JP2001034008A - Production of toner, method for filling toner into toner vessel and toner cartridge - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a toner which is easily filled into a toner cartridge without causing the isolation and re-aggregation of the additive. SOLUTION: A toner having toner particles and an additive and having 2-8 μm number average particle diameter (a) by the Coulter method is passed through a spiral screw to produce the objective toner. The original toner has an average circularity of 0.950-0.995 in the circularity distribution of the particles measured with a flow type particle image analyzer and contains 2-40% by number of particles whose circularity is <0. 950 and the toner is produced by dispersing the additive on toner particles and passing the resulting particles through a screen whose opening (B) satisfies 5<=B/a<=15 to separate and remove coarse particles.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for filling a container with fine powder, and more particularly to a method suitable for filling a container with toner used in an image forming apparatus.

[0002]

2. Description of the Related Art In recent years, in an image forming method using an electrophotographic technique such as a copying machine or a laser printer, a further reduction in size of a machine, a longer life, a reduction in energy consumption, a higher definition of image quality, Reproducibility is required. As one of the methods for achieving such a demand, a method is known in which the average particle diameter and sphericity of toner particles as an electrostatic charge image developer are defined.

Various means have been reported as means for adjusting the average particle size and sphericity of toner particles.
For example, there are a conventional hot water bath method in which toner particles are dispersed in water and heated, a heat treatment method in which the toner particles are passed through a hot air stream, and a mechanical impact method in which mechanical energy is applied to treat the toner particles. Alternatively, Japanese Patent Application Laid-Open No. Sho.
JP-A-9-53856 and JP-A-59-61842 disclose a method of directly producing toner particles using a suspension polymerization method, and a method of dissolving a monomer but dissolving a polymer obtained. Emulsion polymerization method represented by dispersion polymerization method in which toner particles are produced by direct polymerization using an aqueous organic solvent that does not generate water, or soap-free polymerization method in which toner particles are produced by direct polymerization in the presence of a water-soluble polar polymerization initiator Etc.

In particular, when the toner particles are obtained by a so-called polymerization method, the average particle diameter and the sphericity of the toner particles are easily adjusted, and the charge characteristics of each toner particle are made uniform. Therefore, it is possible to reduce so-called “fog” in which poorly charged toner particles are scattered in the non-printing area, and to reduce the amount of waste toner.

As a means for further improving the fluidity, charging characteristics, and environmental resistance of such toner particles, a method of appropriately adding various inorganic fine particles or organic fine particles to the surface of the toner particles has been widely used. The fine particles are called external additives, and various types of external additives are used alone or in combination depending on their functions, effects and the like. These external additives, when present in the surface layer of the toner particles, exhibit their functions best.

However, in the spherical toner, the form of attachment of the external additive on the surface of the toner particles is different from that of the conventional pulverized toner. As a result, release of the external additive and accompanying reaggregation of the external additive were likely to occur.

The inventors of the present invention have conducted detailed studies on this phenomenon. As a result, when an external additive having a low chargeability was used (for example, titanium oxide, alumina, etc.), the external additive was dispersed on toner particles. When a particle having a large particle diameter is used (silica, titanium oxide, alumina, organic resin particles or the like having a size of 100 nm or more) This is more remarkable when a mesh with a small opening is used as a coarse particle removing step after external addition mixing. Was found to occur.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a manufacturing method and a toner cartridge for easily filling a developing container with a toner without releasing and re-aggregating an external additive.

[0009]

Means for Solving the Problems As a result of detailed studies, the present inventors have found a method of easily filling a developing container with a toner without releasing or re-aggregating an external additive. It has been found that the use of the toner cartridge filled by the method of the present invention has improved image quality as compared with the conventionally known method, and has led to the present invention.

That is, the present invention has a number average particle diameter a of 2 to 2 having a toner particle and an external additive by a Coulter method.
In a toner production method for producing a toner by passing a toner having a diameter of 8 μm through a spiral screw,
The toner has a circularity distribution of particles measured by a flow type particle image analyzer of 0.950 to 0.99.
It contains 2 to 40% by number of particles having an average circularity of 5 and a circularity of less than 0.950, and has an aperture (B) of 5 after the external additive is dispersed on the toner particles. ≦ B / a ≦
The present invention relates to a method for producing a toner, characterized in that coarse particles are separated and removed through a screen of No. 15 to produce a toner.

Further, according to the present invention, a toner having toner particles and an external additive, having a number average particle diameter a by a Coulter method of 2 to 8 μm.
m in a toner container through a spiral screw, wherein the toner has a circularity distribution of 0.950 to 0 in particles measured by a flow type particle image analyzer. It contains 2 to 40% by number of particles having an average circularity of 0.995 and a circularity of less than 0.950. After the external additive is dispersed on the toner particles, the aperture (B) becomes 5 ≦ B / a ≦ 15
And separating and removing coarse particles by passing the toner through a screen, and filling the toner into a toner container so as to have a filling rate of 0.3 to 0.5 g / ml.

Further, the present invention relates to a toner cartridge detachably mounted to an image forming apparatus, wherein the toner cartridge has a number average particle diameter a by a Coulter method of 2 to 8 μm, having toner particles and an external additive. A toner cartridge filled with a certain toner via a spiral screw, and the toner has a circularity distribution of particles measured by a flow type particle image analyzer,
Has an average circularity of 0.950 to 0.995, and
It contains 2 to 40% by number of particles having a circularity of less than 0.950. After the external additive is dispersed on the toner particles, the particles are passed through a screen having an aperture (B) of 5 ≦ B / a ≦ 15. And a toner cartridge filled with toner so as to obtain a filling rate of 0.3 to 0.5 g / ml.

[0013]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 shows a schematic diagram of an apparatus used for filling according to the present invention.

The toner is put into the hopper 101, and the spiral screw 103 is rotated by the drive motor 111 to send the toner downward. The toner is the spiral screw 103 and the screw casing 1
After passing through the gap of No. 06, it is discharged from the discharge port 104. The outlet 104 is provided with a chrysanthemum seat 105 in order to prevent the flushing of the toner and the eccentricity of the screw rotating shaft.

Using an apparatus as shown in FIG.
When the toner container is placed in the lower part of the toner container 4, and the toner is filled in the toner container, the toner can be filled in the developing container without giving excessive vibration to the toner particles. The physical properties of the toner are not impaired.

Further, when the toner filled in the developing container by the method of the present invention is compared with the toner filled while applying vibration to the toner particles, the toner filled by the method of the present invention has higher image characteristics. It became clear to have. It is considered that this is because, in addition to the above-described effect of preventing the external additive from being released and re-aggregated, the state of attachment of the fine particles to the surface layer of the toner particles is more preferable.

The improvement of the adhesion state of the fine particles is achieved by the pressure applied when a part of the toner particles pass through the minute gap, that is, the clearance between the outermost edge of the screw portion and the inner wall of the screw casing. It is believed that this has been achieved by sticking to some surface layers of the particles.

In the present invention, the inner diameter D of the screw casing is 12 to 130 mm, the clearance δ between the outermost edge of the screw portion and the inner wall of the screw casing is 0.05 to 3.0 mm, and the rotation speed of the screw is r is preferably 50 to 3000 rpm, and the pitch length W preferably satisfies the following expression.

0.1 × H <W <3.0 × H (where H is the outer diameter of the spiral screw, H = D−2δ)

More preferably, the inner diameter D of the screw casing is 15 to 100 mm, the clearance δ between the outermost edge of the screw portion and the inner wall of the screw casing is 0.10 to 2.5 mm, and the rotation speed r of the screw is Is preferably 50 to 1500 rpm, and the pitch length W satisfies the following expression.

