JPH0387841A - Full-color toner kit and developer - Google Patents

Abstract

PURPOSE:To obtain a color copy which has distinct color tones of a wide range and is highly accurate by using yellow, magenta, cyan, and black toners having specific compsn. and characteristics. CONSTITUTION:The yellow (Y), magenta (M) and cyan (C) toners respectively contain Y, M and C coloring agent-contg. resin particles and >=2 kinds of flowability improving agents. The B toner contains the carbon black-contg. resin particles, the flowability improving agent and a friction decreasing agent. The grain size distribution of these contained agents is 6.0 to 20.0mu volume average grain size; <=5.04mu of the number average grain size is <=40%; >=12.7% of the volume average grain size is <=10%; the flowability index is 5 to 25%; the apparent density is 0.1 to 1.5g/cm<2>; the apparent densities at 100 deg.C and 90 deg.C of the toner are 20<4> to 5X10<6> poise and 5X10<4> to 5X10<6> poise; and the exothermic peak value of the DSC is 58 to 72 deg.C. These toners contain the prescribed ratios of the coloring agents, carbon black and carrier particles.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a toner kit for full-color electrophotography, and in particular uses yellow, magenta, cyan, and black toners to obtain clear, wide-range color tones and high-definition color copies. Related to full color toner kit and developer.

[Conventional technology]

In recent years, there has been a rapid shift from monochrome copying to full-color copying in copying machines, and two-color copying machines and full-color copying machines are being extensively studied and put into practical use. For example, “Journal of Electrophotography Society J Vol 22.
No. 1 (1983) and “Journal of Electrophotography Society J Vol.
25. No, 1. There are also reports on color reproducibility and gradation reproducibility, such as P52 (1986).

However, unlike television, photographs, and color printed matter, they cannot be immediately compared with the real thing, and for people who are used to seeing color images that are more beautifully processed than the real thing, the full-color electrophotographic images that are currently in practical use are not necessarily It is not satisfactory.

Color image formation by full-color electrophotography generally requires 3
All colors are reproduced using toner of three primary colors: yellow, magenta, and cyan.

In this method, first, light from an original is passed through a color-separating light transmitting filter whose color is complementary to the color of the toner, and an electrostatic latent image is formed on the photoconductive layer. Next, develop.

The toner is retained on the support through the transfer process. Next, the above-mentioned steps are sequentially performed several times, and the toners are superimposed on the same support while registering, and a final full-color image is obtained by one fixation.

The developing method used at this time is U.S. Patent No. 2,61
Cascade development method described in US Pat. No. 8,552, U.S. Pat.
There are the magnetic brush method described in No. 874,063, and the touchdown method.

Among these, the most commonly used method is the magnetic brush method. This method uses magnetic particles such as steel and ferrite as carriers. A developer consisting of toner and magnetic carrier is held by a magnet, and the magnetic field of the magnet arranges the developer in a brush shape. When the magnetic brush contacts the electrostatic latent image surface on the photoconductive layer, toner is attracted from the brush to the electrostatic latent image to effect development.

However, this method has extremely low development efficiency because the proportion of consumable toner in the magnetic brush in the development section is small. For example, only 1 to 5% of the total developer may be used. Furthermore, if a large amount of developer is used to increase the developing efficiency, the developing device becomes larger and heavier, making it unsuitable for reducing the size and weight of a copying machine.

In particular, since a full-color copying machine requires at least three of the above-mentioned developing devices, it is impossible to make the full-color copying machine more compact.

In terms of image quality, scratches caused by the magnetic brush appear on the developed image like sweeping marks, and due to the strong mixing of toner and carrier inside the developing device, charging deterioration occurs and toner adheres to non-image areas, causing so-called fog. It has problems such as easy to appear.

In color electrophotography, which requires multiple development steps and the overlapping of several toner layers of different colors on the same support, the following are necessary and sufficient conditions for color toners to have: Can be mentioned.

(1) The fixed toner must be almost completely melted to the point where the shape of the toner particles cannot be discerned, so that it does not diffusely reflect light and interfere with color reproduction. .

(2) The colored toner must have transparency that does not interfere with toner layers of different tones below the toner layer.

(3) Each of the constituent toners must have well-balanced hue and spectral reflection characteristics and sufficient saturation.

Furthermore, the electrophotographic properties of the toner include the following.

(4) It is necessary to have good charging characteristics with little environmental dependence.

(5) Favorable conveyance and mixing properties are required to allow smooth replenishment from the hopper to the developing device and to facilitate mixing with the carrier and residual developer.

(6) The toner must have good storage stability without caking or clumping during handling or storage.

(7) In the cleaning process for removing residual toner on the photoreceptor, the toner must not stick to the photoreceptor or cause cleaning failures.

However, the current situation is that there is no color toner kit that satisfactorily satisfies the above performance.

For example, as described in Japanese Patent Application Laid-Open No. 59-26757 (a color toner kit consisting of three types of toner of three primary colors is used as a full-color toner).

However, while these combinations are relatively balanced for color reproduction, their electrophotographic properties are
There are still points to be improved regarding charging characteristics other than storage stability and durability against repeated copying.

Furthermore, in the above proposal, in order to obtain black by superimposing three colors of toner, subtle differences in tone between these three colors and differences in superposition during constant development and transfer are reflected in the black tone. The complexity of color matching of each color toner during the process and the development-transfer process and fixing process of the copying process must be highly accurate, which naturally complicates the process and causes an increase in costs.

Also, Japanese Patent Application Laid-open No. 53-68234 and U.S. Patent No. 4,51
There are many applications for monochromatic color toners such as No. 8.672, but for full color toners, at least 3 colors, preferably 4 colors are used.
The color balance of the colored toners must be harmonious, and there is no point in discussing only the color reproducibility or electrophotographic characteristics of the colors.

In principle, the three primary colors are yellow and magenta.

With the three colors of cyan, it should be possible to reproduce almost all colors using the subtractive color mixing method.Therefore, full-color copiers currently on the market are configured to use three primary color toners superimposed. ing.

Ideally, this would make it possible to achieve all colors in all density ranges, but in reality, there are still many improvements to be made in terms of the spectral reflection characteristics of toner, color mixing properties when toners are superimposed, and loss of saturation due to subtractive color mixing. It has a certain point.

Obtaining black color by superimposing three colors is more difficult, as described above. In selecting the colorant that determines the tone of these color toners, toner hue 1 of the above six items
Spectral reflection characteristics If emphasis is placed on reproducing one color, sufficient electrophotographic characteristics cannot be imparted, and there will be problems with charging characteristics, durability characteristics due to repeated copying, toner transportability, and storage characteristics, and conversely, toner If emphasis is placed on electrophotographic properties as a material, one has no choice but to select a colorant with poor color tone. That is, it is extremely difficult to satisfy both color reproducibility and electrophotographic properties.

Furthermore, digital color copiers that use laser beams to create latent images on photoreceptors have recently been put into practical use.
Conventional toner cannot faithfully reproduce the laser spot on the photoreceptor, making it difficult to obtain high-definition copies.

[Purpose of the invention]

After intensive research to improve these problems, the inventors of the present invention developed a new black toner for inking in addition to the three primary color toners. A full-color toner kit that exhibits particularly favorable characteristics has been achieved.

An object of the present invention is to provide a full color toner kit having favorable spectral reflection characteristics.

Another purpose is yellow, magenta, and cyan.

An object of the present invention is to provide a full-color toner kit that exhibits good color mixing and fixing properties in a four-color black toner kit and provides a wide range of color tone reproducibility.

Another object is to provide a full color toner kit with sufficient triboelectric charging properties.

Another object is to provide a full color toner kit with good transportability.

Another purpose is to provide a full-color toner kit with no sweeping lines.

Another objective is to provide a full color toner kit with less scattering.

Another object is to provide a high-gloss, full-color toner kit that significantly improves image quality.

Another object of the present invention is to provide a full-color toner kit that is highly durable and resistant to carrier spillage even after repeated copying.

Another object of the present invention is to provide a full-color toner kit that does not cause toner sticking on a photoreceptor or cleaning defects.

Another object of the present invention is to provide a full-color toner kit that faithfully reproduces the latent image on the drum and enables high-definition color copies.

