied from the recording material to the fixing surface of the toner image of the recording material per unit area of the recording material is preferably 0 to 1 × 10 ⁻⁷ g / cm ² . When the coating amount exceeds 1 × 10 ⁻⁷ g / cm ² , the recording material is greatly glared, and the visibility of a character image is significantly impaired.

By the above image forming process, the color toner image having at least the toner of the present invention is fixed on the recording material sheet to obtain the color image formed on the recording sheet.

[0214]

EXAMPLES Production examples and examples relating to the present invention will be shown below, but the present invention is not limited to these.

<Production Example of Anatase Type Titania Sol> A hydrous titanium oxide slurry obtained by thermally hydrolyzing an aqueous solution of titanyl sulfate was neutralized to pH 7 with aqueous ammonia, filtered,
The cake obtained by washing with water is mixed with titanium oxide (TiO ₂
Peptization was carried out with 5% by weight (converted to HCl) of hydrochloric acid, and converted to TiO ₂ to obtain anatase-type titania sol having a concentration of 32% by mass. The average primary particle size of this sol is 7 n
It was m.

<Production Example 1 of Hydrophobic Titanium Oxide Fine Particles> Ilmenite ore containing 50% by weight of TiO ₂ equivalent was used as a starting material. 2 this material at 150 ℃
After drying for an hour, sulfuric acid was added and dissolved to obtain an aqueous solution of TiOSO ₄ . Concentrate this, and use the titania sol with the above anatase crystals as seed.
After adding a mass part, it hydrolyzed at 120 degreeC and obtained the slurry of TiO (OH) ₂ containing an impurity.
This slurry is repeatedly washed with water at pH 5 to 6,
Sulfuric acid, FeSO ₄ , and impurities were thoroughly removed. Then, a high-purity slurry of metatitanic acid (TiO (OH) ₂ ) was obtained.

The pH of the metatitanic acid slurry was adjusted to 8 to
It was adjusted to 9, and the metatitanic acid was sufficiently pulverized with a ball mill. Then, the temperature of the slurry was adjusted to 30 ° C. and the pH was adjusted to about 2 with sufficient stirring. About 6% by weight of metatitanic acid was contained in the slurry. In the slurry, 50 parts by weight of i-C ₄ H ₉ -Si- (OCH ₃ ) as a hydrophobizing agent was added to 100 parts by weight of the metatitanic acid in a solid content.
₃ was added dropwise and reacted with sufficient stirring so that coalescence of particles did not occur. Furthermore, the pH of the slurry was adjusted to 6.5 with sufficient stirring.

This was filtered and dried, and then at 170 ° C. for 2 hours.
Heat treatment is carried out for a period of time to produce hydrophobic titanium oxide fine particles, and thereafter, crushing treatment is repeatedly carried out by a jet mill until aggregates of the hydrophobic titanium oxide fine particles disappear, and 2θ
= 25.0 deg, Ia = 1.13 Kcps, 2θ
= 32.2 deg, Ib = 0.11 Kcps, strength ratio (Ia / Ib) = 10.3, BET specific surface area = 170
Hydrophobic titanium oxide fine particles A having m ² / g, a number average particle diameter of 40 nm and a hydrophobicity of 53% were obtained. An X-ray diffraction chart of the hydrophobic titanium oxide fine particles A is shown in FIG.

<Production Example 2 of hydrophobic titanium oxide fine particles> Titanium tetraisopropoxide was used as a raw material. Using nitrogen gas as a carrier gas, the raw materials are sent to the glass wool of a paper riser heated to 200 ° C to evaporate the raw materials by chemical pumps in small amounts, and thermally decomposed at a temperature of 320 ° C in the reactor, followed by rapid cooling. The product was collected to obtain hydrophilic amorphous titanium oxide fine powder (1). This was baked at 300 ° C. for 2 hours to obtain hydrophilic crystalline titanium oxide fine powder (2).

Then, the titanium oxide fine powder (2) was uniformly dispersed in water, and then the hydrophobizing agent i-C ₄ H ₉ -Si- (OCH
₃ ) ₃ was added dropwise to 100 parts by weight of the titanium oxide fine powder so as to have a solid content of 30 parts by weight while being dispersed so as not to cause the particles to coalesce, and a hydrophobic treatment was performed.

Then, after filtration and drying, the mixture was dried at 120 ° C. for 2 hours.
Heat for 2 hours, then crush with a jet mill and
When θ = 25.7 deg, Ia = 1.15 Kcps, 2
When θ = 31.5 deg, Ib = 0.12 Kcps, strength ratio (Ia / Ib) = 9.6, BET specific surface area = 115
m ² / g, number average particle size = 30 nm, hydrophobicity = 62%
Thus, hydrophobic titanium oxide fine particles B were obtained.

[0222] <Production Example 3 of hydrophobic titanium oxide fine particles> Production Example 1 of hydrophobic titanium oxide fine _{particles, i-C 4 H 9 -Si-} (OCH 3) as a hydrophobizing agent ₃ and C ₆ H ₁₃ -Si
2θ = 24.8de in the same manner as in Production Example 1 except that a mixture of — (OCH ₃ ) ₃ and 1: 1 was used.
When g, Ia = 1.00 Kcps, 2θ = 31.9 de
When g, Ib = 0.12 Kcps, intensity ratio (Ia / I
b) = 8.3, BET specific surface area = 135 m ² / g, number average particle size = 65 nm, and hydrophobicity = 67% of hydrophobic titanium oxide fine particles C were obtained.

<Fourth Production Example of Hydrophobic Titanium Oxide Fine Particles> In the first production example of hydrophobic titanium oxide fine particles, the addition amount of the hydrophobizing agent was set to 20 parts by weight, and the crushing treatment after the hydrophobizing treatment was carried out by hydrophobic titanium oxide. When 2θ = 25.1 deg, I
When a = 0.79 Kcps, 2θ = 30.3 deg I
b = 0.11 Kcps, intensity ratio (Ia / Ib) = 7.
2, BET specific surface area = 345 m ² / g, number average particle size =
Hydrophobic titanium oxide fine particles D having a thickness of 23 nm and a hydrophobicity of 31% were obtained.