0.3 × H <W <2.0 × H

These parameters are defined as the average particle size of 1 to 10
It is considered that there is a correlation with the state of adhesion of the fine particles of 00 nm to the surface layer of the toner particles. That is, the inner diameter D of the screw casing is larger than 130 mm; or the clearance δ between the outermost edge of the screw portion and the inner wall of the screw casing is larger than 3.0 mm; or
When the rotational speed r of the screw is smaller than 50 rpm; or when the pitch length W is larger than 3.0 × H, the pressure applied to the surface layer of the toner particles becomes insufficient, and the fine particles are preferable for the surface layer of the toner particles. Not fixed. Also, the inner diameter D of the screw casing is smaller than 12 mm; or the clearance δ between the outermost edge of the screw portion and the inner wall of the screw casing is smaller than 0.05 mm;
Or, when the rotation speed r of the screw is larger than 3000 rpm; or when the pitch length W is smaller than 0.1 × H, the pressure applied to the toner particle surface layer becomes excessive,
Because the fine particles are fixed and buried in the surface layer of the toner particles,
A stable image cannot be supplied for a long time.

The above-mentioned effect is more remarkable when a screen having a small aperture after external addition according to the present invention is used. That is, when a screen having a small aperture is used, the chance of contact of the toner particles with the screen is further increased, and the external additive is easily released from the toner surface.
However, in the present invention, it is presumed that in order for the external additive, which has become slightly free, to pass through the apparatus as shown in FIG.

FIG. 2 is a schematic sectional view of a classification device suitable for the present invention. The blades 1 inside the cylindrical screen 11
2 rotates at high speed. The toner supplied from the toner supply port 13 collides with the blade 12 to be disaggregated and collides with the screen 11 by centrifugal force, and the toner having a particle size smaller than the aperture passes through the toner collection unit 14. The collected coarse particles move inside the screen and are discharged from the coarse particle discharge port 15. An elastic ball 16 is provided inside the screen 11.
Exists, and strikes the inside of the screen 11 in accordance with the rotation of the blades to prevent clogging.

The feature of the above classifier is that, first of all, the coagulation of the toner is sufficiently released by the rotating blades. In a conventional classifier, rubber balls and the like are placed on a screen or a screen unit and dislodged by their movement. However, the capacity is not sufficient, and the throughput is reduced. In the above classifier, the coagulation is broken by the blade rotating at a high speed, so that it is possible to cause the sufficiently dispersed toner to collide with the screen.

The second feature is that a strong centrifugal force acts on the toner to pass the toner through the screen. In the conventional apparatus, the toner is caused to pass through the screen only by gravity, but in the above-described apparatus, the toner can be given a stronger force to pass through the screen.

The third feature is that an elastic ball inside the screen collides with the screen and gives a slight vibration to prevent clogging. Unlike brushes used in conventional gyro shifters, etc., they only apply micro-vibration to the screen.Since they are very small and small enough, they do not damage the screen. No change in aperture occurs. Further, since the elastic ball is used, no fragments are mixed into the toner.

The blades used in the above classifier may be, for example, those in which a plurality of plate-like blades are attached to a rotary shaft, and the number of rotations is generally in the range of 500 to 2000 rpm. As the screen to be used, any of known materials can be used. However, a resin screen made of a resin such as polyester is preferable because an elastic ball gives a slight vibration. The elastic ball to be used is a general ball of urethane or the like having a diameter of several millimeters, and about 10 balls exhibit a sufficient effect.

As described above, Japanese Patent Application Laid-Open No. 5-293443
In the classifier preferably used in the present invention as shown in Japanese Patent Application Laid-Open Publication No. H07-163, the external additives tend to be loose when the toner aggregates are released and further when the toner passes through the screen. A stable state of attachment is achieved.

As the screen used in the production method of the present invention, any of the conventionally known materials can be used. However, since the screen is subjected to micro-vibration by an elastic ball, the screen is made of resin such as polyester. Are particularly preferred. The elastic ball is a general ball made of polyurethane or the like having a diameter of about several mm, and preferably about 10 balls exhibit a sufficient effect.

In the present invention, the number average diameter a of the toner a
Is 2 to 8 μm, and the opening B of the screen is 5 ≦ B /
It satisfies the relationship of a ≦ 15 and is more effective when it is in the range of 7 ≦ B / a ≦ 10 for improving productivity and suppressing release of external additives. The screen aperture is B /
When a> 15, the effect of removing coarse particles is insufficient, and B /
If a <5, reduction of the processing capacity and release of the external additive are promoted, and even when combined with the above-described filling device, satisfactory products cannot be obtained in terms of quality. If a is smaller than 2 μm, the fluidity of the toner decreases, the dischargeability at the time of filling becomes unstable, and it becomes difficult to control the filling amount.
If the ratio exceeds, development reproducibility for a minute latent image is reduced.

In the present invention, the circularity distribution of the particles measured by the toner flow type particle image analyzer has an average circularity of 0.950 to 0.995 and a circularity of less than 0.950. Another feature is that 2 to 40% by number of particles are contained.

Here, the "flow type particle image analyzer" is a device for statistically analyzing the image of particle imaging.
"Average circularity" is calculated by the arithmetic mean of the circularity determined by the following equation using the apparatus.

[0034]

(Equation 1)

In the above equation, the “perimeter of the particle projection image” is the length of the contour obtained by connecting the edge points of the binarized particle image, and the “perimeter of the equivalent circle” is , The length of the circumference of a circle having the same area as the binarized particle image.

If the average circularity of the toner is less than 0.950, the external additive tends to be unevenly distributed on the surface of the toner. As a result, the image density tends to be unstable, and the average circularity of the toner is 0. If it exceeds 0.995, it becomes difficult to hold the external additive on the toner surface, and as a result, the charging becomes non-uniform and fog is liable to occur.

The toner contains 2 to 40% by number, preferably 3 to 30% by number of particles having a circularity of less than 0.950.

When the content of particles having a circularity of less than 0.950 is 2
If the amount is less than a few percent, the toner is likely to be packed most closely, and as a result, it becomes difficult to control the dischargeability at the time of filling.

When the content of particles having a circularity of less than 0.950 is 4
If it exceeds 0% by number, the fluidity of the toner decreases,
Image degradation such as a decrease in fine line reproducibility is likely to occur.

In the present invention, in particular, the suspension polymerization method comprises:
It is preferable because the particle size distribution of the produced toner particles becomes sharp, and a large amount of wax as a release agent can be contained in the toner particles. Further, a seed polymerization method in which a monomer is further adsorbed on the polymerized toner particles once obtained and then polymerized using a polymerization initiator can also be suitably used in the present invention.

When the toner of the present invention contains toner particles produced by a polymerization method, the toner particles can be specifically produced by the following production method. A releasing agent comprising a low softening point substance, a colorant, a charge control agent, a polymerization initiator, and other additives are added to the monomer, and a homogenizer, a monomer system uniformly melted or dispersed by an ultrasonic disperser is used. Is dispersed in an aqueous phase containing a dispersion stabilizer using a conventional stirrer or a disperser such as a homomixer and a homogenizer. Preferably, the stirring speed and the stirring time are adjusted so that the monomer droplets have a desired size of the toner particles, and the granulation is performed. Thereafter, by the action of the dispersion stabilizer, the particles may be stirred to such an extent that the particle state is maintained and the particles are prevented from settling. The polymerization is performed at a polymerization temperature of 40 ° C. or higher, generally 50 to 90 ° C.

At this time, the circularity distribution can be controlled by the type and amount of the dispersion stabilizer, the stirring ability, the pH of the aqueous phase, and the polymerization temperature.

In the present invention, the circularity distribution of the circle equivalent diameter of the toner is determined by a flow type particle image analyzer FPIA-1000.
(Manufactured by Toa Medical Electronics Co., Ltd.) as follows.

In the measurement, fine dust is removed through a filter, and as a result, the measurement range (for example, a circle equivalent diameter of 0.60 μm or more and 159.21 μm) is placed in 10 ⁻³ cm ³ of water.
m) of a surfactant (preferably Contaminone manufactured by Wako Pure Chemical Industries, Ltd.) in ion-exchanged water having a particle number of 20 or less.
About 10 ml of a solution prepared by adding 0.5% by weight (20 ° C.)
Was prepared by adding about 0.02 g of a measurement sample to the mixture and uniformly dispersing it. As a means for dispersing, an ultrasonic disperser UH-50 manufactured by SMT Co., Ltd. (vibrator is a 5φ titanium alloy chip) was used. Dispersion time should be more than 5 minutes,
At this time, the dispersion medium was appropriately cooled so that the temperature of the dispersion medium did not exceed 40 ° C. Using the above flow type particle image measuring apparatus,
The particle size distribution and circularity distribution of particles having a circle equivalent diameter of 60 μm or more and less than 159.21 μm are measured.