[Summary of the invention]

Its characteristics are at least yellow toner,
In a full-color toner kit for multicolor electrophotography including a magenta toner, a cyan toner, and a black toner, the yellow toner has resin particles containing a yellow colorant and two or more types of fluidity improvers, and the particle size distribution is a volume average particle. Diameter 6.0-10.0μ, number average distribution 5.04μ
The following is 40% or less, and the volume average distribution is 12.7 μ or more
0% or less, the fluidity index is 5% to 25%, the apparent density is 0.2 to 1.5 g/cm3, and the apparent viscosity of the yellow toner at 100°C and 90°C is 104~5x105 poise, 5x105~5x106
It is in the poise range, and the DSC endothermic peak value is 58 to 7.
2°C, the gloss level is 5.0% or more, the yellow colorant is contained in O9l to 12.0 parts by weight per 100 parts by weight of the binder resin, and the chromaticity of the yellow toner is a*-6, 5~
-26.5. b*73.0-93.0 and one 77
．． 0 to 97.0, and has a triboelectric charge characteristic of -10 for a styrene-based resin-coated ferrite carrier having 65% by weight or more of carrier particles of 250 mesh pass and 350 mesh pass, and 20% by weight or less of 400 mesh pass. -50 μc/g, the magenta toner contains magenta colorant-containing resin particles and two or more fluidity improvers, and its particle size distribution is 6.0 to 6.0 μc/g.
10.0μ, the number average distribution of 5.04μ or less is 40% or less, the volume average distribution of 12.7μ or more is 10% or less, the fluidity index is 5% or more and 25% or less, and the apparent density is 0. .2 to 1.5 g/crd, and the apparent viscosity of the magenta toner at 100'C and 90°C is 1.
04~5x105 poise, 5x10'~5x105 poise, DSC endothermic peak value is 58~72℃
and has a gloss level of 5.0% or more, contains 0.1 to 15.0 parts by weight of a magenta colorant per 100 parts by weight of the binder resin, and the chromaticity of the magenta toner is 4 to 60.0. ~80
．． 0. b* -12,0 to -32,0 and L*40.
0 to 60.0, 250 mesh passes.

The cyan toner has a triboelectric charge amount characteristic of -10 to -50 μc/g for a styrene-based resin-coated ferrite carrier having 65% by weight or more of carrier particles of 350 mesh and 20% by weight or less of 400 mesh, and the cyan toner is cyan-based. Contains colorant-containing resin particles and two or more fluidity improvers, the particle size distribution is a volume average particle diameter of 6.0-10.0μ, the number average distribution is 5.04μ or less, 40% or less, and the volume average distribution 12.7μ or more is 10
% or less, the fluidity index is 5% to 25%, the apparent density is 0.2 to 1.5 g/cm3, and the apparent viscosity of the cyan toner at 100°C and 90°C is 1.
04 to 5 x 105 poise, 5 x 105 to 5 x 105 poise, DSC endothermic peak value is 58 to 72°C
The cyan toner has a gloss level of 5.0% or more, contains 0.1 to 15.0 parts by weight of a cyan colorant per 100 parts by weight of the binder resin, and has a chromaticity of a*-8 to -28,0,
b* -30.0 to -50.0 and L book 39.0 to 59.
0, and the triboelectric charge characteristic for a styrene resin-coated ferrite carrier having 65% by weight or more of carrier particles of 250 mesh pass and 350 mesh pass and 20% by weight or less of 400 mesh pass is -10 to -5.
0 μc/g, and the black toner contains resin particles containing carbon black,
Contains a fluidity improver and a friction reducing agent, and its particle size distribution is 6.0-10.0 μm in volume average particle size and 5.0 μm in number average particle size.
04 μ or less is 40% or less, the volume average distribution of 12.7 μ or more is 10% or less, the fluidity index is 5% to 25%, and the apparent density is 0.2 to 1.5 g/crr? The apparent viscosity of the toner at 100° C. and 90° C. is 104 to 5×104 poise, and 5×105 to 5×1
It is in the range of 0.05 poise, and the DSC endothermic peak value is 58.
~72°C, carbon black is contained in 0.1 to 10.0 parts by weight per 100 parts by weight of the binder resin, and the chromaticity of the black toner is a*-2.0 to 3.0. b-tree-1,0-3
．． 0 and L*26.0 to 45.0, and has 65% by weight or more of carrier particles of 250 mesh pass and 350 mesh pass, and 400 mesh pass is 20% by weight or less of triboelectric charge amount for a styrene resin coated ferrite carrier A full color toner kit characterized by a toner having characteristics of -10 to -50 μc/g.

A further object of the present invention is to provide a two-component developer comprising the toners of each color used in the full-color toner kit and a resin-coated ferrite carrier.

[Detailed description of the invention]

An example of a full-color electronic copying machine to which a color electrophotographic method according to the present invention is applied will be described with reference to FIG.

The electrostatic latent image formed on the photosensitive drum 1 by a suitable means is visualized by the developer in the developing device 2-1 attached to the developing unit 2 which reciprocates in the direction of the arrow. This developed toner is transferred by a transfer charger 8 onto a transfer material held on a transfer drum 6 by electrostatic attraction by an adsorption charger 7 .

Next, the developing unit moves for the second color, and the developing unit 2-2
faces the photosensitive drum 1. The toner image is then developed with the developer in the developing device 2-2, and this toner image is also transferred onto the same transfer material as described above.

Further, the third and fourth colors are also processed in the same manner. In this manner, the transfer drum 6 rotates a predetermined number of times while holding the transfer material, and images of a predetermined number of colors are multiple-transferred. The multiple-transferred transfer material is separated from the transfer drum 6 by a separation charger 9, passes through a fixing device 10, and becomes a final full-color copy image.

Further, the replenishment toner supplied to the developing machines 2-1 to 2-4 is supplied from a replenishment hopper 3 provided for each color in a fixed amount based on a replenishment signal via a toner conveying cable 4, and mixed between the respective developing machines. The conveying screw (16 in FIG. 2) is replenished when the developing machine comes to the developing position. This replenishment toner is uniformly mixed with the developer already in the developing device by mixing and conveying screws 16 and 17 shown in FIG. 2 in the developing device so as to have a predetermined developer concentration.

At this time, the mixing ratio of carrier and toner is an extremely important factor from the viewpoint of the developing effect.

That is, the developer attached to the surface of the sleeve containing the magnet rubs against the electrostatic latent image and visualizes the latent image with toner. Toner is gradually consumed from the developing agent, and the ratio of toner to carrier decreases, that is, the concentration of the developer decreases, and the density of the developed image gradually becomes thinner. Therefore, toner is appropriately replenished, but in this case, if more toner is replenished than appropriate, the image density becomes too high and fogging increases. Therefore, in order to continuously obtain images with desirable tones, it is necessary to accurately detect the concentration of the developer.

As a method for detecting developer concentration, Japanese Patent Application Laid-Open No. 53-107
There is a method of detecting the reflection or transmission density of the developer in the infrared region, as in No. 853. According to this method, the change in reflectance, that is, the amount of reflected light, depending on the developer concentration can be greatly reduced, and it has the advantage that it not only improves detection accuracy but also can be used for color copies as well as black and white copies. However, since this method detects the reflected or transmitted light of the toner in the infrared region, it is not possible to use carbon black, iron black, nigrosine dye, etc., which are conventionally widely used as black coloring agents. There was a major problem in that a reflective or transparent coloring agent had to be used.

As a method to solve this problem, coloring agents such as dyes and pigments that reflect or transmit infrared light and are not black, as disclosed in JP-A-48-63727 and JP-A-57-11936, have been proposed. There is a method of appropriately blending two or more types of binder resins, mixing and kneading, and using a blackened toner. It is possible to obtain a substantially black toner by combining non-black colorants.

However, using two or more types of colorants has problems such as difficulty in dispersing them into the binder resin, and higher cost compared to toners using carbon black, which is not completely black but has some color. occured.

In addition, as a method for detecting developer concentration, there is a method in which development is performed once on a photoreceptor and the developer concentration is detected by measuring the density. This method has the advantage that the copy density is stable because the measurement is performed after actual development. Furthermore, it is possible to use carbon black or the like as the black toner. However, the disadvantage of using this four-color method is that the copy machine development process becomes very complex.

In order to solve the above problems, yellow magenta,
For each cyan toner, a method is used to detect the reflection or transmission density of the developer in the infrared range.For black toner, a method is used to develop the developer once on a photoreceptor and then measure the density.Full color toner developer Methods for detecting concentration have been proposed. That is, the above detection method can be realized by using the color toner kit of the present invention.

In other words, the yellow, magenta, and cyan toners have sufficient spectral reflectance in the near-infrared region, and the black toner uses carbon black, making it possible to achieve completely black color at low cost. can.

Each of the yellow, magenta, and cyan toners preferably has a spectral reflectance of 40% or more in the near-infrared region, particularly in the range of 900 to 11,000 nm, more preferably 60% or more,
Particularly preferably, it is 70% or more.

Theoretically, it should be fine if the difference in spectral reflectance between toner and carrier is minute, but if it is less than 40%, the detection ability of the detection device, that is, the spectral transmittance of the fiber, the spectral transmittance of the dichroic mirror, The S/N ratio of the electrical signal processing circuit, the assembly tolerance of the detection device, and other factors that determine detection accuracy are below the limit of the overall power, and it is not possible to stably distinguish between carrier and toner, and the developer concentration cannot be determined quantitatively. It becomes impossible to determine.

The fluidity index, which closely affects the toner transportability and the mixability with the carrier, is preferably 5% or more and 25% or less.