<Fifth Production Example of Hydrophobic Titanium Oxide Fine Particles> In the second production example of hydrophobic titanium oxide fine particles, the addition amount of the hydrophobizing agent was set to 60 parts by weight, and the crushing treatment after the hydrophobizing treatment was carried out by hydrophobic titanium oxide. When 2θ = 25.9 deg, I
I when a = 1.18 Kcps, 2θ = 31.4 deg
b = 0.11 Kcps, intensity ratio (Ia / Ib) = 10.
7, BET specific surface area = 101 m ² / g, number average particle size =
Hydrophobic titanium oxide fine particles E having a thickness of 80 nm and a hydrophobicity of 95% were obtained.

<Production Example 6 of Comparative Hydrophobic Titanium Oxide Fine Particles>
> The metatitanic acid obtained in Production Example 1 of hydrophobic titanium oxide fine particles was heat-treated at 300 ° C. for 5 hours and then sufficiently crushed to obtain a BET specific surface area of 120 m ² / g and a number average particle diameter of 100 nm. Thus, hydrophilic titanium oxide fine powder of hydrophilic anatase type crystal was obtained.

Next, the hydrophilic titanium oxide was dispersed in water, and as a hydrophobizing agent, 20 parts by weight of i-C ₄ H ₉ -Si- was added as a hydrophobizing agent to 100 parts by weight of the hydrophilic titanium oxide.
(OCH ₃ ) ₃ was added dropwise while being sufficiently dispersed to perform a hydrophobic treatment.

Then, after filtering and drying at 120 ° C. for 5 hours, heat treatment at 170 ° C. for 5 hours, and then crushing treatment with a jet mill until aggregates of the hydrophobic titanium oxide fine particles disappear, 2θ = Ia at 25.4 deg
= 1.83 Kcps, 2b = Ib when 2θ = 29.2 deg
= 0.11 Kcps, intensity ratio (Ia / Ib) = 16.
6, BET specific surface area = 90 m ² / g, number average particle size = 1
Hydrophobic titanium oxide fine particles F having a thickness of 30 nm and a hydrophobicity of 55% were obtained.

<Production Example 7 of Comparative Hydrophobic Titanium Oxide Fine Particles>
> The metatitanic acid obtained in Production Example 1 of hydrophobic titanium oxide fine particles was heat-treated at 150 ° C. for 2 hours and then sufficiently crushed to obtain BET specific surface area = 135 m ² / g and average particle size = 90 nm. Hydrophilic, anatase type crystalline hydrophilic titanium oxide fine powder was obtained.

Next, the above-mentioned hydrophilic titanium oxide 10 in water is used.
Relative to 0 parts by weight in terms of solid content of 20 parts by weight of i-C ₄ H ₉ -Si- a (OCH _{3) 3} was added dropwise mixed while thoroughly dispersed as a hydrophobic agent, was subjected to hydrophobic treatment.

Then, filtration and heat treatment at 170 ° C. for 3 hours were carried out, and thereafter, crushing treatment by a jet mill was carried out until aggregates of the hydrophobic titanium oxide fine particles disappeared.

As a result, when 2θ = 25.3 deg, I
When a = 1.45 Kcps, 2θ = 29.4 deg I
b = 0.11 Kcps, intensity ratio (Ia / Ib) = 13.
2, BET specific surface area = 110 m ² / g, number average particle size =
Hydrophobic titanium oxide fine particles G having a thickness of 110 nm and a hydrophobicity of 55% were obtained.

<Production Example 8 of Comparative Hydrophobic Titanium Oxide Fine Particles>
> Oxidation after hydrophobic titanium oxide amorphous titanium oxide fine powder obtained in Production Example 2 of fine particles (1) was uniformly dispersed in water, hydrophobic agents i-C ₄ H ₉ -Si- (the OCH _{3) 3} 100 parts by weight of fine titanium powder was added dropwise with stirring so that the solid content was 20 parts by weight, and a hydrophobic treatment was performed.

Then, after filtration and drying, heat treatment at 120 ° C., crushing treatment by a jet mill, and 2θ
= 39.6 deg, Ia = 0.13 Kcps, 2θ
= 20.6 deg, Ib = 0.04 Kcps, strength ratio (Ia / Ib) = 3.3, BET specific surface area = 120 m
² / g, number average particle diameter = 25 nm, and hydrophobicity = 65% of hydrophobic titanium oxide fine particles H were obtained.

<Production Example 9 of Comparative Hydrophobic Titanium Oxide Fine Particles>
> 2θ = 25.4 in the same manner as in Production Example 2 except that the amorphous titanium oxide fine powder (1) is fired at 800 ° C. for 5 hours in Production Example 2 of hydrophobic titanium oxide fine particles.
When deg, Ia = 1.81 Kcps, 2θ = 29.4
When deg, Ib = 0.12 Kcps, intensity ratio (Ia /
Ib) = 15.1, BET specific surface area = 85 m ² / g, number average particle size = 60 nm, and hydrophobicity = 52% of hydrophobic titanium oxide fine particles I of anatase type crystal were obtained.

<Production Example 1 of Comparative Hydrophobic Titanium Oxide Fine Particles>
0> fine titanium oxide powder mixed with hydrophilic anatase type crystals and rutile type crystals obtained by flame method of titanium tetrachloride (manufactured by Nippon Aerosil Co., Ltd., Titanium)
100 parts by weight of Oxidep 25) was uniformly dispersed in water. Then, 20 parts by weight of i-
_{C 4 H 9 -Si- (OCH 3} ) 3 was added dropwise mixed while dispersing to not particle coalescence was subjected to hydrophobic treatment.

Then, after filtration and drying, the mixture is dried at 120 ° C. for 2 hours.
Heat treatment for an hour, then crushing with a jet mill, and when 2θ = 27.3 deg, Ia = 1.68 Kcp
s, 2θ = 29.2 deg, Ib = 0.12 Kcp
s, intensity ratio (Ia / Ib) = 14.0, BET specific surface area = 65 m ² / g, number average particle size = 55 nm, degree of hydrophobicity =
50% of hydrophobic titanium oxide fine particles J was obtained.

<Production Example 11 of hydrophobic titanium oxide fine particles>
Ia = 1.09 Kcp when 2θ = 25.1 deg, in the same manner as in Production Example 1 of hydrophobic titanium oxide fine particles except that the titania sol having anatase crystals was not used.
When s, 2θ = 32.2 deg, Ib = 0.10 Kcp
s, intensity ratio (Ia / Ib) = 10.9, BET specific surface area = 163 m ² / g, number average particle diameter = 50 nm, and hydrophobic titanium oxide fine particles K having a hydrophobicity of 53% were obtained. Table 2 shows characteristic values of the above-mentioned hydrophobic titanium oxide fine particles.

