JP2002169324A - Developer for electrostatic charge image and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide developer for an electrostatic charge image by which a high-quality image free from image soiling is stably formed over a long term, and an image forming method using the developer. SOLUTION: The developer for an electrostatic charge image is constituted of toner which is obtained by salting out/fusing resin particles incorporating a releasing agent, which consists of specified crystalline ester compound, in binding resin and colorant particles, and carrier constituted by forming a coating resin layer of specified silicone resin on core particles consisting of magnetic substance. This image forming method includes a stage where a toner image is fixed by making recording material on which the toner image developed with the developer for an electrostatic charge image is formed pass through space between a heating roller and a pressure roller.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrostatic image developer used for, for example, a copying machine, a printer, and the like, and an image forming method using the same.

[0002]

2. Description of the Related Art At present, a two-component developer composed of a carrier and a toner is widely used as an electrostatic image developer used in, for example, electrophotography. As a carrier constituting such a two-component developer, while being able to exhibit suitable triboelectrification properties, it is possible to effectively prevent the generation of so-called spent toner, for example,
A resin-coated carrier in which a resin coating layer is formed on core particles made of a magnetic material such as iron, magnetite, or ferrite is preferably used. As such a resin, for example, a styrene acrylic resin, a fluorine resin, a silicone resin and the like are known.

On the other hand, as toner, there is a demand for a reduction in particle size in order to improve the quality of a toner image. Conventionally, pulverized toner produced by a pulverization method has been widely used. In comparison, the energy required to reduce the particle size of the toner is small, and there is no problem such as generation of fine powder due to pulverization. Therefore, a so-called polymerized toner manufactured by a polymerization method is considered to be useful. ing. Here, as the polymerization method toner, for example, a suspension polymerization toner and an associative toner are known, and the associative toner is preferable because its shape can be easily controlled.

However, the associative particles (colored particles) obtained by associating the resin particles with the colorant particles are irregular and have a smooth surface. There is a problem that the chargeability of the toner becomes non-uniform and, as a result, a stable image cannot be formed over a long period of time.

On the other hand, as a method of fixing a toner image formed on a recording material such as transfer paper, a method of fixing a toner image by forming a recording material on which the toner image is formed is passed between a heating roller and a pressure roller. Roll fixing systems are widely used.

However, the heat roll fixing method has a drawback that an image is easily stained due to an offset phenomenon in which a toner in a molten state adheres to a heating roller. For this reason, it has been widely practiced to add a release agent to the toner to impart releasability to the toner itself and improve fixability. When the release agent is added, it is necessary to add the release agent in a large amount or in a finely dispersed state since the release agent is hardly unevenly distributed on the surface of the toner particles. As a method of adding a release agent to a toner obtained by a polymerization method, a method of associating resin particles with release agent particles is known.

However, according to this method, the release agent is released from the associated particles of the resin particles and the release agent particles, and the release agent is fused to a triboelectric charging member such as a carrier to lower the chargeability. In addition, a sufficient amount of release agent cannot be introduced into the obtained associated particles, and the content of the release agent varies between the associated particles to be formed. There is a problem that the releasability cannot be exhibited. In particular, crystalline ester compounds,
When a so-called ester wax is used as a release agent, such a problem is conspicuous because the ester wax itself has a low molecular structure and less entanglement of molecular chains as compared with a so-called polyolefin wax. Appears in

[0008] Further, the image forming method using the toner has problems such as a demand for high image quality of the initial image and prevention of deterioration of image quality and occurrence of image defects due to repeated use. For example, a decrease in gradation, a decrease in fine line reproducibility,
It is necessary to solve problems such as image density change, density unevenness, fog, and the like. The major causes of these problems include difficulty in controlling the toner charge amount and instability. Since the toner charge uses frictional charging, it is extremely difficult to control and stabilize the toner charge. To address these problems, numerous proposals have been made with a binder resin for a toner, a charge control agent, an external additive, other additives, and the like, and the list is complete. However, with the improvement of the performance and reliability of each image forming process using toner, higher image quality and higher durability of the developer have been pursued.

In recent years, the electrophotographic system has been used in various fields. For example, it is used not only in monochrome copying machines but also in fields such as printers that are output terminals of computers, color copying machines, color printers, and the like. As their use advances, the demands on image quality are increasing. In particular, in a multicolor image forming method in which an image is formed by superposing a plurality of toner images using color toners, a slight change in developability (amount of developed toner) due to a minute change in chargeability or the like, and a change in transferability of halftone, The change in the hue of the secondary color due to the superposition is large, and therefore, the requirements for stability such as chargeability are extremely severe.