The fluidity index is one of the indicators of fluidity; the higher the value, the worse the fluidity is, and the lower the value, the better the fluidity is, and the greater the tendency for toner to scatter within the device.

FIG. 2 shows an example of a replenishment-development system using the full-color toner kit of the present invention. If the index is 25% or more, the miscibility with the developer, that is, the miscibility of the replenished toner into the particle aggregate in which some toner is already electrostatically attached to the carrier surface becomes poor. As a result, it becomes impossible to achieve a constant and uniform developer concentration in a short period of time.
The toner concentration locally varies in the developer.

This causes the developing agent to have different developing abilities on the developing sleeve, resulting in non-uniform development for the same latent image potential, resulting in image quality problems such as partial fogging and density unevenness. .

On the other hand, if the fluidity index is less than 5%, it will encourage scattering from the developing sleeve 12 into the machine during development, causing contamination of the charging corotron wire. Furthermore, the fluidity is so good that the toner passes through the toner conveying cable 4 in a jet state and tends to overflow at the toner replenishing port 5.

Toner is replenished from the replenishment hopper 3 to the developing device 2 by rotating a supply screw 13 in the toner transport cable 4 for a certain period of time in accordance with the signal from the developer concentration detector. If the density is less than 0.2, toner retention in the supply screw 16 will be insufficient, and even if the screw rotates for a certain period of time, a larger amount of toner than necessary will be supplied into the developing device.

Also, if it is 1.5 or more, too much will stay in the screw 13,
If the toner transport cable is clogged, the resulting overload may cause the supply screw to break. Therefore, the preferred range for the apparent density is 0.25 to 1.0, more preferably 0.3 to 0.8.

Means for achieving the fluidity index and apparent density of the present invention include binder resin particles having preferred fluidity, and the type and addition of fluidity improvers described in the specification of the present invention. quantity, the preferred particle size distribution of the color toner of the present invention, and the amount of the contained colorant that migrates to the resin particle surface and is exposed, in other words, the quality of the compatibility of the colorant in the binder resin,
It can be obtained by selecting and controlling the type of colorant.

The particle size distribution of the full color toner kit used in the present invention has a volume average diameter of 6.0μ to 10.0μ, preferably 7.0μ to 9.5μ, more preferably 7.5μ to 9.0μ.
0μ, the number average distribution of 5.04μ or less is 40% or less, preferably 30% or less, more preferably 25% or less, and the volume average distribution of 12.7μ or more is 10% or less,
Preferably it is 7% or less, more preferably 5% or less.

By reducing the particle size of the toner as described above, it is possible to faithfully reproduce the laser spot on the photoreceptor in a digital color copying machine, and it is possible to obtain color copies with much higher definition than before.

If the volume average diameter is 10.0μ or more and/or the volume average distribution is 12.7μ or more for 10% or more, the laser spot cannot be reproduced sufficiently, and the roughness of the image, blurring of the text, and so-called scattering will worsen. The trend increases.

In addition, the distribution amount of 5.04μ or less in the number average distribution, the so-called fine powder amount, is closely related to the amount of scattering, and the amount of fine powder of 40% or more is more than twice as much as the amount of fine powder of 20% in a more preferable embodiment. It is known that the amount of These problems include contamination of the charger wire, contamination of part of the developer concentration detector fiber, and inability to move due to the accumulation of flying debris on the sliding parts.Furthermore, the flying toner may enter the non-image area of the electrostatic latent image on the photosensitive drum. This will cause fogging and poor cleaning, significantly shortening the useful life of the copying machine.

According to studies conducted by the present inventors, it has been found that when the amount of scattering is doubled, the service life and periodic cleaning intervals are reduced by 1/2 to 1/4 or less.

In addition, if the volume average diameter is less than 6.0μ, the amount of ultrafine powder increases during toner production, leading to fogging and image quality deterioration, and at the same time, a large amount of time and energy is required for the crushing process during the toner production process, leading to increased costs. .

When the particle size distribution effect of the present invention is applied to, for example, the following development method (hereinafter referred to as J/B development), extremely favorable results can be obtained.

Yellow and magenta in full color development.

Particle size of each cyan and black toner 1 Particle size distribution, degree of aggregation,
It is preferable that the apparent density, amount of triboelectric charge, apparent viscosity, etc. have substantially the same values because it is necessary to use the same image forming method. Therefore, as described above, it is preferable to optimize the types and amounts of colorants, charge control agents, fluidity improvers, and the like.

That is, in FIG. 2, a bias electric field consisting of an AC component and a DC component is applied between the developing sleeve 14 and the photosensitive drum 11 having an electrostatic latent image, and the space formed by the developing sleeve 14 and the photosensitive drum 11 is The volume occupied by the carrier in the developing section of the developing sleeve 14 is 0.5 to 4.
0%, preferably 1.0 to 30%, the electric field of the alternating current component has a frequency of 100 to 3000 Hz, and the peak to beak voltage is set so that the electrostatic latent image is not destroyed and the carrier is developed in the development area. In this method, a voltage is applied to move between the sleeve 14 and the photosensitive drum 11, and in the developing section, the toner on the developing sleeve 14 and the toner adhering to the carrier surface are transferred to the photosensitive drum 11 for development.

The volume ratio of the carrier present in the developing section is (M/h)
It can be determined by X (I/ρ) x [C/(T + C)].

Here, M is the amount of developer applied per unit area of the developing sleeve (g/cm3), and h is the height of the developing section space (cm).
, ρ is the true density of the carrier (g/crr?), C/(T
+C) is the weight percentage of carrier in the developer on the sleeve (
%).

As an example when using the kit and developer of the present invention, M is 0.03 to 0.09 g/c and h is 0.02 to 0.
, 10 cm, p is 4-6 g/c rd,
C/(T+C) can be 91 to 98%.

Further, the amount of charge of the toner on the developing sleeve in J/B development is measured by directly absorbing the developer from the sleeve, separating the toner and carrier, and then guiding the toner to a Faraday gauge.

When the developer of the present invention is used, the charge amount of the toner in the developer on the sleeve in J/B development is -10 to -5.
A value of 0 μc/g can be mentioned.

This developing method has high developing efficiency and is very useful in reducing the weight and/or size of the apparatus, and is preferable for downsizing full-color copying machines.

In terms of image quality, this method allows high image density to be obtained, and also requires less negative development and less fog. The triboelectric charge characteristic range of the full color toner kit of the present invention for a styrene resin-coated ferrite carrier in which carrier particles of 250 mesh pass and 350 mesh pass are 70% by weight or more and 400 mesh pass is 20% by weight or less is -1.
0~-50μC/g% preferably -15~-45μ
c/g% more preferably -20 to -35μc/g
It is.

The above-mentioned coated ferrite carrier has the effect of distinctively bringing out the charging characteristics of color toners in J/B development.

If it is less than -10 μc/g, there will be significant scattering from the developing sleeve during development, resulting in a high temperature environment (30°C).

80% RH), it causes scattering inside the copying machine, making it practically impractical.

Moreover, if it is -50μc/g or more, the toner will adhere firmly to the carrier surface electrostatically under a room temperature and low humidity environment (20°C, 10% RH) and will not transfer onto the photosensitive drum having an electrostatic image. toner transfer becomes impossible. FIG. 3 shows the tendency of the environmental dependence of the amount of triboelectric charge in the examples and comparative examples.

In order to closely match the above-mentioned charge amount, it is necessary to use two or more kinds of fluidity improvers. A toner having a small particle size with a volume average of 6.0 to 10.0 microns, such as the toner of the present invention, tends to have an excessive amount of charge, especially under low humidity conditions, due to an increase in surface area. Therefore, it is necessary to use a fluidity improver with low chargeability, such as alumina or titanium oxide. Furthermore, since the particle size of the toner is small, there are many contact points between the toners, resulting in poor fluidity. However, the above-mentioned alumina, titanium oxide, etc. do not sufficiently improve fluidity. Furthermore, conversely, the amount of charge may decrease too much. Therefore, it is necessary to use a negatively charged fluidity improver with a high fluidity imparting effect such as hydrophobic silica.

That is, by using two or more types of fluidity improvers together, the amount of charge can be made appropriate and sufficient fluidity can be provided. However, in the case of a black toner using carbon black, since carbon black has conductivity, the amount of charge does not become excessive, and there is no need to specifically add a low chargeability substance.

As the low-electrification fluidity improver used in the present invention, all known ones can be used, but preferred ones include alumina and titanium oxide. Preferably B
The specific surface area measured by ET method is preferably in the range of 30 to 200 rd/g, more preferably 80 to 150 rd/g.
It is good to have a range of . The reason is that alumina and titanium oxide, which have an ET specific surface area of more than 200 d/g, have sufficient fluidity, but the toner tends to deteriorate easily.

Deterioration appears as a phenomenon in which the amount of charge changes significantly or the fluidity of the developer worsens when copying continues in a state where toner consumption is low.