[0238]

[Table 2]

<Resin Production Example (Hybrid Resin Production Example 1)> As a vinyl-based copolymer, styrene 1.9mo
1, 2-ethylhexyl acrylate 0.21 mol,
Fumaric acid 0.15 mol, α-methylstyrene dimer 0.03 mol, dicumyl peroxide 0.05 mo
1 in a dropping funnel. In addition, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl)
Propane 7.0 mol, polyoxyethylene (2.2)
3.0 mol of 2,2-bis (4-hydroxyphenyl) propane, 3.0 mol of succinic acid, 2.0 mol of trimellitic anhydride, 5.0 mol of fumaric acid, and 0.2 g of dibutyltin oxide were added to a glass-made 4 liter solution. The flask was placed in a one-necked flask, a thermometer, a stirring rod, a condenser and a nitrogen introducing tube were attached and placed in a mantle heater. Next, after replacing the inside of the flask with nitrogen gas, the temperature was gradually raised with stirring, and the vinyl resin monomer, the cross-linking agent and the polymerization initiator were added from the dropping funnel while stirring at a temperature of 145 ° C. It was added dropwise over 4 hours. Then, the temperature was raised to 200 ° C. and the reaction was carried out for 4 hours to obtain a hybrid resin (1). Table 3 shows the results of molecular weight measurement and acid value measurement by GPC.

<Resin Production Example (Polyester Resin Production Example 1)> Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 3.6 mol, polyoxyethylene (2.2) -2 , 2-bis (4-hydroxyphenyl) propane 1.6 mol, terephthalic acid 1.7 mol, trimellitic anhydride 1.1 mol, fumaric acid 2.4 mol and dibutyltin oxide 0.1 g are made of glass 4 liter four-neck The flask was put into a flask, a thermometer, a stirring rod, a condenser and a nitrogen introducing tube were attached and placed in a mantle heater. Under a nitrogen atmosphere, the reaction was carried out at 215 ° C. for 5 hours to obtain a polyester resin (1). Table 3 shows the results of molecular weight measurement and acid value measurement by GPC.

<Resin Production Example (Vinyl Resin Production Example 1)
> 1000 ml of toluene solvent, 2.4 mol of styrene as a vinyl-based copolymer, and n-butyl acrylate of 0.
26 mol, monobutyl maleate 0.09 mol, di-
0.11 mol of t-butyl peroxide was measured with a thermometer,
It was placed in a 3 liter four-necked flask equipped with a stainless stir bar, a flow-down condenser and a nitrogen inlet tube, and reacted while refluxing toluene while stirring at a temperature of 120 ° C. in a nitrogen atmosphere in a mantle heater, A vinyl resin (1) was obtained. Table 3 shows the results of molecular weight measurement and acid value measurement by GPC.

[0242]

[Table 3]

The waxes used in this example are shown in the table below.

[0244]

[Table 4]

[0245] <Example 1>   Hybrid resin 1 100 parts by weight   Phthalocyanine pigment (cyan colorant) 4 parts by weight   Aluminum complex of di-tert-butylsalicylic acid (negative charge control agent)                                                               4 parts by weight   Wax A 5 parts by weight

The above compounds were sufficiently premixed with a Henschel mixer, melt-kneaded with a twin-screw extrusion-type kneader, cooled, coarsely pulverized with a hammer mill to about 1 to 2 mm, and then finely pulverized with an air jet system. Pulverized with a machine. Further, the obtained finely pulverized product was classified so that the weight average particle diameter was 6.0 μm (the particle diameter of 4.0 μm or less was 21.3 μm).
%, Particle size 5.04 μm or less is 48.5 number%, particle size 8.0 μm or more is 6.1% by volume, particle size 10.08 μm or more is 0.6% by volume. Non-magnetic cyan toner particles were obtained.

100 parts by weight of the cyan toner particles and 1.5 parts by weight of the hydrophobic titanium oxide fine particles A were mixed with a Henschel mixer to obtain a non-magnetic cyan toner. The obtained cyan toner had substantially the same particle size distribution as the cyan toner particles.

The above-mentioned cyan toner and silicon resin-coated ferrite carrier were mixed at a toner concentration of 6% to prepare a two-component type developer, and a color copying machine CLC-800 was prepared.
(Canon, single color mode, A4 size, 28 sheets / min) is removed, and a modified machine without an oil application mechanism is used, and an original document with an image area ratio of 25% is used in a high temperature and high humidity environment (35 ° C / 80 ° C). %), And using an original document with an image area ratio of 10% under a room temperature and low humidity environment (23 ° C./5%), the toner application amount per unit area is set to 0.7 mg / cm ² . 1 in mono color mode
A printing durability test was conducted by outputting 10,000 sheets of unfixed images.

For the unfixed image that was output, a fixed image was prepared using a fixing device in which the fixing roller cleaning device C is removed from the fixing device shown in FIG. Further, a fixing test was conducted under a normal temperature and normal humidity environment (23 ° C., 60%). Further, regarding the evaluation of the feasible region, the fixing device in which the roller cleaning device C is removed from the fixing device shown in FIG. 4 is modified so that the fixing temperature can be manually set.

The above-described two-component type developer has extremely small fluctuations in image density, fog, and toner charge amount in the printing durability test, and has no problem of toner scattering after 10,000 sheets, fixing property, OHP.
The transparency was also good, and very excellent results were obtained. The surface of the OPC photosensitive drum after 10,000 sheets of durability was observed with a scanning electron microscope. As a result, there were no deposits and scratches and the surface condition was good. Physical properties of the toner used in this example are shown in Table 5, and results of this example are shown in Table 6. Each evaluation method will be described below.

<OHP Transparency of Toner> A toner image is transferred onto an OHP sheet and fixed, and the fixed image is transmitted through an overhead projector to observe the projected image on the screen. A = (good); The projected image on the screen is clear and no dull color is seen. B = (no problem in practical use); the projected image on the screen is clear and some dullness of color is seen, but it is at a level where there is no practical problem. C = (problem in practical use); the projected image on the screen lacks sharpness, and dull colors are seen, which is a practical problem. D = (unusable); the projected image on the screen is unclear, and dull colors are seen, which is a level that is impractical.

<Fog> The evaluation of fog was made by Tokyo Denshoku Co., Ltd., REFRECTOMER MODEL TC-6D.
S is used to measure, and for cyan toner images, it is amber
Using a filter, it was calculated from the following formula and evaluated according to the following evaluation criteria. The smaller the value, the less the fog.