[0010]

DISCLOSURE OF THE INVENTION The present invention has been made based on the above circumstances, and its object is to provide:
An object of the present invention is to provide an electrostatic image developer capable of stably forming a high-quality image free of image stains over a long period of time. Another object of the present invention is to provide an image forming method capable of stably forming a high-quality image free from image contamination for a long period of time.

[0011]

The electrostatic image developer of the present invention comprises a toner containing at least a resin, a release agent and a colorant, and a carrier. A resin obtained by salting out / fusing resin particles containing a release agent and colorant particles in a release resin, wherein the release agent is a crystalline ester represented by the following general formula (I): And a carrier coated on a core particle made of a magnetic material with a silicone resin having a structural unit represented by the following general formula (II) and a structural unit represented by the following general formula (III) It is characterized by being formed with a resin layer.

[0012]

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[In the formula, R ¹ and R ² each represent a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, and n is an integer of 1 to 4. Also, R ¹ and R
² may be the same or different from each other. ]

[0014]

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Wherein R ^{3 to} R ⁶ are each a methyl group,
It represents a substituent selected from an ethyl group, a phenyl group, a vinyl group, and a hydroxyl group. R ^{3 to} R ⁶ may be the same or different from each other. ]

The electrostatic image developer of the present invention is an electrostatic image developer comprising at least a toner containing a resin, a release agent and a colorant, and the above-mentioned carrier. A resin obtained by salting out / fusing resin particles containing a release agent and colorant particles, wherein the release agent comprises a crystalline ester compound represented by the general formula (I). And the coefficient of variation of the shape factor is 1
The toner particles are characterized by being 6% or less and having a number variation coefficient of 27% or less in the number particle size distribution.

The electrostatic image developer of the present invention is an electrostatic image developer comprising at least a toner containing a resin, a release agent and a colorant, and the above-mentioned carrier. A resin obtained by salting out / fusing resin particles containing a release agent and colorant particles, wherein the release agent comprises a crystalline ester compound represented by the general formula (I). And the ratio of toner particles having no corners is 50% by number or more, and the number of particles in the number particle size distribution is 27% or less.

The electrostatic image developer of the present invention is an electrostatic image developer comprising at least a toner containing a resin, a release agent and a colorant, and the above-mentioned carrier. A resin obtained by salting out / fusing resin particles containing a release agent and colorant particles, wherein the release agent comprises a crystalline ester compound represented by the general formula (I). And the shape factor is 1.2 to 1.
The ratio of the toner particles in the range of 6 is 65% by number or more, and the variation of the shape coefficient is 16% or less.

According to the image forming method of the present invention, a recording material on which a toner image developed by an electrostatic image developer comprising at least a toner containing a resin, a release agent and a colorant and a carrier is formed. In an image forming method including a step of fixing by passing between a heating roller and a pressure roller, the toner salt-outs / fuses resin particles containing a release agent and colorant particles in a binder resin. Wherein the release agent comprises a crystalline ester compound represented by the following general formula (I), and the carrier comprises a core particle made of a magnetic material and a carrier represented by the following general formula (II) ) And a coating resin layer formed of a silicone resin having the structural unit represented by the following general formula (III).

[0020]

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[Wherein R ¹ and R ² each represent a hydrocarbon group which may have a substituent and has 1 to 40 carbon atoms, and n is an integer of 1 to 4. Also, R ¹ and R
² may be the same or different from each other. ]

[0022]

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Wherein R ^{3 to} R ⁶ are each a methyl group,
It represents a substituent selected from an ethyl group, a phenyl group, a vinyl group, and a hydroxyl group. R ^{3 to} R ⁶ may be the same or different from each other. ]

The image forming method of the present invention is directed to a recording material on which a toner image developed by an electrostatic image developer comprising at least a toner containing a resin, a release agent and a colorant, and the above-mentioned carrier is formed. And fixing the toner by passing between a heating roller and a pressure roller, the toner is formed by salting out resin particles containing a release agent and colorant particles in a binder resin. Wherein the release agent is a crystalline ester compound represented by the general formula (I), and the coefficient of variation of the shape factor is 16% or less; The toner is characterized by comprising toner particles having a number variation coefficient of 27% or less in the number particle size distribution.