Furthermore, alumina and titanium oxide having an ET specific surface area of less than 30 d/g tend to have difficulty obtaining sufficient fluidity even when used in combination with other fluidity imparting agents. Further, the dispersion of the fluidity imparting agent tends to be insufficient, resulting in fogging of the image.

Furthermore, as a negatively charged fluidity improver with a high fluidity imparting effect, any known fluidity improver can be used, but preferred is a fine powder produced by vapor phase oxidation of a silicon halogen compound. , so-called dry process silica or fumed silica, which are manufactured by conventionally known techniques. For example, it utilizes the thermal decomposition oxidation reaction of silicon tetrachloride gas in an oxyhydrogen flame, and the basic reaction formula is as follows.

5iCj? 4+2H2+02 →SiO□+4HCfAlso, in this manufacturing process, it is also possible to obtain a composite fine powder of silica and other metal oxides by using other metal halide compounds, such as aluminum chloride or titanium chloride, together with the silicon halide compound. , also include them.

The average primary particle size of the particles is desirably within the range of o, ool to 2μ, particularly preferably 0.002μ.
It is preferable to use silica fine powder within the range of ~0.2μ.

Furthermore, it is more preferable to use treated silica fine powder obtained by hydrophobicizing silica fine powder produced by gas phase oxidation of the silicon halogen compound. Among the treated silica fine powders, it is particularly preferred that the silica fine powders be treated so that the degree of hydrophobicity as measured by a methanol titration test is in the range of 30 to 8o.

Hydrophobicity can be imparted by reaction with fine silica powder or chemical treatment with an organosilicon compound that physically adsorbs it.

In a preferred method, fine silica powder produced by vapor phase oxidation of a silicon halide is treated with an organosilicon compound.

Examples of such organosilicon compounds are hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane,
Allyl phenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, ρ-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate , vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyljethoxysilane,
Hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane and St.
There are dimethylpolysiloxa containing a hydroxyl group bonded to. These may be used alone or in a mixture of two or more.

The particle size of the treated silica fine powder is 0.003-0.
It is preferable to use one in the range of 1μ. Commercially available products include Taranox-500 (Talco), AERO
3IL R=972 (Japan Aerosil Co., Ltd.), etc.

It is also preferable to add a friction reducing agent to the toner according to the present invention in order to prevent toner from sticking to the photoreceptor and poor cleaning during the cleaning process for removing residual toner on the photoreceptor. It is also preferred to add friction reducers. Friction reducers include iron oxide, chromium oxide,
Examples include calcium titanate, strontium titanate, barium titanate, magnesium titanate, cerium oxide, zirconium oxide, and zinc oxide.

Friction reducers are often used in monochromatic copies of black, and the other three colors already contain two or more types of fluidity improvers as mentioned above, making it difficult to disperse them sufficiently. It is desirable to add it to toner.

In full color toner kits, toner fixability is an extremely important factor from the viewpoint of color mixing.

The toner particles are stacked in multiple layers on the transfer support, and the colors are mixed in one fixing process, producing a variety of colors depending on the amount of toner covered on the transfer material, making it easy to distinguish the toner particles under a microscope. If the fixing properties are too poor, the fixed toner particles will diffusely reflect light, resulting in a cloudy image with reduced saturation, which will lead to a reduction in color reproducibility.

Furthermore, when copying onto an OHP film, poor fixing properties result in poor light transmittance, and although the desired color tone is almost reproduced in reflected light, it may appear dark gray in transmitted light.

However, if only fixing performance is considered, the fixing device becomes complicated and costs increase due to high-temperature offset, wrapping around the fixing roller, and a device that applies a large amount of oil to prevent such problems. Furthermore, oil marks on the copied images can significantly degrade the quality.

However, the present invention has an apparent viscosity of 5xlO at 90°C.
'~5xlO'boids, preferably 7.5x105~
2 X 104 boys, more preferably 104-104
poise, and the apparent viscosity at 100°C is 104~
5 x 104 boys, preferably 104~3.0 x 1
04 poise, more preferably 104 to 2 x 104 poise, ensures the fixing properties, color mixing properties, and high temperature offset resistance of the full color toner.

In particular, the absolute value of the difference between the apparent viscosity P1 at 90°C and the apparent viscosity P2 at 100°C is 2 x 104 <
It is preferable that P2-P,l<4X10@.

At the same time, the endothermic peak value measured by DSC (differential thermal analysis) is also correlated with fixing properties; too high a peak value will worsen fixing properties, and too low a peak value will cause problems with storage stability, especially during shipping. The temperature may rise in the hold and cause blocking in the toner bottle.

However, for the fixing properties of color toner, this temperature of 90°C
Good results cannot be expected unless both the apparent viscosity at 100°C and the DSC endothermic peak temperature are satisfied.

In the present invention, the temperature of the endothermic peak of DSC is 58 to 72
°C, preferably 61-70 °C, more preferably 70-6
It is desirable that the temperature be within the range of 2°C.

The apparent viscosity and DS at 90°C and 100°C of the present invention
In order to achieve the endothermic peak value of C, the monomer composition of the binder resin, the monomer type, the crosslinking agent, the selection of the initiator, and the manufacturing conditions must be carefully set. General printed matter and photographs have a fairly glossy surface, which serves to improve image quality.

Since the full-color copying method uses a different image forming method than printing, image glossiness is a much more important factor in improving the quality of color electrophotographic images than in the case of printing, photography, etc.

The glossiness range is 5.0% or more, more preferably 7.0% or more.
It is 0% or more. If it is less than 5.0%, the color tone reproducibility will be poor and the image will be dull and dull, significantly lowering the image quality.

This glossiness is closely correlated with the thermal properties of the binder resin and the compatibility of the colorant contained in the resin. Unidispersity etc. must also be taken into consideration.

When using a full-color toner kit, its chromaticity determines the range of color reproducibility, and each color, such as yellow, magenta, cyan, and black, must be balanced.

If the yellow, magenta or cyan toner has an extremely low saturation or is out of hue, the degree of freedom in color reproducibility of the color hexabon shown in FIG. 4 will be limited.

Green is obtained by superimposing cyan and yellow toners, but it is the one that is most likely to be desaturated compared to the other superimposed colors, namely blue and red.

Therefore, unless the chromaticity of cyan and yellow is above a certain level, it is impossible to obtain green with good tone and saturation.

Therefore, the colorant should be selected with as much saturation as possible and with consideration for color balance. Specifically, the chromaticity color circle in Figure 4 should be made into a preferable hexagonal shape to obtain the maximum area. You must choose accordingly.

Furthermore, each color of magenta, cyan, and yellow has a reflectance of 40%, which is sufficient to distinguish it from carrier in developer detection.
It must be something like the above.

Therefore, the chromaticity range of each toner used in the present invention needs to have the following values.

Yellow toner: a* is -6,5 to -26,5, preferably -11,5
~-21,5, more preferably -12,5 ~-20,
5, b* is 73.0-93.0. Preferably 78.0~
88.0°, more preferably 79.0-87.0°L wood is 77.0-97.0°. Preferably 82.0 to 92.0
゜More preferably 83.0-91.0゜Magentatona m: a* is 60.0-80.0, preferably 615.0-
75.0°, more preferably 66.0-74.0°b*
is −12,0 to −32,0, preferably −17,0 to
-27,0, more preferably -18,0 to -26,0
°L* is 40.0 to 60.0. Preferably 40.0-5
5.0°, more preferably 44.0 to 54.0, cyan toner: -8 to -28.0, preferably -10.0 to -
27.0, more preferably -14.0 to -25.0° b* is -30°0 to -50.0. Preferably -33,
0 to -45,0, more preferably -35,0 to -44
,0°L* is 39.0~59.0. Preferably 44.0
~59.0°, more preferably 45.0~57.0,
Black toner: -2.0 to 3. O, preferably -1.0 to 2.
0°b tree is -1.0~3.01 preferably 0~2.0,
L* is 26.0-45.0, preferably 30.0-4
0.0 Furthermore, it is preferable that the relationship between each color toner of the color kit of the present invention satisfies the following conditions on the chromaticity diagram.

(i) Angle between cyan and yellow: 1456
±15° (ii) Angle between cyan and magenta =
956 ± 15° (iii) Angle between magenta and yellow: 120' ± 10° Here, the angle between cyan and yellow is the coordinate of cyan and the zero point and the coordinate of yellow and zero on the chromaticity diagram. Connect each point with a straight line, part 2
It refers to the angle formed by the straight lines of the book. The same applies to cyan and magenta, and magenta and yellow.

As the binder resin for toner of the present invention, the following can be used as long as the gist of the present invention is not impaired.