[Formula 3] Fog (reflectance) (%) = reflectance of standard paper (%)-reflectance of non-image part of sample (%)

A: Fog is 1.0% or less, which is a good level. B: 1.0% to 2.0%, which is a level with no practical problems. C: 2.0 to 4.0%, which is a practically problematic level. D: It is 4.0% or more, which is a level that is not practical.

<Toner scattering> Developing device after 10,000 sheets of durability,
Observe the degree of toner contamination around the in-body developing device. A: Staining by the toner around the developing device and the developing device in the main body is not observed at all. B: Contamination due to a slight amount of toner is observed in the developing device, but there is no practical problem. C: Contamination due to toner around the developing device and the developing device in the main body is observed, which is a problem in practical use. D: The developing device and the periphery of the developing device in the main body are markedly contaminated with the toner, and the main body function is adversely affected.

<Highlight Reproducibility> An image having a Macbeth image density of 0.3 to 0.6 is output, and the uniformity of density and the degree of roughness are visually evaluated. A: A good output image with excellent uniformity of image density. B: The image density is slightly lacking in uniformity, but there is no practical problem. C: The image density is poor in uniformity of the image density and is a rough output image, which is a problematic level in practical use. D: The uniformity of the image density is extremely poor, and the output image is rough, which is a level that is not practical.

<Surface of Photoreceptor> After scanning 10,000 sheets, 30 sites on the surface of the photoreceptor are observed with a scanning electron microscope. A: No deposits such as toner and scratches are observed. B: Adhered substances such as toner and scratches are observed at several places, but they do not appear as image defects, and are at a level where there is no practical problem. C: Adhered substances such as toner and scratches are observed at ten or more places and appear as image defects, which is a practical problem. D: A large number of adhered substances such as toner and scratches are observed, which appear as remarkable image defects, which is at an impractical level.

Example 2 A two-component developer was prepared in the same manner as in Example 1 except that the hydrophobic titanium oxide fine particles B were used, and the same experiment as in Example 1 was carried out.
Even after 10,000 sheets of running, the fluctuation of the toner charge amount is small, the image density is high and stable, a fog-free and high-definition reproducible high-definition image is obtained, and toner scattering does not occur, and good results are obtained. Was obtained. In addition, no deposits or scratches were found on the surface of the photoreceptor after the durability test.

Example 3 A two-component type developer was prepared in the same manner as in Example 1 except that the hydrophobic titanium oxide fine particles C were used, and the same experiment as in Example 1 was conducted.
Even after 10,000 sheets of durability, the fluctuation of the toner charge amount was small, the image density was high and stable, and a good image without fog was obtained. In addition, good results were obtained without toner scattering. Furthermore, no deposits or scratches were found on the surface of the photoreceptor after the durability test.

Since the toner of this example is slightly higher in cohesion than the toner of Example 1 in terms of reproducibility of the highlight portion, it was not at a level causing practical problems.

Example 4 A two-component type developer was prepared in the same manner as in Example 1 except that the hydrophobic titanium oxide fine particles D were used, and the same experiment as in Example 1 was carried out. After ten thousand sheets, the toner charge amount was slightly reduced, the image density was slightly increased, some fog was observed, and a very small amount of toner was scattered. However, these phenomena were not at a level that caused practical problems. In addition, no deposits or scratches were found on the surface of the photoreceptor after the durability test.

<Example 5> A two-component type developer was prepared in the same manner as in Example 1 except that the hydrophobic titanium oxide fine particles E were used, and the same experiment as in Example 1 was conducted. After ten thousand sheets, the charge amount of the toner slightly increased, so that the image density slightly decreased, but no fog or toner scattering was observed, and good results were obtained.

Further, the surface of the photoreceptor after the endurance is slightly scratched, which is considered to be caused by the aggregate of hydrophobic titanium oxide fine particles,
Was observed, but there was no image defect and it was not at a level causing a problem in practical use.

<Example 6> The weight average particle size produced in the same manner as in Example 1 is 2.5 μm (8 when the particle size is 4.0 μm or less.
A two-component developer was prepared in the same manner as in Example 1 except that negative triboelectrically chargeable non-magnetic cyan toner particles (1.3% by number) were used, and the same experiment as in Example 1 was conducted. In either of the environments, the image density slightly decreased after 10,000 sheets of durability and some fog and toner scattering occurred, but this was not a practically problematic level.

It is considered that this is because the weight average particle diameter of the cyan toner particles was small and the charge amount per unit weight was high, so that the image density was slightly lowered. In addition, since it is difficult to smoothly charge the carrier with contact with the carrier, it is presumed that insufficiently charged toner is generated, and some fog and toner scattering occur.

Example 7 Negative triboelectrically-charged non-magnetic cyan toner particles having a weight average particle diameter of 9.5 μm (particle size of 4.0 μm or less is 5.3% by number) manufactured in the same manner as in Example 1. A two-component type developer was prepared in the same manner as in Example 1 except that the above was used, and the same experiment as in Example 1 was performed. The reproducibility level was rather poor and the image was slightly lacking in fineness. However, it was not at a level that caused practical problems.

This is because the cyan toner particles have a large weight average particle diameter, and therefore the particle diameter of 4 μm which greatly contributes to the fine line reproducibility.
It is considered that this is because there are few toner particles of m or less.

Example 8 The weight average particle diameter is 6.5 μm in the same manner as in Example 1 except that a magenta colorant (dimethylquinacridone pigment) is used in place of the cyan colorant.
m (19.3% by number of particles having a particle size of 4.0 μm or less) of non-magnetic magenta toner particles having negative triboelectrification properties are produced, and 100 parts by mass of the magenta toner particles and 1.3 parts by mass of the hydrophobic titanium oxide fine particles A are used. And were mixed to obtain a non-magnetic magenta toner.

Then, a two-component type developer was obtained in the same manner as in Example 1, and an image forming test was conducted in the same manner as in Example 1 at a process speed of 28 sheets / minute in A4 size of a single color mode. As in No. 1, a good magenta image was obtained, showing good environmental stability and good multi-sheet durability.