The outline of the measurement is described in the catalog of FPIA-1000 (June 1995 version) issued by Toa Medical Electronics Co., Ltd., the operation manual of the measuring apparatus, and Japanese Patent Application Laid-Open No. 8-1364.
No. 39, which is as follows.

The sample dispersion liquid is passed through a flow path (spread along the flow direction) of a flat and flat transparent flow cell (thickness: about 200 μm). The strobe and the CCD camera are mounted on the flow cell so as to be positioned on opposite sides of the flow cell so as to form an optical path that intersects with the thickness of the flow cell. While the sample dispersion is flowing, strobe light is irradiated at 1/30 second intervals to obtain an image of the particles flowing through the flow cell, so that each particle has a range parallel to the flow cell 2
Photographed as a two-dimensional image. The diameter of a circle having the same area is calculated as the equivalent circle diameter from the area of the two-dimensional image of each particle. Further, the circularity of each particle is calculated by dividing the perimeter of a circle (equivalent circle) having the same area as the two-dimensional image of each particle by the perimeter of the two-dimensional image of each particle.

As shown in Table 1, the results (frequency% and cumulative%) can be obtained by dividing the range of 0.06 to 400 μm into 226 channels (divided into 30 channels per octave). In the actual measurement, the equivalent circle diameter is 0.
The particles are measured in a range of 60 μm or more and less than 159.21 μm.

[0048]

[Table 1] *) The upper limit of the particle size range does not include the numerical value and represents “less than”.

Japanese Patent Application Laid-Open No. 9-304968 discloses the relationship between the weight average particle size of the toner and the opening ratio of the sieve, but the external additive used when a spherical toner is used as the toner as in the present invention. There is no description at all about the point of suppressing detachment of the toner and stably adhering the external additive onto the toner particles for a long period, which is different from the present invention.

Similarly, Japanese Patent Application Laid-Open No. Hei 7-31177 discloses the structure of a turbo screener used in the embodiment of the present invention as a toner sieving apparatus.
No. 3688 discloses the use of the ultrasonic sieve used in the examples of the present invention, but does not mention the shape of the toner and the adhesion state of the external additive in any of them. Are different.

One feature of the present invention is that the number average particle diameter of the toner is 2 to 8 μm. If the number average particle diameter of the toner is smaller than 2 μm, it becomes difficult to discharge the toner quantitatively during the filling operation of the toner, and as a result, overflow or scattering from the toner container tends to occur.
On the other hand, when the thickness exceeds 8 μm, the development reproducibility for a fine latent image is reduced.

As the external additive in the present invention, it is possible to use organic or inorganic fine particles which are generally widely known as external additives. Specifically, examples of inorganic fine particles include metal oxides (such as aluminum oxide, titanium oxide, strontium titanate, cerium oxide, magnesium oxide, chromium oxide, tin oxide, and zinc oxide), nitrides (such as silicon nitride), and carbides (such as silicon nitride). Metal salts (such as calcium sulfate, barium sulfate, and calcium carbonate), fatty acid metal salts (such as zinc stearate and calcium stearate), carbon black, and silica can be used. Examples of the organic fine particles include homopolymers or copolymers of monomer components such as styrene, acrylic acid, methyl methacrylate, butyl acrylate, and 2-ethylhexyl acrylate, which are used in a binder resin for a toner, obtained by an emulsion polymerization method or a spray drying method. Polymers can be used.

If necessary, a plurality of these fine particles can be used in combination.

In particular, in the present invention, it is preferable to use titanium oxide, aluminum oxide, and silica-treated fine particles thereof, which have low charging ability, as the external additive. That is, the above-mentioned external additive having a small chargeability has a smaller electrostatic adhesion to the toner particle surface as compared with silica fine particles having a high chargeability which have been widely used as an external additive in the related art, and the coarse additive is used in the coarse particle separation step. When passing through a screen,
The toner particles become slightly free. However, in the present invention, since a filling step is performed in the next step, release is suppressed for a long time.

The external additive used in the toner of the present invention has a weight average particle diameter of 10 to 4 from the viewpoint of imparting fluidity.
00 nm, preferably 10 to 100 nm. If it is larger than 400 nm, toner charging due to poor fluidity becomes non-uniform, and as a result, toner scattering, fogging and the like occur. On the other hand, when the thickness is smaller than 10 nm, the toner is easily embedded on the surface of the toner, and the deterioration of the toner occurs quickly.

Further, the above-mentioned external additive (A) which is present in the form of primary particles or secondary particles on the toner particles, and a non-spherical inorganic fine powder produced by combining a plurality of particles. (B) is more preferable.

That is, the external additive (A) adheres to the surface of the toner particles appropriately, thereby making the charge on the surface of the toner particles uniform, sharpening the charge amount distribution of the toner, and improving the fluidity of the toner. The non-spherical inorganic fine powder (B) functions as a spacer for toner particles, thereby suppressing the embedding of toner particles in the external additive (A). .

In general, when toner particles having little irregularities on the surface and having a nearly spherical shape are contacted with a member for imparting triboelectric charge to the toner such as carrier particles, an external additive externally added to the surface of the toner particles is used. Where the toner particles escape, the toner particles are easily buried on the surface of the toner particles, and the toner tends to deteriorate.

However, as described above, the toner of the present invention has an average circularity of 0.950 to 0.995, and the content of particles having a circularity of less than 0.950 is approximately 2 to 40% by number, and is close to a spherical shape. Although it is a toner, since the external additive (A) and the non-spherical inorganic fine powder (B) are provided on the toner particles, the external additive (A) can be effectively embedded in the surface of the toner particles. It is to suppress.

The non-spherical inorganic fine powder (B) used in the present invention has a shape factor SF-1 on toner particles of more than 150, preferably more than 190, and more preferably more than 200. This is effective in suppressing the embedding of the agent (A) on the surface of the toner particles.

Shape factor SF of non-spherical inorganic fine powder (B)
When -1 is 150 or less, the non-spherical inorganic fine powder (B) itself is easily embedded on the surface of the toner particles, and the effect of suppressing the external additive (A) from being embedded is reduced.

The shape factor SF-1 of the non-spherical inorganic fine powder (B) on the toner particles was measured by FE-SEM.
Perform at a magnification of 10,000 times.

In the present invention, SF-1 representing the shape factor is obtained by randomly sampling 100 particle images using FE-SEM (S-800) manufactured by Hitachi, Ltd. Image analysis device (L
uzex3), analyzed, and defined a value calculated from the following equation.

[0064]

(Equation 2) (In the formula, MXLNG indicates the absolute maximum length of the measurement particle on the image, and AREA indicates the projected area of the measurement particle.)

The non-spherical inorganic fine powder (B) preferably has an average major axis on the toner particles of preferably from 120 to 600 nm, more preferably from 130 to 500 nm.

The non-spherical inorganic fine powder (B) has an average major axis of 1
When it is less than 20 nm, the spacer effect of suppressing the external additive (A) from being embedded in the toner surface is small. As a result, the developability / transferability of the toner is reduced and the image density is easily reduced. If it exceeds, the above-mentioned spacer effect can be expected, but it is easily released from the toner surface, and as a result, the photoreceptor is liable to be scraped, scratched, and the like.

The toner according to the present invention generally contains a binder resin and a colorant as main components.

As the binder resin of the toner according to the present invention,
Styrenes such as polystyrene and polyvinyltoluene and their substituted homopolymers; styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene- Ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate Copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer , Styrene-pig Styrene copolymers such as ene copolymers, styrene-isoprene copolymers, styrene-maleic acid copolymers, styrene-maleic acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, Examples include polypropylene, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, paraffin wax, carnauba wax and the like. These can be used alone or in combination.

As the colorant used in the toner according to the present invention, carbon black, a magnetic substance, and those toned to respective colors using the following yellow / magenta / cyan colorants are used.