For example, polystyrene, chloropolystyrene, poly-α-
Methylstyrene, styrene-chlorostyrene copolymer,
Styrene-propylene copolymer, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, styrene-
Vinyl acetate copolymer, styrene-maleic acid copolymer,
Styrene-acrylate copolymer (styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-phenyl acrylate) copolymers, etc.), styrene-methacrylate ester copolymers (styrene-methyl methacrylate copolymers, styrene-ethyl methacrylate copolymers, styrene-butyl methacrylate copolymers, styrene-phenyl methacrylate copolymers) etc.), styrene-based resins (monopolymers or copolymers containing styrene or styrene substitutes) such as styrene-α-methyl chloroacrylate copolymer, styrene-acrylonitrile-acrylic acid ester copolymer,
Vinyl chloride resin, styrene-vinyl acetate copolymer, rosin-modified maleic acid resin, phenyl resin, epoxy resin, polyester resin, low molecular weight polyethylene, low molecular weight polypropylene, ionomer resin, polyurethane resin, silicone resin, ketone resin, ethylene-ethyl Examples include acrylate copolymers, xylene resins, polyvinyl butyral resins, etc. Particularly preferred resins for carrying out the present invention include styrene-acrylic acid ester resins and polyester resins.

In particular, the following formula (wherein R is ethylene or propylene group, X, y
are each a positive integer of 1 or more, and the average value of x+y is 2 to 10. ) as a diol component, and a carboxylic acid component consisting of a divalent or higher carboxylic acid, its acid anhydride, or its lower alkyl ester (for example, fumaric acid, maleic acid, maleic anhydride).

A polyester resin obtained by cocondensation polymerization with at least phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc.) is more preferable because it has sharp melting characteristics.

As the carrier used in the present invention, for example, surface-oxidized or unoxidized metals such as iron, nickel, copper, zinc, cobalt, manganese, chromium, rare earths, alloys or oxides thereof, and ferrites can be used. There are no special restrictions on the manufacturing method.

Further, a system in which the surface of the carrier is coated with a resin or the like is particularly preferred in the above-mentioned J/B development method. As a method for this, any conventionally known method can be applied, such as a method in which a coating material such as a resin is dissolved or suspended in a solvent and applied and adhered to the carrier, or a method in which a powder is simply mixed.

Substances that adhere to the carrier surface vary depending on the toner material, but include polytetrafluoroethylene, monochlorotrifluoroethylene polymer, polyvinylidene fluoride, silicone resin, polyester resin, metal complex of ditertiary butylsalicylic acid, styrene resin, and acrylic. It is appropriate to use one or more of these resins, polyacid, polyvinyl butyral, nigrosine, aminoacrylate resin, basic dye and its lake, fine silica powder, fine alumina powder, etc., but the invention is not necessarily limited thereto.

The amount of the above compound to be treated may be appropriately determined so that the carrier satisfies the above conditions, but generally the total amount is 0.1 to 30% by weight (preferably 0.5 to 30% by weight) based on the carrier of the present invention.
20% by weight) is desirable.

The average particle size of these carriers is preferably 20 to 100μ, preferably 25 to 70μ, more preferably 30 to 65μ.

A particularly preferred embodiment is a Cu-Zn-Fe ternary ferrite whose surface is coated with, for example, styrene-2-ethylhexyl acrylate or styrene-2-acrylate.
0.01 to 5% by weight, preferably 0.1 to 1% by weight of styrene resin such as ethylhexyl-methyl methacrylate
Examples include coated ferrite carriers having the above-mentioned average particle size, in which carrier particles of 250 mesh passes and 350 mesh passes account for 65% by weight or more, and carrier particles of 400 mesh passes account for 20% by weight or less.

The coated ferrite carrier has a sharp particle size distribution, provides favorable triboelectric charging properties for the color toner kit of the present invention, and has the effect of improving electrophotographic characteristics.

When preparing a two-component developer by mixing with the color toner according to the present invention, the mixing ratio is 2.0% by weight to 9% by weight, preferably 3.0% by weight as a toner concentration in the developer.
~8.0% by weight usually gives good results. If the toner concentration is less than 2.0%, the image density will be too low to be practical, and if it is more than 9.0%, fogging and in-machine scattering will increase and the useful life of the developer will be shortened.

The amount added to the colorant-containing resin particles is 1
The amount is 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight. If it is less than 0.01 part by weight, it will not be effective in improving fluidity, and if it is more than 10 parts by weight, it will promote fogging, smearing of characters, and scattering inside the machine.

Magenta, cyan, and yellow colorants suitable for the purpose of the present invention include the following pigments or dyes. still,
In the present invention, C and I have poor light resistance.

Disperse Y164. C,1,5olve
Colorants such as nt Y77 and C01,5olvent Y93 cannot be recommended.

Examples of dyes include C,! , Direct Red 1, C
,1, Direct Red 4, C,1, Acid Red 1
, C,1, Basic Red 1, C,1, Modern Red 30, C,1, Direct Blue 1, C,1, Direct Blue 2, C91, Acid Blue 9, c, r,
Acid Blue 15, C, 1, Basic Blue 3, C
, 1, Basic Blue 5, C, 1, Mordand Blue, etc.

Pigments include Naphthol Yellow S1 Hansa Yellow G1 Permanent Yellow NCG, Permanent Orange GTR, Pyrazolone Orange, Benzidine Orange G
1 Permanent Red 4R, Watching Red Calcium Salt, Brilliant Carmino 3B, Quinacridone Red, Fast Violet B1 Methyl Violet Lake, Phthalocyanine Blue, Fast Sky Blue,
There is Indan Stremburu-BC, etc.

Preferred pigments are disazo yellow, insoluble azo, quinacridone, and copper phthalocyanine, and suitable dyes are basic dyes and oil-soluble dyes.

Particularly preferably C, I, Pigment Yellow 17, C,
1, Pigment Yellow 15, C,! , Pigment Yellow 13, C,1, Pigment Yellow 14, C,I.

Pigment Yellow 12, C, 1, Pigment Red 5
, C,1, Pigment Red 3, C,1, Pigment Red 2, C,1, Pigment Red 6, C,1, Pigment Red 7, C,1, Pigment Red 122, C,
1, Pigment Red 202, C,1, Pigment Blue 15, C1■, Pigment Blue 16, or Ba with the phthalocyanine skeleton substituted with 2 to 3 carboxybenzamidomethyl groups, having the structural formula (I) shown below.
These include copper phthalocyanine pigments, which are salts.

As a dye, c4. Solvent Red 49, C, I.

Solvent Red 52, C, 1, Solvent Red 10
9, C,1, Paysic Red 12, C,1, Paysic Red 1, C,1, Paysic Red 3b, etc.

The content of yellow toner, which is sensitive to the transparency of OHP films, is 10% of the binder resin.
12 parts by weight or less, preferably 0 parts by weight
．． 5 to 7 parts by weight is desirable.

If the amount is 12 parts by weight or more, the reproducibility of green and red, which are mixed colors of yellow, and human skin color in images is poor.

For other magenta and cyan color toners,
The amount is desirably 15 parts by weight or less, more preferably 0.1 to 9 parts by weight, based on 100 parts by weight of the binder resin.

All known carbon blacks such as channel black, furnace black, and lamp black can be used as the carbon black used in the black toner of the present invention. Its content is 10 parts by weight or less per 100 parts by weight of the binder resin;
More preferably, the amount is 7 parts by weight or less.

It is also preferable to add a charge control agent to the toner according to the present invention in order to stabilize the negative charge characteristics. In this case, a colorless or light-colored negative charge control agent that does not affect the color tone of the toner is preferred. Examples of negative charge control agents include organometallic complexes such as metal complexes of alkyl-substituted salicylic acids (for example, chromium complexes or zinc complexes of di-tert-butylsalicylic acid). When a negative charge control agent is added to the toner, it is added in an amount of 0.000 parts by weight per 100 parts by weight of the binder resin.
It is good to add 1 to 10 parts by weight, preferably 0.5 to 8 parts by weight.

Each measurement method (1) to (10) of the present invention will be described below.

(1) Particle size distribution measurement: A Coulter Counter TA-n model (manufactured by Coulter Co., Ltd.) is used as the measuring device, and an interface (manufactured by Nikkaki Machinery Co., Ltd.) that outputs the number average distribution and volume average distribution and CX-1 are used.
A personal computer (manufactured by Canon) is connected, and the electrolyte is 1% NaCj! using primary sodium chloride. Prepare an aqueous solution.

As a measurement method, the electric field aqueous solution 100 to 150 m j
! 0.1 to 5 ml of a surfactant, preferably an alkylbenzene sulfonate as a dispersant, and further 0.5 to 50 mg of a measurement sample are added therein.

The electrolytic solution in which the sample was suspended was dispersed for about 1 to 3 minutes using an ultrasonic disperser, and then dispersed for 2 to 3 minutes using a 100μ aperture using the Coulter Counter TAU type.
The particle size distribution of 40μ particles is measured and the volume average distribution and number average distribution are determined.

From the volume distribution and number distribution obtained, the volume average particle diameter is 6.35μ or less in the number average distribution, and 20μ in the volume average distribution.
．． Obtain each person over 2μ.