Example 9 A yellow colorant (CI Pigment Yellow 1) was used instead of the cyan colorant.
Negative triboelectrically chargeable non-magnetic yellow toner particles having a weight average particle size of 6.3 μm (particle size of 4.0 μm or less is 20.6% by number) are obtained in the same manner as in Example 1 except that 7) is used. 100 parts by weight of the yellow toner particles produced and 1.0 part by weight of the hydrophobic titanium oxide A were mixed to obtain a non-magnetic yellow toner. Then, a two-component type developer was obtained in the same manner as in Example 1, and an image development test was conducted in the same manner as in Example 1 at a process speed of 40 sheets / min of monochromatic mode A4 size. In addition, a good yellow image was obtained, showing good environmental stability and good durability for multiple sheets.

Example 10 Example 1 is repeated except that 3 parts by mass of carbon black is used instead of the cyan colorant.
Similarly, the weight average particle size is 6.3 μm (particle size 4.0 μm
m is 21.9% by number), and non-magnetic black toner particles having negative triboelectric charging properties are produced.
Part by mass and 1.0 part by mass of hydrophobic titanium oxide A were mixed to obtain a non-magnetic black toner. Then, a two-component type developer was obtained in the same manner as in Example 1, and an image development test was conducted in the same manner as in Example 1 at a process speed of 40 sheets / min of monochromatic mode A4 size. In addition, a good black image was obtained, showing good environmental stability and good durability for multiple sheets.

Next, the cyan two-component developer prepared in Example 1, the magenta two-component developer prepared in Example 8, and the yellow one prepared in Example 9 were prepared. A two-component developer for color and a two-component developer for black color prepared in this example were used to perform an image-forming test in a full-color mode with the full-color copying machine.
A high-quality full-color image faithfully reproducing the original full-color image was obtained.

Example 11 Polyester resin 1 is used in place of hybrid resin 1, aluminum complex of di-tert-butylsalicylic acid (negative charge control agent)
In the same manner as in Example 1 except that 6 parts by weight of is used to produce negative triboelectrically chargeable non-magnetic cyan toner particles having a weight average particle size of 6.1 μm. A non-magnetic cyan toner was obtained by mixing with 1.0 part by mass of titanium oxide A. Then, a two-component type developer was obtained in the same manner as in Example 1, and an image forming test was conducted in the same manner as in Example 1 at a process speed of monochromatic mode A4 size 40 sheets / min. In addition, a good cyan image was obtained. Although the fixing temperature range was slightly narrowed and the image density was slightly lowered, it exhibited relatively good environmental stability and durability for multiple sheets.

<Example 12> 50 parts by mass of polyester resin 1 and 50 parts by mass of vinyl resin 1 were used in place of hybrid resin 1, and 6 parts of an aluminum complex of di-tert-butylsalicylic acid (negative charge controlling agent) was used. Negative triboelectrically chargeable non-magnetic cyan toner particles having a weight average particle diameter of 6.4 μm were produced in the same manner as in Example 1 except that 100 parts by weight of cyan toner particles and hydrophobic titanium oxide were used. A non-magnetic cyan toner was obtained by mixing with 1.0 part by mass of A. Then, a two-component type developer was obtained in the same manner as in Example 1, and an image development test was conducted in the same manner as in Example 1 at a process speed of 40 sheets / min of monochromatic mode A4 size. In addition, a good cyan image was obtained. Although the fixing temperature range was slightly narrowed and the image density was slightly lowered, it exhibited relatively good environmental stability and durability for multiple sheets.

Example 13 Using vinyl resin 1 in place of hybrid resin 1, di-tert-butylsalicylic acid aluminum complex (negative charge control agent) 6
Negative triboelectrically chargeable non-magnetic cyan toner particles having a weight average particle diameter of 6.2 μm were produced in the same manner as in Example 1 except that 100 parts by weight of cyan toner particles and hydrophobic titanium oxide were used. A non-magnetic cyan toner was obtained by mixing with 1.0 part by mass of A. Then, a two-component developer is obtained in the same manner as in Example 1, and a single color mode A is obtained in the same manner as in Example 1.
When an image output test was carried out at a process speed of 40 sheets of 4 sizes / minute, a good cyan image was obtained as in Example 1. Although the fixing temperature range was slightly narrowed and the image density was slightly lowered, it exhibited relatively good environmental stability and durability for multiple sheets.

<Example 14> Hydrophobic titanium oxide fine particles K
A two-component type developer was prepared in the same manner as in Example 1 except that was used, and the same experiment as in Example 1 was conducted.
Since the toner charge amount slightly decreased after 10,000 sheets of durability under high temperature and high humidity environment, the image density became slightly high, some fog was observed, and a very small amount of toner scattering occurred. However, these phenomena were not at a level that caused practical problems. In addition, on the surface of the photoreceptor after the endurance, no deposits or scratches that could pose a problem in practical use were observed.

Example 15 The weight average particle size is 6.4 μm (particle size of 4.0 μm or less is 24.1) in the same manner as in Example 1 except that wax B is used instead of wax A.
Negative triboelectrically chargeable non-magnetic cyan toner particles (number%) were produced, and 100 parts by weight of the cyan toner particles and 1.0 part by weight of the hydrophobic titanium oxide A were mixed to obtain a non-magnetic cyan toner. Then, a two-component developer is obtained in the same manner as in Example 1, and in the same manner as in Example 1, single color mode A4 size 40
When an image output test was conducted at a process speed of one sheet / minute, a good cyan image was obtained as in Example 1. Although the fixing temperature range was slightly narrowed and the image density was slightly increased, it showed relatively good environmental stability and durability for multiple sheets. In addition, on the surface of the photoreceptor after the endurance, no deposits or scratches that could pose a problem in practical use were observed.

Example 16 The weight average particle diameter is 6.4 μm (particle diameter of 4.0 μm or less is 21.8) in the same manner as in Example 1 except that wax D is used instead of wax A.
Negative triboelectrically chargeable non-magnetic cyan toner particles (number%) were produced, and 100 parts by weight of the cyan toner particles and 1.0 part by weight of the hydrophobic titanium oxide A were mixed to obtain a non-magnetic cyan toner. Then, a two-component developer is obtained in the same manner as in Example 1, and in the same manner as in Example 1, single color mode A4 size 40
When an image output test was conducted at a process speed of one sheet / minute, a good cyan image was obtained as in Example 1. Although the fixing temperature range was slightly narrowed and the image density was slightly increased, it showed relatively good environmental stability and durability for multiple sheets. In addition, on the surface of the photoreceptor after the endurance, no deposits or scratches that could pose a problem in practical use were observed.