According to the image forming method of the present invention, there is provided a recording material on which a toner image developed by an electrostatic image developer comprising at least a toner containing a resin, a release agent and a colorant, and the above-mentioned carrier is formed. And fixing the toner by passing between a heating roller and a pressure roller, the toner is formed by salting out resin particles containing a release agent and colorant particles in a binder resin. Wherein the release agent is a crystalline ester compound represented by the above general formula (I), and the ratio of the toner particles having no corners is 50% by number or more. , Wherein the toner particles have a number variation coefficient of 27% or less in the number particle size distribution.

According to the image forming method of the present invention, there is provided a recording material on which a toner image developed by an electrostatic image developer comprising a toner containing at least a resin, a release agent and a colorant, and the above-mentioned carrier is formed. And fixing the toner by passing between a heating roller and a pressure roller, the toner is formed by salting out resin particles containing a release agent and colorant particles in a binder resin. The release agent is obtained by fusing, wherein the release agent comprises the crystalline ester compound represented by the general formula (I), and has a shape factor in a range of 1.2 to 1.6. Wherein the ratio of the toner particles is 65% by number or more, and the variation coefficient of the shape coefficient is 16% or less.

[0027]

According to the developer of the present invention, it is composed of an associative toner obtained by salting out / fusing resin particles containing a release agent and colorant particles, and a specific silicone resin-coated carrier. This suppresses the release agent from migrating to the carrier and adhering to the carrier. As a result, stable chargeability is obtained, and a high-quality image free from image contamination is formed.

According to the silicone resin-coated carrier, since the surface energy of the silicone resin constituting the resin coating layer is small, deterioration of the carrier can be suppressed more effectively than in the case of the conductive carrier, and the chargeability can be stabilized. Although it is not possible to obtain a sufficiently high quality image simply by combining a normal association type toner and a silicone resin-coated carrier, according to the present invention, the separation in the binder resin is not possible. The above object is attained by using a specific associative toner obtained by salting out / fusing resin particles containing a molding agent together with colorant particles in an aqueous medium and combining this with a silicone resin-coated carrier. be able to.

That is, according to this specific associative toner, since the release agent is present in the toner particles (associative particles) in a fine domain structure, the adhesion of the release agent (ester wax) itself And the coating resin of the carrier is a specific silicone resin, so that the release agent can be prevented from adhering to the carrier, and the chargeability can be further stabilized. In addition, since the dispersion of the release agent (dispersion area / dispersion amount) and the surface state among the toner particles can be reduced, sufficient releasability is ensured, and a high-quality image free from image contamination can be obtained. Obtainable.

Further, by using toner composed of toner particles having a shape coefficient variation coefficient of 16% or less and a number variation coefficient in the number particle size distribution of 27% or less, the chargeability of the toner is stabilized. And a high-quality image can be formed over a long period of time.

The ratio of the toner particles having no corners is set to 50% by number or more, and the number variation coefficient in the number particle size distribution is set to 2%.
By using a toner composed of toner particles controlled to 7% or less, the chargeability of the toner can be stabilized, and a high-quality image can be formed for a long period of time.

Further, a toner [C] having a percentage of toner particles having a shape coefficient in the range of 1.2 to 1.6 of 65% by number or more and a variation coefficient of the shape coefficient of 16% or less is used. Accordingly, the chargeability of the toner can be stabilized, and a high-quality image can be formed for a long period of time.

In a multicolor image forming method in which an image is formed by superimposing a plurality of toner images using color toners, stable chargeability can be obtained between toner particles of each color, so that transfer characteristics are stable and secondary The change in color hue is reduced, and a high-quality color image can be formed.

[0034]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The developer of the present invention is a two-component developer composed of a toner and a carrier containing at least a resin, a release agent and a colorant. The carrier is formed by forming a coating resin layer made of a silicone resin on core particles made of a magnetic material.

Examples of the magnetic material constituting the core particles of the carrier include ferrite represented by the following general formula (IV).

[0036]

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[Wherein, M represents a light metal selected from Ca, Li, and Mg, x and y are each 2 or 1, and a + b = 1. ]

In the above general formula (IV), x and y are moles, and it is preferable that x <y is satisfied from the viewpoint of magnetic properties. x is from 15.0 to 40.
0 mol%, preferably 20.0 to 30.0 mol%
It is. By satisfying this range, a predetermined magnetic property can be surely imparted to the carrier, and an appropriate polishing effect is exerted on the photoreceptor, so that a high-quality image can be reliably formed. it can.