(2) Fluidity index measurement: Fluidity index is used as a means of measuring the fluidity characteristics of a sample (toner with external additives, etc.), and the larger the value of this fluidity index, the lower the fluidity of the sample. judge it as bad.

As a measuring device, a powder tester (manufactured by Micron Co., Ltd. for wire use) is used.

The measurement environment is 23° C. and 60% RH.

(1) After leaving the toner in the measurement environment for 12 hours, 5.
Measure g accurately.

(2) Place the opening on the shaking table from above at 150μ, wire diameter 104μ (
100 mesh), opening 75μ, wire diameter 52μ (200
Set a sieve with an opening of 38μ and a wire diameter of 27μ (400 mesh) on top of each other.

(3) Gently sift 5.0 g of precisely weighed toner (10 g
0 mesh) and vibrate for 15 seconds at an amplitude of 1 mm.

(4) Gently weigh the amount of toner remaining on each sieve.

Fluidity index (%) = a + b + c (3) Measurement of apparent density: Using a powder tester (manufactured by Micron for wires), the apparent density is measured. For measurement, a 60-mesh fluid was set on a shaking table, and a pre-weighed apparent density measuring cup (inner capacity: 100 cc) was placed directly below it.

Next, set the rheostat scale to 2.0 and start vibration.

The sample to be measured is gently flowed out from the top of the vibrating 60 mesh sieve into the measuring cup.

When the cup is filled with a heaping amount of sample, the vibration is stopped, the top surface of the cup is scraped off with a blade, and the sample is accurately weighed using a balance.

Since the measuring cup has an internal capacity of 10° C., the appearance can be determined from density (g/cm 3 )=weight of sample ÷ 100.

Note that the sample used was one that had been left in an environment of 23° C. and 60% RH for about 12 hours, and the measurement environment was 23° C. and 60% RH.

(4) Apparent viscosity measurement: Flow tester CFT-500 model (manufactured by Shimadzu Corporation) is used. The sample is a 60mesh bath product with a temperature of about 1.0-
Weigh 1.5g. Using a molding machine, 100kg
Pressure is applied for 1 minute with a load of /cm3.

This pressurized sample is subjected to flow tester measurement under the following conditions at room temperature and normal humidity (temperature: 20-30° C., humidity: 30-70% RH) to obtain a temperature-apparent viscosity curve. From the obtained smooth curve, the apparent viscosity at 90° C. and 100° C. is determined, and this is used as the apparent viscosity with respect to the temperature of the sample.

RATE TEMP 6. OD/M (℃1 minute)
SET TEMP 70. ODEG (℃)M
AX TEMP 200.0 DECINTE
RVAL 3. ODEGPREHEAT
300. OSEC (seconds) LOAD 20
．． OKGF (kg) DIE (DIA) 1
．． 0 MM (mm) DIE (LENG)
1.0 MMPLUNGER1,00M2(c rr
f) (5) Chromaticity measurement: A solid image of seven colors in total is prepared: yellow, magenta, cyan, black, magenta-yellow, magenta=cyan, and cyan=yellow, which are superimposed colors of red and blue-green.

At this time, using a laser color copying machine (manufactured by Canon),
Yellow, magenta, cyan, black developer density from 9 to
It is preferable to use an image which is set to 10% and is imaged at a potential contrast of 150 to 250 V at 23° C. and in a 60% RH environment.

The spectral reflectance of these solid images is measured in the range of 390 to 730 nm using a CA-35 type high-speed spectrophotometer (manufactured by Murakami Color Research Co., Ltd.).

The transfer paper used during the measurement is plain paper such as Sunflower paper, and the image density is within 1.5±0.2 for each color. It is preferable to use an RD-914 type reflection densitometer (manufactured by Macbeth Co., Ltd.) to measure the image density.

Next, based on JIS standard Z-8722, "Method for measuring object color using 2-degree visual field .

That is, first, using a C light source as the light source, a 2-degree field of view as the isochromatic number, and the spectral reflectance of the sample every 10 nm from 390 to 730 nm, the stimulus values of x, y, and z are determined according to the following formula.

X=ΣR(λ)・S(λ)・i(λ) Y=ΣR(λ)・S(λ)・y(λ) ), y(λ
).

i(λ), and the spectral reflectance of the sample is R(λ).

Furthermore, from these x, y, and z values, the chromaticity (a** + b*r L*) is obtained from the following equation.

a" = 500 [(X/XO)""-(Y/Y□)
“Kob*=200 [(Y/Yo)”” (z/z
o)""]L*=116 (Y/Yo)'/"-16
However, Xo, Yo, and Zo are the stimulus values of the light source color, and Xo=
ΣS(λ)·i(λ) Y0=ΣS(λ)·y(λ) (6) Endothermic peak value measurement by DSC: DSC is an abbreviation for differential thermal analysis.

In the present invention, measurement is performed using a differential thermal analysis measuring device (DSC measuring device), DSC-7 (manufactured by PerkinElmer).

The measurement sample has a weight of 5 to 20 mg, preferably l Om
Accurately weigh g.

This is placed in an aluminum pan, and using an empty aluminum pan as a reference, the measurement is performed at room temperature at a temperature increase rate of 10° C./min within the measurement temperature range of 30° C. to 200° C.

In this temperature raising process, the temperature at which the endothermic peak of the main peak in the temperature range of 40 to 100° C. is obtained is defined as the endothermic peak value of the present invention.

(7) Frictional charge measurement: The measurement method will be explained in detail using drawings.

FIG. 6 is an explanatory diagram of an apparatus for measuring the amount of triboelectric charge of toner. First, in a metal measurement container 22 with a 500-mesh screen 23 at the bottom, the toner and carrier whose triboelectric charge amount is to be measured are mixed at the same mixing ratio as when actually used as a developer, and the mixture is heated for 50 to 100 m. I! The mixture (developer) is placed in a large capacity polyethylene bottle, shaken by hand for about 10 to 40 seconds, about 0.5 to 1.5 g of the mixture (developer) is added thereto, and the metal lid 24 is closed. The weight of the entire measuring container 22 at this time is measured as W+(g).

Next, in the suction device 21 (at least the part in contact with the measurement container 22 is an insulator), suction is performed from the suction port 27, and the air volume control valve 26 is adjusted to increase the pressure of the vacuum gauge 25 to 250 mm A.
Let it be q. In this state, suction is performed for a sufficient period, preferably 2 minutes, to remove the toner by suction. The potential of the electrometer 29 at this time is assumed to be V (volt). Here, 28 is a capacitor, and the capacitance is C (μF). In addition, the weight of the entire measurement container after suction is measured and is defined as W2 (g). The amount of triboelectric charge (μc/g) of this toner is calculated as shown in the following formula.

The carrier used for measurement is a 250 mesh pass.

70-90% by weight of 350 mesh carrier particles
A ferrite carrier coated with a styrene resin is used. That is, a ferrite carrier coated with 0.2 to 0.7% by weight of styrene-2-ethylhexyl acrylate-methyl methacrylate is used.

The sample toner and carrier used in the measurement were at 23°C.

After being left in a 60% RH environment for at least 12 hours, it is used to measure the amount of charge.

Further, the measurement of the amount of triboelectric charge is performed in an environment of 23° C. and 60% RH.

(8) Glossiness measurement: Measurement is performed using a VG-10 type glossmeter (manufactured by Nihon Denki), using each solid image used for chromaticity measurement as a sample image.

For measurement, first set the voltage to 6V using a constant voltage device.

Next, the light emission angle and light reception angle are adjusted to 60'.

Using a zero point adjustment and a standard plate, place the sample image on the sample stage after setting the standard, then stack three sheets of white paper on top, perform measurement, and read the value shown on the indicator in % units.

At this time, set the S and S/10 switch SW to S and set the angle.

Set the sensitivity switch SW to 46-60.

Note that a sample with an image density of 1.5±0.1 is used.

(9) Spectral reflectance measurement: After each transfer of yellow, magenta, cyan, and black, unfixed images are prepared.

Since the developer concentration is detected by measuring the reflectance of each color toner particle and carrier in the near-infrared region, it is necessary to measure the unfixed image and read the reflectance of the toner particles on the transfer material.

The spectral reflectance is measured in the range of 700 to 11050 nm using a DK-2A spectrophotometer (manufactured by Beckman) as an apparatus.

(IO) Hydrophobization degree measurement: The methanol titration test is an experimental test to confirm the hydrophobization degree of silica fine powder having a hydrophobized surface.

The "methanol titration test" defined herein for evaluating the degree of hydrophobization of treated silica fine powder is carried out as follows. Sample silica fine powder 0.2g in capacity 250mj
! Add to 50 mj7 of water in an Erlenmeyer flask. Methanol is titrated from the burette until all of the silica is wetted. At this time, the solution in the flask is constantly stirred using a magnetic cooler. The end point is observed when the entire amount of fine silica powder is suspended in the liquid, and the degree of hydrophobization is expressed as the percentage of methanol in the liquid mixture of methanol and water when the end point is reached.