Comparative Example 1 A two-component type developer was prepared in the same manner as in Example 1 except that the hydrophobic titanium oxide fine particles F were used, and the same experiment as in Example 1 was conducted.
After 10,000 sheets of durability, the toner charge amount drastically decreased, and the charge amount distribution width was wide, resulting in a marked increase in image density.
Toner scattering occurred. These phenomena remarkably occurred especially in a high temperature and high humidity environment. Further, when the surface of the OPC photosensitive drum after the durability was observed, it was found that many deep scratches were generated on the entire surface, and these scratches appeared as image defects.

The hydrophobic titanium oxide fine particles F used in this comparative example have a large strength ratio (Ia / Ib) and contain a large number of aggregates, and when externally added to the toner particles, sufficient toner fluidity is obtained. In addition to not being obtained, the photoreceptor surface was damaged. Further, since there are hydrophobic titanium oxide fine particles whose surface is not uniformly treated with a hydrophobizing agent, the controllability of the charge amount of the toner is low, which causes the above-mentioned adverse effects. It is thought to have occurred.

Comparative Example 2 A two-component type developer was prepared in the same manner as in Example 1 except that the hydrophobic titanium oxide fine particles G were used, and the same experiment as in Example 1 was carried out. After 10,000 sheets, the charge amount of the toner decreased, and the charge amount distribution width became broad, so that the image density increased and fogging and toner scattering occurred. These phenomena remarkably occurred especially in a high temperature and high humidity environment. Further, when the surface of the OPC photosensitive drum after the durability test was observed, it was found that many deep scratches were generated on the entire surface, and these scratches appeared as image defects.

The hydrophobic titanium oxide fine particles G used in this comparative example have grown crystals because they are fired before the hydrophobic treatment, and have a large strength ratio (Ia / Ib) and a large number of aggregates. In addition, when externally added to the toner particles, not only the fluidity was not sufficiently obtained, but also the surface of the OPC photosensitive drum was damaged. Further, since there are hydrophobic titanium oxide fine particles whose surface is not uniformly treated with a hydrophobizing agent, the controllability of the charge amount of the toner is low, which causes the above-mentioned adverse effects. It is considered to be a thing.

Comparative Example 3 A two-component type developer was prepared in the same manner as in Example 1 except that the hydrophobic titanium oxide fine particles H were used, and the same experiment as in Example 1 was conducted.
Even after 10,000 sheets of durability, the fluctuations in the toner charge amount and the image density were at a level that did not pose a problem. Further, although fog and toner scattering were observed, they were at a level without problems.

However, when the surface of the OPC photosensitive drum was observed after the durability test, it was confirmed that there were many scratches but toner was attached. Then, the portion to which the toner is attached appears as an image defect, which is at a level not suitable for practical use.

Since the hydrophobic titanium oxide fine particles H used in this comparative example have a small intensity ratio (Ia / Ib) and do not have a clear high peak in X-ray diffraction, they are non-crystalline hydrophobic titanium oxide fine particles. Therefore, since the hydrophobic titanium oxide fine particles have no crystal growth at all, the particles become soft, and even the fine particles having an average particle diameter of 25 nm have a low ability to impart abrasiveness to the toner,
It is considered that the toner attached to the surface of the OPC photosensitive drum could not be removed.

Comparative Example 4 A two-component developer was prepared in the same manner as in Example 1 except that the hydrophobic titanium oxide fine particles I were used, and the same experiment as in Example 1 was carried out. After ten thousand sheets, the toner charge amount decreased, and the charge amount distribution width widened, so that the image density increased and fogging and toner scattering occurred. Further, when the surface of the OPC photosensitive drum after the durability test was observed, it was found that many scratches were generated on the entire surface, and these scratches appeared as white spots on the image.

Since the hydrophobic titanium oxide fine particles I used in this comparative example are obtained by subjecting the hydrophobic titanium oxide fine powder obtained by firing at high temperature for a long time to the hydrophobic treatment, the strength ratio (I
a / Ib) was large, the BET ratio surface was small, and a large amount of aggregate was contained. When the hydrophobic titanium oxide fine particles I are externally added to the toner particles, the fluidity of the toner is not sufficiently obtained, the highlight reproducibility level is poor, and it is difficult to control the charge amount of the toner well. It was It is also understood that the aggregate of the fine particles of the hydrophobic titanium oxide damaged the surface of the OPC photosensitive drum.

Comparative Example 5 A two-component type developer was prepared in the same manner as in Example 1 except that the hydrophobic titanium oxide fine particles J were used, and the same experiment as in Example 1 was carried out. After 10,000 sheets, the charge amount of the toner decreased and the charge amount distribution was broadened, so that the image density increased and fogging and toner scattering occurred. Further, it was observed that many deep scratches were formed on the entire surface of the OPC photosensitive drum after the durability test, and these scratches appeared as image defects.

The hydrophobic titanium oxide fine particles J used in this comparative example contained anatase type and rutile type crystals and had a large strength ratio (Ia / Ib), so that the BET specific surface area was small and aggregates were formed. When a large amount of the hydrophobic titanium oxide fine particles were externally added to the toner particles, sufficient fluidity of the toner was not obtained and the surface of the OPC photosensitive drum was damaged. Further, it is difficult to control the charge amount of the toner satisfactorily, and it is considered that these causes cause the above-mentioned adverse effects.

Comparative Example 6 Two components were prepared in the same manner as in Example 1 except that hydrophobic silica fine particles (R972 manufactured by Nippon Aerosil Co., Ltd.) were used in place of the hydrophobic titanium oxide fine particles A. A system developer was prepared and an image development test was conducted in the same manner as in Example 1. After 10,000 sheets of durability, the charge amount of the toner increased and the charge amount distribution was broadened, so that the image density significantly decreased, and fog and toner scattering occurred.

Comparative Example 7 The weight average particle size was 6.1 μm (25.3% by number of particles having a particle size of 4.0 μm or less) in the same manner as in Example 1 except that the wax E was used instead of the wax A. Non-magnetic cyan toner particles having negative triboelectrification property were produced, and 100 parts by mass of the cyan toner particles and 1.0 part by mass of the hydrophobic titanium oxide A were mixed to obtain a non-magnetic cyan toner.

Then, a two-component type developer was obtained in the same manner as in Example 1, and an image formation test was conducted in the same manner as in Example 1 at a process speed of 40 sheets / minute for a single color mode A4 size. The width became narrow, the OHP transparency was poor, and the image density was slightly reduced. In addition, fine line reproducibility was poor, and good image quality could not be obtained. In addition, on the surface of the photoreceptor after the endurance, no deposits or scratches that could pose a problem in practical use were observed.