If necessary, the core particles may contain, for example, Mn.
Heavy metals such as can be added. In this case,
The proportion of the heavy metal is preferably less than 10.0 mol%. When this ratio is 10.0 mol% or more, the metal tends to be affected by the inclusion of other metals, and for example, the magnetic properties of the carrier may be deteriorated.

On the other hand, the silicone resin constituting the coating resin layer has a structural unit represented by the above general formula (II) and a structural unit represented by the above general formula (III), and is a tough film. Since a structure is formed, those having a crosslinked structure are preferable.

In the formula, R ^{3 to} R ⁶ each represent a substituent selected from a methyl group, an ethyl group, a phenyl group, a vinyl group and a hydroxyl group. R ^{3 to} R ⁶ may be the same or different from each other. Particularly, in the combination of R ³ and R ^4, a combination of a hydroxyl group and a methyl group and a combination of a methyl group and a methyl group are preferable from the viewpoint of adhesiveness. The resin having this configuration is preferable in that a crosslinked film can be formed by using a curing agent described later. Furthermore, modified types such as alkyl-modified, phenol-modified and urethane-modified ones can also be used. The ratio of the structural unit represented by the general formula (II) to the structural unit represented by the general formula (III) is preferably (II) :( III) = 1: 99 to 70:30, more preferably (II) ) :( III) = 5: 95-5
0:50.

It is preferable that a silane coupling agent is added to the silicone resin constituting the coating resin layer because the charge amount and the like can be adjusted. Here, the addition amount of the silane coupling agent is preferably 5 to 50 parts by mass, more preferably 7 to 45 parts by mass, based on 100 parts by mass of the silicone resin.
If the amount exceeds 50 parts by mass, the coating resin layer to be formed cannot have sufficient hardness, so that the desired durability cannot be obtained and it is difficult to form a high-quality image for a long period of time. Becomes On the other hand, when the addition amount is less than 5 parts by mass, a sufficient charge-imparting ability to toner particles may not be obtained. As a silane coupling agent,
It is preferably an alkoxysilane having an amino group or an amine at the terminal, and examples thereof include those having structures represented by the following formulas (1) to (14).

[0043]

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Among the above silane coupling agents, alkoxysilanes having an amine at the terminal such as those in the formulas (1), (2), (3), (5) and (6) are preferred. Can be. It is presumed that the reason is that the active hydrogen of the amine present at the terminal makes it easy to be taken into the resin and the chargeability can be stabilized. Further, by using a compound having an amine at the terminal, the number of crosslinking points can be increased, and a more dense crosslinked structure can be formed.

It is preferable to use a curing agent to form a cross-linked structure in the silicone resin. As the curing agent, an oxime-type curing agent represented by the following general formula (V) is suitably used.

[0046]

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[Wherein, R ⁷ represents a substituent selected from the group consisting of a methyl group, an ethyl group, a propyl group, a phenyl group and derivatives thereof, and R ⁸ and R ⁹ represent
Each represents a substituent selected from the group consisting of a methyl group, an ethyl group, a propyl group, and derivatives thereof.
R ⁸ and R ⁹ may be the same or different from each other. ]

Specific examples of the oxime type curing agent include compounds represented by the following formulas (15) to (19).

[0049]

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Here, the addition amount of the curing agent is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, per 100 parts by mass of the resin. When the amount of the curing agent added is within this range, a dense crosslinked structure can be formed, and a coating resin layer having excellent durability can be reliably formed. In addition, when the addition amount exceeds 10 parts by mass, it is difficult to obtain a sufficient degree of cross-linking because a reaction residue remains on the contrary, and as a result, the denseness of the coating resin layer is reduced, so that the durability is reduced. .

The coating amount of the silicone resin is preferably from 0.01 to 10% by mass, more preferably from 0.1 to 5% by mass, based on the core particles. When the silicone resin coating amount is less than 0.01% by mass, it becomes difficult to form a uniform coating resin layer on the surface of the core particles, and a desired chargeability may not be obtained. On the other hand, if it exceeds 10% by mass, the thickness of the coating resin layer becomes excessively large, so that granulation of carrier particles is likely to occur, and it is difficult to obtain uniform chargeability between the carrier particles.

The means for forming the coating resin layer on the core particles is not particularly limited. For example, a means in which a suitable amount of a silicone resin and, if necessary, a silane coupling agent and a curing agent are blended is used. Dissolve in an appropriate solvent, apply it to the core particles by a method such as spray drying, dipping or pan coating, and then remove the solvent by drying, and further heat the core particles to form a crosslinked silicone resin. A resin-coated carrier having a coated resin layer formed thereon can be obtained.