The present invention will be described in detail below with reference to examples and drawings. In addition, "%" and "part" indicate weight % and weight part.

In the present invention, each color toner may be stored in a toner container such as an individual bottle during storage, or a four-color toner kit may be constructed within the copying machine after the toner is replenished into the copying machine. Also, one toner container is divided into four chambers, and each chamber contains magenta.

Cyan, yellow or black toner may be retained to form a full color toner kit form. In any case, four color toners are ultimately present as a kit in the full-color copying machine, forming the full-color toner kit of the present invention.

Example 1 A full color toner kit was obtained using 100 parts by weight of a polyester resin obtained by condensing propoxylated bisphenol and fumaric acid, and the following prescription amounts of a colorant and a charge control agent.

The manufacturing method is to sufficiently premix the above prescribed amounts using a Henschel mixer, melt-knead at least twice using an A* roll mill, and after cooling, coarsely grind the mixture to approximately 1 to 2 mm using a hammer mill. Then, it was pulverized to a particle size of 40 μm or less using an air jet type pulverizer.

Further, the obtained finely pulverized product was classified to select a particle size of 2 to 23μ so as to have the particle size distribution of the present invention, and 100 parts by weight of each classified product was added with fine silica powder treated with hexamethyldisilazane as a fluidity improver. 0.5 parts by weight, magenta, cyan,
Each yellow toner has a specific surface area of Zo according to the BET method.
A color toner was prepared by adding 0.3 parts by weight of alumina fine powder of o rrr/H and 0.5 parts by weight of strontium titanate to the black toner.

Also, styrene-2-ethylhexyl acrylate-methyl methacrylate (copolymerization ratio 45:25:35)
Cu-Zn-Fe coated with about 0.5% by weight of
4% for magenta, 5.5% for cyan and yellow, and 5% for black. %
The mixture was mixed to obtain a toner concentration of , and was used as a developer.

FIG. 5 shows the spectral reflectance in the near-infrared region of these color toners other than black and the coated carrier used. It was found that the difference in reflectance was large between 900 and 11,000 nm.

A copying test was conducted using a color electrophotographic apparatus having an OPC photosensitive drum and a replenishment/development system shown in FIGS. 1 and 2.

Development and transfer of each color toner was performed in the following order: magenta toner, cyan toner, yellow toner, and black toner. During transfer, the transfer commutation flowed to the transfer corotron is 140 mA for magenta toner and 1 for cyan toner.
80 m A, 230 m for yellow toner
A, black toner was used at 290 mA.

An example of the replenishment-development system used in the present invention is as follows.
The replenishment toner sent by the supply screw 13 in the toner transport cable 4 is connected to the developing device 2 at the toner replenishing port 5 and is supplied into the developing device.

When the developing device rotates and comes to a position facing the photosensitive drum 1, the replenishing toner is uniformly mixed with the developer within a very short time by the mixing and conveying screws 16 and 17.
The developer has a constant developer concentration.

The developer is made into a constant amount by the developer regulating blade 15 on the developing sleeve 12, and is subjected to reversal development using the J/B development method at the opposing portion of the photosensitive drum 1 having a negatively charged electrostatic latent image. In this method, negatively charged toner is transferred onto a photosensitive drum. In this example, the distance between the sleeve and the photosensitive drum in the development area was set to 600 μm.

Using this method, we were able to obtain a full-color image with much higher definition than before, which faithfully reproduces the original color chart without fog even after printing 20,000 sheets in full-color mode. Also, transportation within the copying machine.

Detection of developer concentration was also good and stable image density was obtained.

Even when an OHP film was used, the toner permeability was very favorable. Furthermore, no cleaning defects occurred.

The amount of triboelectric charge of the yellow magenta, cyan, and black toners of the present invention is -28.5 μc/g, respectively! -29
,2μc/g, 30,1μc/g,
-29, 8 μc/g. FIG. 3 shows the environmental dependence of the amount of triboelectric charge of cyan toner.

The chromaticity diagram at this time is shown in FIG. 4, and the values and glossiness of each color toner are as follows.

The developer of each color in the development area in this example is shown below.

Table 90°C2 The apparent viscosity at 100°C and the endothermic peak value of DSC were as follows.

The table further shows the particle size distribution, degree of aggregation, and apparent density of the toner composition of the present invention.

Table Example 2 Coloring agent for magenta: C, 1, Paysic Red 12-1
．． A durability test was conducted in the same manner as in Example 1, except that 0 parts by weight and 0.3 parts by weight of C. Obtained. Table 4 shows the physical properties of the toner used.

Example 3 Coloring agents for cyan were C, Y, Pigment Blue 15, 5.
The test was conducted in the same manner as in Example 1, except that the yellow colorant was changed to 2.5 parts of C, R, and Disperse Yellow 54. A desirable image with no fog and good color balance was obtained. Table 4 shows the physical properties of the toner used.

Example 4 A test was conducted in the same manner as in Example 1 except that the yellow colorant was changed to 5.0 parts by weight of C.1 and Pigment Yellow 13, but there were problems with durable conveyance and developer mixability. Performance was achieved that was not possible. Table 4 shows the physical properties of the toner used.

Example 5 A 15,000-sheet durability test was carried out in the same manner as in Example 1 except that the black colorant was changed to 3.2 parts of channel carbon black, and a high-definition and fog-free image was obtained. or,
No cleaning defects occurred. Table 4 shows the physical properties of the toner used.

Comparative Example 1 In Example 1, the volume average diameter of the black toner was 12.2μ.
, when the particle size distribution was set to a broad particle size distribution of 31.1% below 5.04μ and 15.1% above 12.7μ, during full color durability, the back of the transfer paper was lost after 0.5 million copies due to black toner scattering inside the machine. caused dirt. In addition, the laser spot was not faithfully reproduced, resulting in poor halftone reproducibility.

Comparative Example 2 In Example 1, when only fine silica powder was added to the cyan toner, charge-up with the carrier occurred, and the image density was considerably reduced to 0.7 or less as measured by a Macbeth reflection densitometer.

Comparative Example 3 Tested in the same manner as in Example 1 except that the magenta colorant was changed to 3.0 parts by weight of C.1 and Pigment 57, but the color saturation was low and color reproducibility was poor. .

The a* of magenta toner is 63.1. b* is -3,5,
L* was 24.0, and all values deviated from the values specified in the present invention.

[Brief explanation of drawings]

FIG. 1 shows a schematic cross-sectional view of a color electrophotographic copying machine to which the color toner kit of the present invention is applied;
The figure shows an enlarged sectional view of the replenishment system and development system of the copying machine shown in Fig. 1, and Fig. 3 shows environmental changes and frictional electrification of the cyan toner of Example 1 and the magenta toner of Comparative Example 2. FIG. 4 is a graph showing the relationship between the amount and the chromaticity of the yellow toner, magenta toner, cyan toner, and black toner in Example 1, the chromaticity of red color due to the superposition of magenta toner and yellow toner, and the magenta toner. FIG. 5 is a chromaticity diagram showing the chromaticity of blue color resulting from the superposition of cyan toner and cyan toner, the chromaticity of green color resulting from the superposition of cyan toner and yellow toner, and the chromaticity of magenta toner of Comparative Example d. 6 is a graph showing the relationship between wavelength and spectral reflectance of each toner other than black used in Example 1 and carrier, and FIG. 6 is a diagram schematically showing an apparatus for measuring the amount of triboelectric charge of toner. be. Φ II; Submerged in ξ, 4 days, 2, development 9-F"l;:) 2kk t+:yi< 1 koku 15: Confined audience forest - F !6~/ 7:, x-order, transportation worker T-sukusoyuu pandemonium

Claims (5)