Examples of the yellow colorant include condensed azo compounds, isoindolinone compounds, anthraquinone compounds,
Compounds represented by azo metal complexes, methine compounds and allylamide compounds are used. Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 6
2, 74, 83, 93, 94, 95, 109, 110,
111, 128, 129, 147, 168, 180, Solvent Yellow 162, 163 and the like are preferably used.

Examples of the magenta colorant include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds and perylene compounds. Specifically, C.I.
I. Pigmentlets 2, 3, 5, 6, 7, 23, 4
8: 2, 48: 3, 48: 4, 57: 1, 81: 1, 1
22, 144, 146, 166, 169, 177, 18
4, 185, 202, 206, 220, 221, 254
Is particularly preferred.

As the cyan coloring agent used in the present invention, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds and the like can be used.
Specifically, C.I. I. Pigment Blue 1, 7, 15,
15: 1, 15: 2, 15: 3, 15: 4, 60, 6
2, 66 and the like can be particularly preferably used.

These colorants can be used alone or as a mixture or in the form of a solid solution.

When the colorant of the present invention is a color toner,
It is selected from the viewpoints of hue angle, saturation, lightness, weather resistance, OHP transparency, and dispersibility in toner. The amount of the colorant added is
It is used by adding 1 to 20 parts by weight to 100 parts by weight of the resin.

When a magnetic material is used as a black colorant, unlike other colorants, 40 to 100 parts by weight of resin is used.
Used by adding 150 parts by weight.

In the toner of the present invention, a charge control agent can be used if necessary.

The charge control agents used in the present invention include:
Although a known toner can be used, in the case of a color toner, a charge control agent which is colorless, has a high toner charging speed, and can stably maintain a constant charge amount is particularly preferable.

Specific examples of the negative compound include metal compounds of salicylic acid, naphthoic acid, dicarboxylic acid and derivatives thereof, sulfonic acid, high molecular compounds having carboxylic acid in the side chain, boron compounds, urea compounds, silicon compounds as negative compounds. A compound, calixarene and the like can be used, and a quaternary ammonium salt, a high molecular compound having the quaternary ammonium salt in a side chain, a guanidine compound, an imidazole compound and the like are preferably used as the positive system.

The charge control agent is preferably used in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of the resin. However, in the present invention, the addition of a charge control agent is not essential, and in the case of using a two-component developing method, frictional charging with a carrier is used. It is not always necessary to include a charge control agent in the toner by actively utilizing frictional charging with the sleeve member and the sleeve member.

In the toner of the present invention, a substance having a low softening point, so-called wax, can be used if necessary.

The low softening point substance used in the toner of the present invention includes polymethylene wax such as paraffin wax, polyolefin wax, microcrystalline wax, Fischer-Tropsch wax, amide wax, higher fatty acid, long-chain alcohol, ester wax. And derivatives thereof such as graft compounds and block compounds, and those having a sharp endothermic peak in a DSC endothermic curve from which low molecular weight components have been removed are preferred.

The wax preferably used is a linear alkyl alcohol having 15 to 100 carbon atoms, a linear fatty acid, a linear acid amide, a linear ester, or a montan derivative. It is also preferable that these waxes have impurities such as liquid fatty acids removed in advance.

Further, preferably used wax is
A low molecular weight alkylene polymer obtained by radical polymerization of alkylene under high pressure or a Ziegler catalyst or another catalyst under low pressure; an alkylene polymer obtained by thermally decomposing a high molecular weight alkylene polymer; Separated and purified low-molecular-weight alkylene polymer that is produced; from hydrocarbon polymer distillation residue obtained from the synthesis gas consisting of carbon monoxide and hydrogen by the Age method, or from synthetic hydrocarbon obtained by hydrogenating the distillation residue. And polymethylene wax obtained by extracting and separating a specific component. An antioxidant may be added to these waxes.

The low softening point substance used in the present invention is DS
The C endothermic curve preferably has an endothermic main peak in a region of 40 to 90 ° C (more preferably 45 to 85 ° C). Further, the endothermic main peak has a half width of 1
A material having a low softening point having a sharp melt property of 0 ° C. or less (more preferably 5 ° C. or less) is preferable. In particular, an ester wax whose low softening point substance is an ester wax mainly containing an ester compound of a long-chain alkyl alcohol having 15 to 45 carbon atoms and a long-chain alkyl carboxylic acid having 15 to 45 carbon atoms is preferable.

As a method for producing toner particles by a polymerization method, a releasing agent, a coloring agent, a charge control agent, a polymerization initiator and other additives are added to a polymerizable monomer, and a homogenizer, an ultrasonic disperser, or the like is used. The monomer composition uniformly dissolved or dispersed in the above is dispersed in an aqueous phase containing a dispersion stabilizer by a homomixer or the like. The granulation is stopped when the desired toner particle size is obtained from the droplets of the monomer composition. Thereafter, by the action of the dispersion stabilizer, the particles may be stirred to such an extent that the particle state is maintained and the particles are prevented from settling. The polymerization temperature is 40 ° C. or higher, generally 5
The polymerization is carried out at a temperature of 0 to 90 ° C. Further, for the purpose of obtaining a predetermined molecular weight distribution, the temperature may be raised in the latter half of the polymerization reaction, and further, in the latter half of the reaction to remove unreacted polymerizable monomers, by-products, and the like, or after completion of the reaction. Part of the aqueous medium may be distilled off. After the reaction, the generated toner particles are collected by washing and filtration, and dried. In the suspension polymerization method, water is usually 300 to 100 parts by weight of the monomer composition.
It is preferable to use 3000 parts by weight as a dispersion medium.

The shape factor of the toner particles is controlled by controlling the type and amount of the dispersion stabilizer, the stirring conditions, the pH of the aqueous layer and the polymerization conditions, and the molecular weight of the additives when producing the toner particles by the above polymerization method. Can be adjusted.

In the present invention, when toner particles are obtained by a suspension polymerization method, styrene, o (m-, p-)-methylstyrene, m (p-)-
Styrene monomers such as ethylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (meth)
Octyl acrylate, dodecyl (meth) acrylate,
(Meth) acrylic ester based monomer such as stearyl (meth) acrylate, behenyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate Ene monomers such as butadiene, isoprene, cyclohexene, (meth) acrylonitrile, and acrylamide are preferably used. These can be used alone or generally in the published Polymer Handbook, 2nd Edition II.
I-P139-192 (John Wiley & Son
The glass transition temperature (Tg) of the glass is 40
The monomers are appropriately mixed and used so as to show a temperature of from -80 ° C.
If the theoretical glass transition temperature is less than 40 ° C., there arises a problem in terms of the storage stability of the toner and the durability stability of the developer,
On the other hand, when the temperature exceeds 80 ° C., the fixing point rises. In particular, in the case of a full-color toner, the color mixture of each color toner becomes insufficient, resulting in poor color reproducibility. Not preferred.

In the method of obtaining toner particles using the suspension polymerization method, it is particularly preferable to add a polar resin at the same time from the viewpoint of allowing the polymerization reaction of the polymerization monomer to be carried out without inhibition. As the polar resin used in the present invention, a copolymer of styrene and (meth) acrylic acid, a maleic acid copolymer, a polyester resin, and an epoxy resin are preferably used. It is particularly preferable that the polar resin does not contain an unsaturated group capable of reacting with a monomer in the molecule.

As the polymerization initiator used in the present invention, for example, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile,
1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis-4-methoxy-2,4-
Azo-based polymerization initiators such as dimethylvaleronitrile and azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-
A peroxide-based polymerization initiator such as dichlorobenzoyl peroxide and lauroyl peroxide is used.

The weight average particle diameter of the toner can be measured by various methods such as Coulter Counter TA-II or Coulter Multisizer (manufactured by Coulter Co.). In the present invention, Coulter Counter Multisizer TA-II ( Interface (manufactured by Coulter Inc.) to output the number distribution and volume distribution
And PC9801 personal computer (NEC)
And the electrolyte is 1-grade sodium chloride.
% NaCl aqueous solution is prepared. For example, ISOTON
R-II (manufactured by Coulter Scientific Japan) can be used. As a measuring method, a surfactant, preferably an alkylbenzenesulfonate, is used as a dispersant in 100 to 150 ml of the electrolytic aqueous solution in an amount of 0.1 to 5 m.
and 2 to 20 mg of the measurement sample. The electrolytic solution in which the sample was suspended was subjected to dispersion treatment for about 1 to 3 minutes using an ultrasonic disperser, and the volume and the number of toner particles having a size of 2 μm or more were measured by using the 100 μm aperture as the aperture by the Coulter counter multisizer type. The distribution and number distribution were calculated. Then, a volume-based weight average particle diameter (D4: the median value of each channel is a representative value of the channel) obtained from the volume distribution according to the present invention was obtained.