Comparative Example 8 The weight average particle diameter is 6.3 μm (the particle diameter of 4.0 μm or less is 22.0% by number) in the same manner as in Example 1 except that the wax C is used instead of the wax A. Non-magnetic cyan toner particles having negative triboelectrification property were produced, and 100 parts by mass of the cyan toner particles and 1.0 part by mass of the hydrophobic titanium oxide A were mixed to obtain a non-magnetic cyan toner.

Then, a two-component type developer was obtained in the same manner as in Example 1, and an image output test was conducted in the same manner as in Example 1 at a process speed of 40 sheets / minute in a single color mode A4 size. The width became narrow, OHP transparency was poor, and the image density was slightly increased. In addition, fine line reproducibility was poor, and good image quality could not be obtained. Further, toner adhesion was observed on the surface of the photoreceptor after the durability test.

[0294]

[Table 5]

[0295]

[Table 6]

[0296]

The toner of the present invention comprises a binder resin, a colorant,
And a wax-containing toner particle and a hydrophobic titanium oxide fine particle, and a peak temperature of a maximum endothermic peak in a temperature range of 30 to 150 ° C. is in a range of 50 to 100 ° C. in an endothermic curve in a differential thermal analysis measurement. And the hydrophobic titanium oxide fine particles are 2θ = 2 in X-ray diffraction.
Since the ratio of the maximum strength to the minimum strength in the range of 0.0 to 40.0 deg is 5.0 or more and 12.0 or less, it has good chargeability, fluidity, and transferability, and is high in each environment. A fine and high-quality image can be stably provided.

Further, in the toner of the present invention, due to the polishing effect of the hydrophobic titanium oxide fine particles contained therein, the adhered matter does not occur on the surface of the photoreceptor even after long-term use, and the adhered matter on the surface of the photoreceptor does not occur. When it occurs, it is polished and removed, so that a high-quality image without image defects can be stably provided.

Further, in the present invention, the binder resin is any one of a polyester resin, a hybrid resin having a polyester unit and a vinyl copolymer unit, and a mixture of the polyester resin and the vinyl copolymer. A resin selected from sufficient high temperature offset resistance,
It is even more effective in achieving heat resistance and blocking resistance.

In the present invention, the binder resin has an acid value of 1 to 4
When it is 0 mgKOH / g, it is more effective in achieving excellent charging stability in each environment.

Further, in the present invention, when the toner has an organometallic compound, it is more effective in controlling the viscoelastic property and triboelectric charging property of the toner.

Further, in the present invention, the hydrophobic titanium oxide fine particles are prepared by adding a silane coupling agent to the dispersion liquid in which the metatitanic acid particles are dispersed to hydrophobize the metatitanic acid particles to obtain the hydrophobicized metatitanic acid particles. Separate from the solution,
The particles produced by heating the separated metatitanic acid particles are more effective in enhancing the fluidity imparting ability to the toner and the polishing ability of the photoreceptor surface.

Further, in the present invention, as the hydrophobic titanium oxide fine particles, titania sol having anatase type crystal structure is added as a seed to the titanium-containing aqueous solution, and the titanium component in the titanium-containing aqueous solution is hydrolyzed to obtain metatitanic acid particles, A silane coupling agent is added to the dispersion liquid in which the obtained metatitanic acid particles are dispersed, to make the metatitanic acid particles hydrophobic,
It is even more effective in suppressing the occurrence of drum scratches in durability when it is produced by separating the hydrophobized metatitanic acid particles from the solution and subjecting the separated metatitanic acid particles to heat treatment.

Further, in the present invention, when the BET specific surface area of the hydrophobic titanium oxide fine particles is 100 to 350 m ² / g, the fluidity with respect to the toner is improved, the polishing ability with respect to the photoconductor is controlled, and the environment-friendly property is improved. It is even more effective in achieving stable chargeability.

Further, in the present invention, when the number average particle diameter of the hydrophobic titanium oxide fine particles is 1 to 100 nm, it is much more effective in realizing a suitable polishing property.

In the present invention, the hydrophobic titanium oxide fine particles having a hydrophobicity of 40 to 90% are more effective in controlling the triboelectric chargeability of the toner.

Further, in the present invention, when the weight average particle diameter of the toner is 3 to 9 μm, the image density is sufficient, and it is more effective in obtaining an image excellent in highlight reproducibility and fine line reproducibility. is there.

Further, in the present invention, the hydrophobic titanium oxide fine particles are 2θ = 20.0 to 40.0 deg in X-ray diffraction.
Within the range of 2θ = 24.0 to 26.0 deg
And the minimum strength of 2θ = 28.0 to 33.0 deg is more effective in imparting fluidity to the toner and improving the charging stability of the toner.

Further, in the present invention, the hydrophobic titanium oxide fine particles are more effective when treated with a silane coupling agent, and 1 to 60 parts by weight of the silane coupling agent is added to 100 parts by weight of the hydrophobic titanium oxide fine particles. Is more effective when treated with.

Further, in the present invention, the hydrophobic titanium oxide fine particles are more effective when treated with an alkylalkoxysilane coupling agent, and 1 to 60 parts by weight of alkylalkoxy are used per 100 parts by weight of the hydrophobic titanium oxide fine particles. It is even more effective when treated with a silane coupling agent.

Further, in the present invention, if the hydrophobic titanium oxide fine particles are externally added in an amount of 0.1 to 5 parts by weight per 100 parts by weight of the toner particles, it is more effective in controlling the fluidity of the toner.

In the present invention, the particle size is 4 μm based on the number distribution.
When 8 to 70% by number of toner particles having a particle diameter of m or less is contained, it is more effective in stably forming a high quality image for a long period of time.

Further, in the present invention, the degree of aggregation of the toner is 2-3.
When it is 5%, it is more effective in obtaining a toner having excellent fluidity and developability.

In the present invention, depending on the kind of colorant,
Non-magnetic cyan toner particles, non-magnetic magenta toner particles,
Various toners such as non-magnetic yellow toner particles and non-magnetic black toner particles can be formed, which is even more effective in obtaining a high-quality, full-color image that can be obtained stably over a long period of time.

[Brief description of drawings]

FIG. 1 X of hydrophobic titanium oxide fine particles used in the present invention
It is a figure which shows an example of a line diffraction chart.

FIG. 2 is a schematic explanatory view showing a specific example of a developing device using a non-magnetic one-component toner.