[Claims] (1) A full-color toner kit for multicolor electrophotography having at least a yellow toner, a magenta toner, a cyan toner, and a black toner, the yellow toner having resin particles containing a yellow colorant and two or more types of fluidity improvers, The particle size distribution is a volume average particle size of 6.0 to 10.0μ and a number average particle size of 5.04μ.
The following is 40% or less, and the volume average distribution is 12.7 μ or more
0% or less, a fluidity index of 5% to 25%, an apparent density of 0.2 to 1.5 g/cm^3, and an apparent viscosity of the yellow toner at 100°C and 90°C of 10^ 4-5 x 10^5 poise, 5 x 10^4-5
×10^6 poise, DSC endothermic peak value is 58 to 72°C, gloss level is 5.0% or more, and yellow coloring agent is 0.1 to 100 parts by weight of binder resin.
12.0 parts by weight, and the chromaticity of the yellow toner is a.
^*-6.5~-26.5, b^*73.0~93.0
and L^*77.0-97.0, 65% by weight of carrier particles with 250 mesh pass and 350 mesh on.
A toner having a triboelectric charge characteristic of -10 to -50 μc/g against a styrene resin-coated ferrite carrier having the above properties and a 400 mesh pass of 20% by weight or less, the magenta toner comprising magenta colorant-containing resin particles and It has two or more types of fluidity improvers, and its particle size distribution has a volume average particle size of 6.0 to 10.0μ and a number average particle size of 5.04μ.
The following is 40% or less, and the volume average distribution is 12.7 μ or more
0% or less, a fluidity index of 5% to 25%, an apparent density of 0.2 to 1.5 g/cm^3, and an apparent viscosity of the magenta toner at 100°C and 90°C of 10^ 4-5 x 10^5 poise, 5 x 10^4-5
×10^6 poise, DSC endothermic peak value is 58 to 72°C, gloss is 5.0% or more, and magenta colorant is added to 100 parts by weight of binder resin from 0.1 to
Contains 15.0 parts by weight, and the chromaticity of the magenta toner is a^
*60.0~80.0,b^*-12.0~-32.0
and L^*40.0-60.0, 65% by weight of carrier particles with 250 mesh pass and 350 mesh on.
The cyan toner is a toner having a triboelectric charge characteristic of -10 to -50 μc/g with respect to a styrene resin-coated ferrite carrier having a 400 mesh pass of 20% by weight or less, and the cyan toner comprises cyan colorant-containing resin particles. and has two or more fluidity improvers, and its particle size distribution has a volume average particle size of 6.0 to 10.0 μ and a number average particle size of 5.04
μ or less is 40% or less, volume average distribution of 12.7 μ or more is 10% or less, fluidity index is 5% to 25%, and apparent density is 0.2 to 1.5 g/cm^3. ,
The apparent viscosity of the cyan toner at 100°C and 90°C is 10^4 to 5 x 10^5 poise, 5 x 10^4 to 5
×10^6 poise, DSC endothermic peak value is 58 to 72°C, gloss is 5.0% or more, and cyan colorant is 0.1 to 100 parts by weight of binder resin. 1
5.0 parts by weight, and the chromaticity of the cyan toner is a^*
-8 to -28.0, b^* -30.0 to -50.0 and L^* 39.0 to 59.0, and contains 65% by weight or more of carrier particles of 250 mesh pass and 350 mesh on. In addition, the toner has a triboelectric charge characteristic of -10 to -50 μc/g with respect to a styrene-based resin-coated ferrite carrier having a 400 mesh pass of 20% by weight or less, and the black toner is composed of resin particles containing carbon black, fluidized The particle size distribution has a volume average particle size of 6.0 to 10.0 μm and a number average particle size distribution of 5.0 μm.
04 μ or less is 40% or less, the volume average distribution of 12.7 μ or more is 10% or less, the fluidity index is 5% or more and 25% or less, and the apparent density is 0.2 to 1.5 g/cm^3. , the apparent viscosity of the black toner at 100°C and 90°C is 10^4 to 5 x 10^5 poise, 5 x 10^4 to
5×10^6 poise, DSC endothermic peak value is 58 to 72° C., carbon black is contained in 0.1 to 10.0 parts by weight per 100 parts by weight of the binder resin, and the black toner The chromaticity of is a^*-2.0~3.0, b^*-
1.0 to 3.0 and L^*26.0 to 45.0,
250 mesh pass, has 65% by weight or more of carrier particles of 350 mesh on, and 400 mesh pass is 20
The triboelectric charge characteristic for the styrene resin-coated ferrite carrier is -10 to -50 μc/g by weight% or less.
A full color toner kit that is characterized by being a toner that is. (2) In a yellow developer having a yellow toner and a resin-coated ferrite carrier, the resin-coated ferrite carrier is a styrene-based resin-coated ferrite carrier, and the yellow toner includes yellow colorant-containing resin particles and two or more types of fluidity. The toner has a particle size distribution of a volume average particle diameter of 6.0 to 10.0μ and a number average distribution of 5.
04 μ or less is 40% or less, the volume average distribution of 12.7 μ or more is 10% or less, the fluidity index is 5% or more and 25% or less, and the apparent density is 0.2 to 1.5 g/cm^3. , the apparent viscosity of the yellow toner at 100°C and 90°C is 10^4 to 5x10^5 poise, 5x10^
It is in the range of 4 to 5 x 10^6 poise, the DSC endothermic peak value is 58 to 72 °C, the gloss is 5.0% or more, and the yellow colorant is 0% per 100 parts by weight of the binder resin.
．． The yellow toner contains 1 to 12.0 parts by weight, and the chromaticity of the yellow toner is a^*-6.5 to -26.5, b^*73.0 to 93.
．． 0 and L^*77.0 to 97.0, and has 65% by weight or more of carrier particles of 250 mesh pass and 350 mesh on, and 400 mesh pass is 20% by weight or less for a styrene resin coated ferrite carrier. A yellow developer characterized by having a triboelectric charge characteristic of -10 to -50 μc/g. (3) In a magenta developer having a magenta toner and a resin-coated ferrite carrier, the resin-coated ferrite carrier is a styrene-based resin-coated ferrite carrier, and the magenta toner contains magenta colorant-containing resin particles and two or more types of fluidity. The toner contains an improving agent, and the particle size distribution of the toner is a volume average particle size of 6.0 to 10.0 μm and a number average particle size of 5 μm.
．． 04μ or less is 40% or less, volume average distribution is 12.7μ
10% or less, and the liquidity index is 5% or more and 25%
The apparent density is 0.2 to 1.5 g/cm^3, and the apparent viscosity of the magenta toner at 100°C and 90°C is 10^4 to 5 x 10^5 poise, 5 x 10
It is in the range of ^4 to 5 x 10^6 poise, the DSC endothermic peak value is 58 to 72 °C, the gloss is 5.0% or more, and the magenta colorant is added to 100 parts by weight of the binder resin. The magenta toner contains 0.1 to 15.0 parts by weight, and the chromaticity of the magenta toner is a^*60.0 to 80.0, b^*-12.0 to
-32.0 and L^*40.0 to 60.0, and 25
The triboelectric charge characteristic for a styrene-based resin-coated ferrite carrier having 65% by weight or more of carrier particles of 0 mesh pass and 350 mesh pass and 20% by weight or less of 400 mesh pass is -10 to -50 μc/g. A magenta developer characterized by (4) In a cyan developer having a cyan toner and a resin-coated ferrite carrier, the resin-coated ferrite carrier is a styrene-based resin-coated ferrite carrier, and the cyan toner contains resin particles containing a cyan colorant and two or more types of fluidity. Contains an improving agent, and the particle size distribution of the toner has a volume average particle size of 6.0 to 10.0 μm and a number average particle size of 5.0 μm.
4 μ or less is 40% or less, the volume average distribution of 12.7 μ or more is 10% or less, the fluidity index is 5% or more and 25% or less, and the apparent density is 0.2 to 1.5 g/cm^3. , the apparent viscosity of the cyan toner at 100°C and 90°C is 10^4 to 5 x 10^5 poise, 5 x 10^4 to
It is in the range of 5 × 10^6 poise, the DSC endothermic peak value is 58 to 72 ° C., and the gloss is 5.0% or more,
Add cyan colorant from 0.1 to 100 parts by weight of binder resin.
Contains 15.0 parts by weight, and the chromaticity of the cyan toner is a^*
-8 to -28.0, b^* -30.0 to -50.0 and L^* 39.0 to 59.0, and contains 65% by weight or more of carrier particles of 250 mesh pass and 350 mesh on. A cyan developer characterized in that the toner is a toner having a triboelectric charge amount characteristic of -10 to -50 μc/g with respect to a styrene resin-coated ferrite carrier having a 400 mesh pass of 20% by weight or less. (5) In a black developer having a black toner and a resin-coated ferrite carrier, the resin-coated ferrite carrier is a styrene-based resin-coated ferrite carrier, and the black toner includes resin particles containing carbon black,
The toner contains a fluidity improver and a friction reducing agent, and has a volume average particle diameter of 6.0 to 10.0 μm, a number average particle size of 5.04 μm or less of 40%, and a volume average particle size of 12.0 μm or less.
7μ or more is 10% or less, and the fluidity index is 5% or more2
5% or less, apparent density 0.2 to 1.5 g/cm^
3, and the apparent viscosity of the black toner at 100°C and 90°C is 10^4 to 5x10^5 poise, 5x10
It is in the range of ^4 to 5 x 10^6 poise, has a DSC endothermic peak value of 58 to 72 °C, and contains 0.1 to 10.0 parts by weight of carbon black per 100 parts by weight of the binder resin, The chromaticity of the black toner is a^*-2.0 to 3.0, b
^*-1.0 to 3.0 and L^* 26.0 to 45.0, having 65% by weight or more of carrier particles of 250 mesh pass and 350 mesh on, and 20% by weight or less of 400 mesh pass The triboelectric charge characteristic for the styrene resin-coated ferrite carrier is -10 to -50μ
A black developer characterized by c/g.