[0091]

EXAMPLES The present invention will be described below in more detail with reference to Examples, which should not be construed as limiting the present invention. "Department"
Means "parts by weight".

Example 1 In 700 parts of ion-exchanged water,
The 0.1M-Na ₃ PO ₄ aqueous solution 450 parts was charged, 50 ° C.
TK homomixer (manufactured by Tokushu Kika Kogyo)
And stirred at 10,000 rpm. To this, 70 parts of a 1.0 M CaCl ₂ aqueous solution was added, and hydrochloric acid was further added thereto to obtain a pH 6.0 containing a calcium phosphate compound.
Was obtained.

On the other hand, (monomer) 170 parts of styrene 30 parts of n-butyl acrylate (colorant) I. Pigment Blue 15: 3 15 parts (Charge control agent) Salicylic acid metal compound / salicylic acid compound 2 parts / 0.1 part (Polar resin) Saturated polyester 20 parts (Acid value 10 mgKOH / g, Peak molecular weight: 15,000) (Release) Agent) behenyl stearate 30 parts (crosslinking agent) divinylbenzene 0.5 part The above formulation was heated to 60 ° C, and uniformly dissolved and dispersed at 9000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo). did. Into this, 5 parts of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition.

The polymerizable monomer composition was charged into the aqueous medium, and the mixture was stirred at 8000 rpm with a TK homomixer at 60 ° C. in an N ₂ atmosphere to granulate the polymerizable monomer composition. did.

Thereafter, while stirring with a paddle stirring blade, 5 hours later, the temperature was raised at a rate of 40 ° C./Hr. At 80 ° C. for 5 hours. After completion of the polymerization reaction, the remaining monomer was distilled off under reduced pressure. After cooling, hydrochloric acid was added to dissolve the calcium phosphate salt, followed by filtration, washing with water, and drying to give a number average particle size of 6.
2 μm colored toner particles were obtained.

For 100 parts of the toner particles, 0.7 part of a titanium oxide fine powder having a number average particle diameter of 30 nm, surface-treated with a silane coupling agent, and a number average particle diameter of 35 parts
After adding 0.7 parts of silica fine powder having a particle diameter of 0.1 nm and surface-treated with a coupling agent, the mixture is uniformly stirred using a Henschel mixer manufactured by Mitsui Mining Co., Ltd. Obtained.

Classifier 1: As shown in FIG. 2, seven polyurethane balls having a diameter of 6.5 mm are used as the elastic balls 16, and the openings B are used as the screens 11.
Was made of 46 μm polyethylene (B / a = 7.
42).

This toner is supplied to the toner cartridge No. 1 was charged. At this time, the filling rate was 0.41 g / ml.

FIG. 3 is an enlarged view of a spiral screw portion. In FIG. 3, D is the inner diameter of the screw casing, δ is the clearance between the outermost edge of the screw part and the inner wall of the screw casing, r is the number of rotations, and W is the pitch length of the screw part. Table 2 shows the set values.

[0100]

[Table 2]

The shape factor SF of the titanium oxide fine powder (1) existing on the toner particles of the above-mentioned suspension polymerization cyan toner 1
-1 was 115, and the similar silica fine powder (1) had a shape factor SF-1 of 180.

The number average particle diameter of the suspension polymerized cyan toner 1 measured by a Coulter counter was 6.2 μm, and the average circularity was 0.985 and the circularity was 0 in the circularity distribution measured by a flow type particle image analyzer. The number of toner particles less than 0.950 was 10% by number.

The two-component cyan developer (1) was prepared by mixing the above suspension polymerized cyan toner 1 and the following carrier I for development at a toner concentration of 8%.

(Production of carrier I for development) After mixing and dispersing a phenol / formaldehyde monomer (50:50) in an aqueous medium, 0.25 μm surface-treated with isopropoxytriisostearoyl titanate was used based on the weight of the monomer. 600 parts of magnetite particles, 0.6 μm
Was dispersed uniformly, and the monomer was polymerized while appropriately adding ammonia to obtain a magnetic particle-encapsulated spherical magnetic resin carrier core material (average particle diameter: 33 μm, saturation magnetization: 38 Am ² / kg).

The carrier core material includes:

[0106]

(Equation 3)

On the other hand, toluene 20 parts, butanol 20
Parts, 20 parts of water and ice 40 parts is taken up in a four-necked flask, with stirring CH ₃ SiCl ₃ 15 mol of (CH _{3) 2} Si
40 parts of a mixture with 10 mol of Cl ₂ and a catalyst were added, and the mixture was further stirred for 30 minutes, and then subjected to a condensation reaction at 60 ° C. for 1 hour. Thereafter, the siloxane is thoroughly washed with water, and toluene-
It was dissolved in a mixed solvent of methyl ethyl ketone and butanol to prepare a silicone varnish having a solid content of 10%.

The silicone varnish was prepared by adding 20 parts of ion-exchanged water to 100 parts of the siloxane solid component,
2.0 parts of a curing agent represented by the following formula, 1.0 part of an aminosilane coupling agent represented by the following formula (2), and 5.0 parts of a silane coupling agent represented by the following formula (3) are simultaneously added to the carrier coating solution. I was prepared.

[0109]

(Equation 4)

The carrier coating solution I was applied to 100 parts of the surface-modified carrier core material using a coating machine (a Spira coater manufactured by Okada Seiko Co., Ltd.) so that the resin coating amount was 0.5 part. Thus, a coated carrier I (developer carrier I) was obtained.

The carrier I for development had a low volume resistivity of 4 × 10 ¹³ Ω · cm and a coercive force of 55 Oersted according to the following measurement method.

Measurement of Volume Resistance The volume resistance was measured using the cell shown in FIG. That is, the cell A is filled with the sample 143, and the lower electrode 141 and the upper electrode 1 are contacted with the filled sample 143.
42, a DC voltage of 1000 V was applied between the electrodes, and the current flowing at that time was measured by an ammeter. Incidentally, reference numeral 144 denotes an insulator. The measurement conditions were as follows: the contact area S of the filled sample 143 with the cell was S = 2 cm ² ,
The thickness d is 3 mm, and the load on the upper electrode is 15 kg.

As a device for measuring magnetic properties , a BHU-60 type magnetization measurement device (manufactured by RIKEN) is used. About 1.0 g of a measurement sample is weighed, packed in a cell having an inner diameter of 7 mmφ and a height of 10 mm, and set in the above-mentioned apparatus. In the measurement, an applied magnetic field is gradually applied to change up to 1000 Oe. Next, the applied magnetic field is decreased, and finally a hysteresis curve of the sample is obtained on the recording paper. From this, the saturation magnetization, residual magnetization, and coercive force are obtained.

The two-component developer (1) is charged into the developing device 63a of the first image forming unit Pa of the image forming apparatus shown in FIG. 5, and the cylindrical cyan toner cartridge (59a) is placed in the toner hopper. 65a, the toner concentration of the two-component developer (1) in the developing device 63a is 7%
The toner density is controlled by using an inductance detection toner density detection means (not shown) so that the toner feeding member 66 can be maintained at about 9%.
While the suspension polymerization toner 1 was supplied to the developing device 63a via the line a, 30,000 sheets of cyan single color continuous copying were performed at 23 ° C./65% RH.

In the first image forming unit Pa of the above-mentioned image forming apparatus, the following photosensitive member No. is used as the photosensitive drum 61a. The following magnetic brush charger No. 1 was used as the primary charger 62a. 1 and the photosensitive drum 61
a The magnetic brush charger is rotated in the counter direction at a speed of 120% with respect to the movement direction, and a charging bias voltage in which a 1 kHz, 1.2 kVpp AC voltage is superimposed on a -700 V DC component is applied. Photoconductor drum 6
1a was primarily charged to -700V.