FIG. 3 is a schematic sectional view showing an example of an image forming apparatus using the toner of the present invention.

FIG. 4 is a schematic configuration diagram showing an example of a fixing unit to which the toner of the present invention is applied.

[Explanation of symbols]

1 photosensitive drum 2 Corona charger 3 Laser exposure optical system 3a polygon mirror 3b lens 3c mirror 4Y, 4C, 4M, 4B developing device 5 Transfer device 5a transfer drum 5b Transfer charger 5c Adsorption charger 5d Inner charger 5e Outside charger 5f transfer sheet 5g suction roller 5h Separation charger 6 cleaning device 7a, 7b, 7c cassette 8a Separation claw 8b Separate push up roller 9 Heat and pressure fixing device 10 trays 11 Pre-exposure lamp 12 Potential sensor 13 Drum light intensity detection means 24Y, 24C, 24M, 24B Eccentric cam 30 manuscripts 31 Platen glass 32 exposure lamp 33 lenses 34 Full color sensor 39 Fixing roller 40 pressure roller 41,44 core metal 42, 45 RTV silicone rubber layer 43 Polytetrafluoroethylene (PTFE) layer 46,47 Halogen heater 48a, 48b Thermistor 49a, 49b control device 56 nonwoven web 61 Electrostatic image carrier 62 toner carrier 63 hopper 64 supply roller 65 Toner coating blade 66 bias power supply C fixing roller cleaning device C1 Pressure roller cleaning blade E light image

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03G 9/08 361 (72) Inventor Yasuhiro Ichikawa 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Co., Ltd. (72) Inventor Takaaki Kaji 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Kazuhiko Hayami 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Yojiro Hotta 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Makoto Kambayashi 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. F-term (reference) 2H005 AA01 AA06 AA08 AA21 AB02 CA02 CA08 CA14 CA18 CA25 CB07 DA01 EA03 EA05 EA10

Claims (22)

[Claims] 1. A toner comprising toner particles containing a binder resin, a colorant, and a wax, and hydrophobic titanium oxide fine particles, wherein the toner has a temperature of 30 to 150 ° C. in an endothermic curve in differential thermal analysis measurement. The maximum endothermic peak temperature in the range of 50 to 100 ° C., and the hydrophobic titanium oxide fine particles are 2
A toner having a ratio of maximum intensity to minimum intensity in the range of θ = 20.0 to 40.0 deg is 5.0 or more and 12.0 or less. 2. The binder resin is selected from a polyester resin, a hybrid resin having a polyester unit and a vinyl copolymer unit, and a mixture of a polyester resin and a vinyl copolymer. 2. The toner according to claim 1, wherein the toner is a resin that is used. 3. The acid value of the binder resin is 1 to 40 mg KO.
The toner according to claim 1 or 2, wherein the toner is H / g. 4. The toner according to claim 1, further comprising an organometallic compound. 5. The hydrophobic titanium oxide fine particles, wherein a silane coupling agent is added to a dispersion liquid in which metatitanic acid particles are dispersed to make the metatitanic acid particles hydrophobic, and the hydrophobized metatitanic acid particles are removed from a solution. The toner according to any one of claims 1 to 4, which is produced by heating the separated metatitanic acid particles. 6. The hydrophobic titanium oxide fine particles are obtained by adding titania sol having an anatase type crystal structure as a seed to an aqueous titanium-containing solution to hydrolyze a titanium component in the aqueous titanium-containing solution to obtain metatitanic acid particles. A silane coupling agent is added to the dispersion liquid in which the metatitanic acid particles are dispersed, the metatitanic acid particles are made hydrophobic, the hydrophobized metatitanic acid particles are separated from the solution, and the separated metatitanic acid particles are heat-treated. The toner according to claim 1, wherein the toner is generated by the above. 7. The hydrophobic titanium oxide fine particles are BET.
7. The toner according to claim 1, having a specific surface area of 100 to 350 m ² / g. 8. The toner according to claim 1, wherein the hydrophobic titanium oxide fine particles have a number average particle diameter of 1 to 100 nm. 9. The toner according to claim 1, wherein the hydrophobic titanium oxide fine particles have a hydrophobicity of 40 to 90%. 10. The toner according to claim 1, which has a weight average particle diameter of 3 to 9 μm. 11. The hydrophobic titanium oxide fine particles have a maximum intensity of 2θ = 24.0 to 26.0 deg in a range of 2θ = 20.0 to 40.0 deg in X-ray diffraction,
The toner according to any one of claims 1 to 10, wherein the minimum strength is 2θ = 28.0 to 33.0 deg. 12. The toner according to claim 1, wherein the hydrophobic titanium oxide fine particles are treated with a silane coupling agent represented by the following general formula. Embedded image R _m SiY _n [wherein R represents an alkoxy group, m represents an integer of 1 to 3, Y represents an alkyl group, a vinyl group, a phenyl group, a methacryl group, an amino group, an epoxy group, A mercapto group or a derivative thereof, and n represents an integer of 1 to 3] 13. The toner according to claim 12, wherein the hydrophobic titanium oxide fine particles are treated with 1 to 60 parts by weight of a silane coupling agent per 100 parts by weight of the hydrophobic titanium oxide fine particles. 14. The hydrophobic titanium oxide fine particles are treated with an alkylalkoxysilane coupling agent represented by the following general formula.
4. The toner according to any one of 3 above. [Chemical 2] [In formula, n shows the integer of 4-12 and m shows the integer of 1-3. ] 15. The hydrophobic titanium oxide fine particles are treated with 1 to 60 parts by weight of an alkylalkoxysilane coupling agent per 100 parts by weight of the hydrophobic titanium oxide fine particles. The toner according to any one of items. 16. The hydrophobic titanium oxide fine particles are externally added in an amount of 0.1 to 5 parts by weight with respect to 100 parts by weight of the toner particles. toner. 17. The toner according to claim 1, wherein the toner contains 8 to 70% by number of toner particles having a particle diameter of 4 μm or less based on the number distribution. 18. The toner according to claim 1, wherein the toner has an aggregation degree of 2 to 35%. 19. The toner according to claim 1, wherein the toner particles are non-magnetic cyan toner particles. 20. The toner according to claim 1, wherein the toner particles are non-magnetic magenta toner particles. 21. The toner according to claim 1, wherein the toner particles are non-magnetic yellow toner particles. 22. The toner according to claim 1, wherein the toner particles are non-magnetic black toner particles.