Further, the first image forming unit Pa is in contact with the surface of the photosensitive drum 61a between the transfer section and the charging section and between the charging section and the developing section. It does not have a cleaning unit for removing and collecting the transfer residual toner present thereon, and the developing device 63a removes the transfer residual toner present on the surface of the photosensitive drum 61a after the transfer process into the two-component developer during development. A configuration was adopted in which a simultaneous development and cleaning method of removing and collecting using a magnetic brush was performed. At the time of development in the developing device 63a, the development contrast is 250 V and the fog removal inversion contrast is −
The development was performed while the voltage was set to 150 V and a discontinuous AC voltage shown in FIG. 7 was applied to the developing sleeve.

(Photoconductor No. 1) Photoconductor No. 1 Reference numeral 1 denotes an OPC photoreceptor using an organic photoconductive material for negative charging.
The following five functional layers are provided on a 30 mm aluminum cylinder.

The first layer is a conductive layer having a thickness of about 20 μm and is provided for smoothing defects of the aluminum cylinder and for preventing the occurrence of moire due to reflection by laser exposure. is there.

The second layer is a positive charge injection preventing layer (undercoat layer), which serves to prevent positive charges injected from the aluminum substrate from canceling out negative charges charged on the surface of the photoreceptor. This is a medium resistance layer having a thickness of about 1 μm, the resistance of which is adjusted to about 10 ⁶ Ω · cm by −66-610-12-nylon and methoxymethylated nylon.

The third layer is a charge generation layer, which is a layer having a thickness of about 0.3 μm in which a disazo pigment is dispersed in a resin, and generates a positive and negative charge pair by receiving laser exposure.

The fourth layer is a charge transport layer, in which hydrazine is dispersed in a polycarbonate resin, and is a P-type semiconductor. Therefore, the negative charges charged on the photoreceptor surface cannot move through this layer, and only the positive charges generated in the charge generation layer can be transported to the photoreceptor surface.

[0122] The fifth layer is a charge injection layer, a particle size of about to SnO ₂ ultrafine particles in a photocurable acrylic resin, to increase further the charging member and the contact time of the photosensitive member, performing uniform charging It is a dispersion of 0.25 μm tetrafluoroethylene resin particles. Specifically, 160 parts by weight of oxygen-deficient, low-resistance SnO ₂ particles having a particle diameter of about 0.03 μm per 100 parts by weight of resin, 30 parts by weight of tetrafluoroethylene resin particles, and a dispersant 1.2 parts by weight are dispersed.

Thus, the photosensitive member No. The volume resistance value of the surface layer of No. 1 is 3 × 10 ⁵ Ω · cm in the case of the charge transport layer alone.
It has been reduced to 8 × 10 ¹¹ Ω · cm.

(Magnetic Brush Charger No. 1) MgO 5
Parts, 8 parts of MnO, 4 parts of SrO, and 83 parts of Fe ₂ O ₃ , each of which is atomized, granulated by adding and mixing water, and calcined at 1300 ° C. while adjusting the oxygen concentration to adjust the particle size.
A ferrite carrier core material having an average particle size of 28 μm (saturation magnetization: 63 Am ² / kg, coercive force: 55 Oersted) was obtained.

To the above carrier core material, 10 parts of isopropoxy triisostearoyl titanate was added in an amount of 99 parts of hexane /
What was mixed with 1 part of water was subjected to surface treatment so as to be 0.1 part, and further,

[0126]

(Equation 5)

The volume resistivity of the magnetic particles a measured by the same method as the volume resistivity of the developing carrier I was 4 × 10 ⁷
Ω · cm, and the weight loss on heating was 0.15 part.

The magnetic brush charger No. Reference numeral 1 denotes a magnetic brush formed by magnetically constraining the magnetic particles a on the surface of a conductive non-magnetic sleeve containing a magnet roll therein. When charging, the magnet roll is fixed and the conductive non-magnetic sleeve is fixed. Rotate.

In the above 30,000-sheet continuous copy test, solid uniformity of the initial image, fog after 30,000-sheet durability, durability due to the difference in image density between the initial image and the image after 30,000-sheet durability, initial and 3 The transferability after the endurance of 10,000 sheets was evaluated. Furthermore, under low humidity (10 ° C / 10% RH) and high humidity (40 ° C /
80% RH) at 23 ° C for 1 month
Images were extracted under / 65% RH (NN), and the storage stability was evaluated.

As shown in Table 3, as shown in Table 3, the image density was stable, there was no problem in fog and transferability, and very good results were obtained.

An original manuscript provided with five circles each having a diameter of 20 mm and having an image density of 1.5 as measured by a solid uniform reflection densitometer RD918 (manufactured by Macbeth) is copied, and the image density of the image portion is determined by the reflection density. The difference between the maximum value and the minimum value at that time was measured with a total RD918.

An original manuscript provided with a circle having a diameter of 20 mm and having an image density of 1.5 as measured by an image density reflection densitometer RD918 (manufactured by Macbeth) is copied, and the image density of the image portion is measured by the reflection densitometer RD.
918.

Fog amount The average value (Dr) of the reflection density obtained by measuring 10 points of the paper before image formation is subtracted from the worst value (Ds) of the reflection density obtained by measuring 10 points of the non-image area (white background) after image formation. Value (Dr-D
Let s) be the fog amount.

The reflection density was measured by a reflection densitometer (TOK).
REFLE manufactured by YO DENSHOKU CO, LTD
CTOMETER MODEL TC-6DS) was used.

When the fog amount is 1.2% or less, a good image having substantially no fog is obtained, and when the fog amount exceeds 1.5%, the image is fuzzy and unclear.

Solid white spots The number of white spots of about 100 μm or more is calculated in the above-mentioned five image portions of 20 mm. If the number is 5 or less, a good image having substantially no problem occurs, but if the number exceeds 10, an image with deteriorated quality is obtained.

<Example 2> In Example 1, the screen B of the classifier was 74 μm (B / a = 1).
1.9), except that the polyethylene cartridge is used. No. 2 was prepared and image-forming was carried out. As a result, although the quality of solid white spots was slightly lowered, it was at a level having no practical problem at all. At this time, the filling rate was 0.42 g / ml. This is presumed to be due to the fact that B / a became large and coarse particle removal was slightly insufficient.

<Example 3> In Example 1, the size of the screen of the classification device was 35 μm (B / a = 5.6).
5), except that the polyethylene cartridge is used. No. 3 was prepared and an image was formed. When left at 40 ° C./80% RH, fog was slightly deteriorated, but at a practically acceptable level. At this time, the filling rate was 0.40 g / ml. This is presumed to be due to the fact that the external additive tended to be loose from the toner particles due to the small aperture of the screen, and the storage stability was slightly reduced.

Comparative Example 1 Polyester resin obtained by condensing propoxylated bisphenol with fumaric acid and trimellitic acid 100 parts Phthalocyanine pigment 4 parts Aluminum compound of di-tert-butylsalicylic acid 4 parts Low molecular weight polypropylene 4 copies

The above raw materials were premixed by a Henschel mixer, melt-kneaded by a twin-screw extruder, and kneaded.
After cooling, the mixture was roughly pulverized to about 1 to 2 mm using a hammer mill, and then finely pulverized by a pulverizer using an air jet method. Further, except that toner particles obtained by classifying the obtained finely pulverized product were used, toner cartridge No. When preparing No. 4, the filling rate was as small as 0.28 g / ml,
Attempts to fill further overflowed the toner container, greatly reducing productivity. This is presumed to be due to the fact that the toner was hard to clog because of the irregular shape of the toner. The number average particle diameter of this toner is 6.1 μm,
The average circularity was 0.932, and the number of toner particles having a circularity of less than 0.950 was 43% by number.

<Comparative Example 2> In the same manner as in Comparative Example 1, except that the toner particles were subjected to spheroidizing treatment in a hot water bath, the toner cartridge No. 5 was made and imaged.
Evaluation was stopped because fog became worse at 10,000 sheets. This is presumed to be due to the fact that the toner was too spherical, so that the external additive was detached, and the charge of the toner became non-uniform.
The number average particle diameter a of this toner is 5.9 μm, and B / a =
8.00, average circularity 0.996, circularity 0.950
The toner particles were less than 1.3% by number. The filling factor was 0.43 g / ml.

<Comparative Example 3> In Example 1, the size of the screen of the classifier was 104 μm (B / a = 1).
6.8), except that the polyethylene cartridge is used. No. 7 was produced and image formation was performed, and the evaluation was stopped because the quality of solid white spots deteriorated from the beginning. This is presumed to be because coarse particles were insufficiently removed due to the large B / a. At this time, the filling rate was 0.41 g / ml, and the number average particle diameter, average circularity, and the like were the same as those in Example 1.

<Comparative Example 4> In Example 1, the size of the screen of the classification device was 28 μm (B / a = 4.3).
1) except that the toner cartridge No. 1) is used. When trying to produce No. 8, the screen was severely clogged, the productivity was remarkably reduced, and it was difficult to evaluate the filling rate. Further, when image formation was performed with this toner, the evaluation was stopped because the fog quality deteriorated from the beginning. This is presumably because the external additive was detached from the toner particles when passing through the screen. At this time, the number average particle diameter, the average circularity, and the like were the same as in Example 1.

<Example 4> A filling rate of 0.45 g / ml was obtained in the same manner as in Example 1 except that the inorganic fine powder (B) was changed to a silica fine powder treated with a coupling agent having a number average particle diameter of 28 nm. Toner cartridge No. No. 9 was prepared and imaged. Good results were obtained at 30,000 sheets, although fog and solid uniformity were slightly deteriorated. This is because the number average particle diameter of the toner at this time, B /
a, average circularity, etc. were the same as in Example 1, but SF-1 of the silica fine particles was slightly smaller at 141, and the titanium oxide fine particles of the other external additive were embedded in the toner particles due to durability, so that the toner particles tended to be slightly disturbed. It is presumed that it was.

<Example 5> In Example 1, the inorganic fine powder (A) having an average particle size of 25 with SF-1 of 138 was used.
In the same manner, except that γ-type alumina treated with a coupling agent having a filling rate of 0.38 g / ml was used. No. 10 was produced and image formation was performed, but good results were obtained although the solid uniformity was slightly lowered at 30,000 sheets. In this case, the number average particle diameter, B / a, average circularity and the like of the toner at this time were the same as those in Example 1, but the SF-1 of the alumina fine particles was slightly larger, and the fluidity of the toner was slightly imparted. It is presumed that it has deteriorated.

<Example 6> As the inorganic fine powder (B), S
A toner cartridge N having a filling rate of 0.42 g / ml in the same manner except that a rutile type titanium oxide treated with a coupling agent having an average particle diameter of 40 nm and F-1 of 158 was used.
o. No. 11 was produced and imaged, and the result was 40 ° C./8
Good results were obtained although fog was slightly deteriorated when left at 0% RH. This is because the number average particle diameter, B / a, average circularity and the like of the toner at this time were the same as those in Example 1, but the material of the inorganic fine powder (B) was titanium oxide. This is presumed to be due to the fact that the adhesiveness to the product was slightly weak, and it became slightly free when stored under high humidity.

<Example 7> In the same manner as in Example 1, except that the titanium oxide fine powder was increased to 1.5 parts by weight, the toner cartridge No. having a filling rate of 0.52 g / ml was used. No. 6 was produced, and image formation was carried out. At 10,000 sheets, solid uniformity was deteriorated, but was at a practically acceptable level. This is presumably because the toner filling rate was high and uniform discharge from the toner cartridge was not achieved, resulting in uneven toner concentration in the developing device. The number average particle diameter, B / a, average circularity, and the like of this toner were the same as in Example 1.

<Eighth Embodiment> In the first embodiment, a gyro shifter shown in FIG. 4 was used as a classifier, and an ultrasonic oscillator (not shown) was attached to a styrene screen 31 having an aperture of 46 μm to prevent clogging. The toner cartridge No. is manufactured in the same manner except that the toner is produced from 32 and the coarse particles are discharged from 33 while preventing. 12, and good results were obtained.

Example 9 (Production Example of Magenta Toner Cartridge) 170 parts of styrene 30 parts of 2-ethylhexyl acrylate 15 parts of quinacridone pigment 3 parts of Cr di-tert-butylsalicylate compound 3 parts of saturated polyester 10 parts (acid Value: 10 mgKOH / g, peak molecular weight: 9,100 ・ Ester wax: 40 parts (Mw: 450, Mn: 400, Mw / Mn: 1.25, melting point: 70 ° C., viscosity: 6.5 mPa · s, Vickers hardness: 1. 1, SP value: 8.6)

A polymerizable monomer composition was prepared in the same manner as in Example 1 and charged into the aqueous medium prepared in Example 1, and then subjected to the same steps as described above to obtain a magenta toner cartridge No. 13 was obtained. The number average particle diameter of this toner is 6.1 μm, B / a = 7.54, and the average circularity is 0.98.
6. 9% of the toner particles had a circularity of less than 0.950, and the toner filling rate was 0.42 g / ml.

(Production Example of Black Toner Cartridge) 170 parts of styrene 30 parts of 2-ethylhexyl acrylate 15 parts of carbon black 3 parts of di-tert-butylsalicylic acid Cr compound 3 parts of saturated polyester 10 parts (acid value 10 mg KOH / g, 40 parts of ester wax (Mw: 500, Mn: 400, Mw / Mn: 1.25, melting point 70 ° C., viscosity: 6.5 mPa · s, Vickers hardness: 1.1, SP value: 8.6)

A polymerizable monomer composition was prepared in the same manner as in Example 1 and charged into the aqueous medium prepared in Example 1, and the same procedure was followed to obtain the black toner cartridge No. 14 was obtained. The number average particle diameter of this toner is 6.0 μm, B / a = 7.67, and the average circularity is 0.98.
6. The toner particles had a circularity of less than 0.950, 10%, and the toner filling rate was 0.41 g / ml.

(Production Example of Yellow Toner Cartridge) 170 parts of styrene 30 parts of n-butyl acrylate I. Pigment Yellow 93 15 parts ・ Di-tert-butylsalicylic acid Cr compound 3 parts ・ Saturated polyester 10 parts (acid value 10 mgKOH / g, peak molecular weight 9,100) ・ Diester wax 40 parts (Mw: 480, Mn: 410, Mw / Mn: 1.17, melting point: 73 ° C, viscosity: 10.5 mPa · s, Vickers hardness: 1.0, SP value: 9.1)

A polymerizable monomer composition was prepared in the same manner as in Example 1 above, and then charged into the aqueous medium prepared in Example 1, and the mixture was treated at 60 ° C. under a N ₂ atmosphere under a CLEA mixer. And stirred at 12,000 rpm for 10 minutes.
The polymerizable monomer composition was granulated. Thereafter, the temperature was raised at 80 ° C. while stirring the aqueous medium with a paddle stirring blade, and a polymerization reaction was performed for 10 hours.

After completion of the polymerization reaction, the mixture was cooled, hydrochloric acid was added to dissolve calcium phosphate, and then filtered, washed with water and dried. 15 was obtained. The number average particle size of this toner is 6.3 μm, B / a = 7.3.
0, the average circularity was 0.984, the toner particles having a circularity of less than 0.950 were 13%, and the toner filling rate was 0.41 g / ml.

Using the above-mentioned yellow toner, magenta toner and black toner, and using the same carrier as in Example 1, a yellow developer, a magenta developer and a black developer were produced.

The image forming apparatus shown in FIG.
A yellow developer is used for 63a and a yellow toner cartridge is used for 59a. Hereinafter, a magenta developer / magenta toner cartridge is used for the Pb unit, and the unit Pc is used for the Pb unit.
Using the cyan developer / cyan toner cartridge used in Example 1 and the black developer / black toner cartridge in the unit Pd, a full-color image durability evaluation of 10,000 sheets was performed in the same manner as in Example 1. As in Example 1, good results were obtained.

[0158]

[Table 3]

[0159]

According to the present invention, the toner can be easily filled into the toner cartridge without releasing and re-aggregating the external additive of the toner, and the image quality due to the durability can be improved.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of an apparatus used in the present invention.

FIG. 2 is a schematic diagram of a classification device used in the present invention.

FIG. 3 shows an enlarged view of a spiral screw part of the filling device.

FIG. 4 is a schematic view of another embodiment of the classification device used in the present invention.

FIG. 5 is a schematic view showing an example of a suitable image forming apparatus capable of performing the image forming method of the present invention.

FIG. 6 is a diagram showing an alternating electric field used in the first embodiment.

FIG. 7 is an explanatory diagram of an apparatus used for measuring a volume resistance value.

[Explanation of symbols]

 59a Toner cartridge 60a Transfer bias applying means (may be grounded) 61a Photoconductor drum 62a Primary charger 63a Developing device 64a Transfer blade 65a Toner hopper 66a Replenishment roller 67a Exposure device 68 Transfer material carrier 69 Separation charger 70 Fixing Device 71 Fixing roller 72 Pressure roller 73 Web 75, 76 Heating means 78 Temperature detecting means 79 Transfer belt cleaning device 80 Driving roller 81 Belt driven roller 82 Belt neutralizer 83 Registration roller 84 Feed roller 101 Hopper 103 Spiral screw 104 Discharge Outlet 112 stirring blade

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03G 15/08 112 G03G 9/08 374 507 375 381 384 15/08 507B 507L (72) Inventor Yasuyuki Katsuta Tokyo 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Yuji Moriki 3-30-2, Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Yuji Mikuri Shimomaruko, Ota-ku, Tokyo 3-30-2 Canon Inc. F term (reference) 2H005 AA08 AA15 AA21 AB03 AB06 AB09 CB07 CB13 EA05 EA07 2H030 AD01 AD03 BB02 BB23 BB41 2H077 AA01 AA37 AC04 AC16 AD02 AD06 AD31 BA03 CA19 EA24 GA13

Claims (16)

[Claims] 1. A method for producing a toner having a number average particle diameter a of 2 to 8 μm by a Coulter method and having a toner particle and an external additive passed through a spiral screw. In the circularity distribution of the particles measured by the particle image analyzer, 0.950 to 0.99
It contains 2 to 40% by number of particles having an average circularity of 5 and a circularity of less than 0.950. After the external additive is dispersed on the toner particles, the aperture (B)
Is passed through a screen of 5 ≦ B / a ≦ 15 to separate and remove coarse particles to produce a toner. 2. The toner according to claim 1, wherein the external additive has an average major axis of 10 or more present as primary particles or secondary particles on the toner particles.
From 400 to 400 nm and the shape factor SF-1 from 100 to 13
0, and at least a non-spherical inorganic fine powder (B) having a shape factor SF-1 larger than 150, which is generated by coalescing a plurality of particles. The method for producing a toner according to claim 1. 3. The inorganic fine powder (A) has fine particles selected from the group consisting of aluminum oxide fine particles, titanium oxide fine particles, and silica-treated fine particles thereof. Production method of toner. 4. The method according to claim 2, wherein the non-spherical inorganic fine powder (B) has silica fine particles. 5. The toner particles are produced by a polymerization method in which a polymerizable monomer composition containing at least a polymerizable monomer and a colorant is subjected to suspension polymerization in an aqueous medium in the presence of a polymerization initiator. 2. The method according to claim 1, wherein
5. The method for producing a toner according to any one of items 1 to 4. 6. An inner diameter D of the screw casing is 12 to
130 mm, the clearance δ between the outermost edge of the screw portion and the inner wall of the screw casing is 0.05 to
3.0 mm, and the screw rotation speed r is 50 to 30.
The method according to any one of claims 1 to 5, wherein the rotation speed is 00 rpm, and the pitch length W satisfies the following expression. 0.1 × H <W <3.0 × H (where H is the outer diameter of the spiral screw, H = D−2δ) 7. A method of filling a toner container, comprising a toner having toner particles and an external additive and having a number average particle diameter a by a Coulter method of 2 to 8 μm into a toner container through a spiral screw. The toner has a circularity distribution of particles measured by a flow type particle image analyzer of 0.950 to 0.99.
Containing 2 to 40% by number of particles having an average circularity of 5 and a circularity of less than 0.950. After the external additive is dispersed on the toner particles, the aperture (B)
Characterized in that the toner is passed through a screen satisfying 5 ≦ B / a ≦ 15 to separate and remove coarse particles, and the toner is filled in the toner container so as to have a filling rate of 0.3 to 0.5 g / ml. How to fill the toner. 8. The toner according to claim 1, wherein the external additive has an average major axis of 10 or more present as primary particles or secondary particles on the toner particles.
From 400 to 400 nm and the shape factor SF-1 from 100 to 13
0, and at least a non-spherical inorganic fine powder (B) having a shape factor SF-1 larger than 150, which is generated by coalescing a plurality of particles. The method for filling a toner container with a toner according to claim 7. 9. The method according to claim 8, wherein the inorganic fine powder (A) has fine particles selected from the group consisting of aluminum oxide fine particles, titanium oxide fine particles, and silica-treated fine particles thereof. Of filling the toner into the toner container. 10. The non-spherical inorganic fine powder (B) has silica fine particles.
5. The method for filling a toner container with a toner according to item 1. 11. The toner particles are produced by a polymerization method in which a polymerizable monomer composition containing at least a polymerizable monomer and a colorant is subjected to suspension polymerization in an aqueous medium in the presence of a polymerization initiator. 11. The method according to claim 7, wherein the toner container is filled with a toner. 12. The screw casing having an inner diameter D of 12
And the clearance δ between the outermost edge of the screw portion and the inner wall of the screw casing is 0.05 to
3.0 mm, and the screw rotation speed r is 50 to 30.
The method for filling a toner container with toner according to any one of claims 7 to 11, wherein the rotation speed is 00 rpm, and the pitch length W satisfies the following expression. 0.1 × H <W <3.0 × H (where H is the outer diameter of the spiral screw, H = D−2δ) 13. A toner cartridge detachably mounted in an image forming apparatus, comprising: a toner having toner particles and an external additive, having a number average particle diameter a by a Coulter method of 2 to 8 μm. A toner cartridge filled through a spiral screw, wherein the toner has a circularity distribution of particles measured by a flow type particle image analyzer of 0.950 to 0.99.
Containing 2 to 40% by number of particles having an average circularity of 5 and a circularity of less than 0.950. After the external additive is dispersed on the toner particles, the aperture (B)
A toner cartridge filled with toner so as to have a filling rate of 0.3 to 0.5 g / ml by separating coarse particles by passing through a screen of 5 ≦ B / a ≦ 15. 14. An image forming apparatus comprising: (i) a charging step of charging a latent image carrier for carrying an electrostatic latent image; and (ii) forming an electrostatic latent image on the charged latent image carrier. (Iii) forming an electrostatic latent image on the latent image carrier with cyan toner;
A developing step of forming a color toner image by developing with a color toner selected from the group consisting of a magenta toner, a yellow toner and a black toner; and (iv) transferring the color toner image formed on the latent image carrier to a transfer material. The above steps (i) to (iv) are repeated twice or more successively using a color toner of another color to form a multicolor color toner image on the transfer material. 14. The toner cartridge according to claim 13, wherein the toner cartridge is a multi-color or full-color image forming apparatus. 15. The transfer section, the charging section in the charging step, and the developing section in the developing step in the transfer step, the transfer section, the charging section, and the developing section in the moving direction of the latent image carrier. The developing unit is arranged in this order, and between the transfer unit and the charging unit and between the charging unit and the developing unit, the latent image carrier is brought into contact with the surface of the latent image carrier. There is no cleaning member for recovering the toner remaining on the body surface. In the cleaning step, during the developing step, the developing device holding the toner is held by the latent image carrier. A developing simultaneous cleaning method is used in which an electrostatic latent image is developed with the toner and the developing device collects toner remaining on the surface of the latent image carrier to clean the surface of the latent image carrier. The toner according to claim 14, wherein: Cartridges. 16. The toner cartridge according to claim 13, wherein said image forming apparatus has a plurality of charging steps, latent image forming steps, developing steps, and transferring steps.