In the case of forming a coating resin layer by such a method, the above-mentioned coating operation is repeated two or more times to obtain a more uniform coating resin layer. It is preferable to form a coating resin layer. Here, the resin coating amount in the first coating step is preferably 40 to 95% by mass, more preferably 45 to 90% by mass of the entire resin covering amount. The resin coating amount in the second and subsequent final coating steps is preferably 5% by mass or more of the total resin coating amount, and more preferably 10 to 60% by mass.
If the resin coating amount is too small, it is difficult to make the coating resin layer to be formed uniform, and unevenness occurs on the surface of the coating resin layer, and as a result, a low resistance portion is formed. With use, problems such as peeling of the coating resin layer and adhesion of carriers due to a decrease in resistance are likely to occur.

The carrier obtained as described above preferably has a volume average particle size of 10 to 100 μm, more preferably 25 to 80 μm, and still more preferably 35 to 70 μm. When the volume average particle size is smaller than 10 μm, the carrier particles tend to adhere to the photoreceptor, making it difficult to form a high quality image.
On the other hand, when the volume average particle size is larger than 100 μm, the magnetic brush formed on the developing sleeve becomes coarse, and it becomes difficult to form a high quality image. Here, the volume average particle diameter of the carrier was determined by taking a photograph of the carrier particles enlarged 250 times with a scanning electron microscope, measuring the maximum major axis diameter of the carrier particles based on the photograph, and measuring this measurement by 500 times. For each carrier particle,
It is obtained by calculating their average value.

Regarding the particle size distribution of the carrier particles, 25
15% by mass or less of carrier particles having a size of less than 15 μm, 1 to 35% by mass of carrier particles having a size of 25 μm or more and less than 37 μm,
3 to 70% by mass of carrier particles having a size of from 44 μm to less than 44 μm;
It is preferable that 0% by mass, 45% by mass or less of carrier particles of 63 μm or more and less than 75 μm, and 20% by mass or less of carrier particles of 75 μm or more. When the particle size distribution satisfies the above range, variations in chargeability and magnetic properties among carrier particles can be reduced, and a high-quality image can be stably formed for a long period of time. This particle size distribution has an opening of 25 μm, 37 μm,
Using standard sieves of 44 μm, 63 μm, and 75 μm, the sieves are stacked in the order of opening size, and 100.0 g of a carrier is placed at the top. Next, the number of horizontal turns =
The sieve was obtained by sieving at 285 times / min and the number of vibrations = 150 times / minute for 15 minutes, and measuring the remaining amount of each sieve and the mass flowing out from the lowermost layer.

The resistance of the carrier is preferably 10 ⁶ Ωcm or more, more preferably 10 ⁸ Ωcm to 1 Ωcm.
0 ¹³ Ωcm. When the resistance of the carrier is less than 10 ⁶ Ωcm, carrier adhesion due to injection of electric charge from the photoreceptor surface to carrier particles is likely to occur,
It is difficult to form a high quality image. here,
The method of measuring the resistance of the carrier is as follows. That is, the cross-sectional area of the measuring cell as a 1 cm ^2, the carrier 1
g as a measurement sample, put into the measurement cell, measure its height (h), apply a load of 1 kg to the cell filled with the measurement sample, and apply a voltage (V) between the upper electrode and the lower electrode. Then, the flowing current (i) was measured, and the resistance was determined using the following equation. The current value used was a value 30 seconds after the voltage was applied. Further, the measurement environment condition is a normal temperature and normal humidity environment (20 ° C./50% RH).

[0057]

## EQU1 ## Carrier resistance [Ωcm] = V / (i × h)

The toner constituting the developer of the present invention is a toner containing a binder resin, a colorant, and a release agent, wherein the resin particles containing the release agent in the binder resin, the colorant, It is composed of associative toner particles obtained by salting out / fusing the particles.

The release agent constituting the toner is a crystalline ester compound represented by the above general formula (I) (hereinafter, referred to as a “specific ester compound”). It can be suitably synthesized by a dehydration condensation reaction.

Formula (I) representing a specific ester compound
In the above, R ¹ and R ² each represent a hydrocarbon group which may have a substituent. The number of carbon atoms in the hydrocarbon radical R ¹ is 1 to 40, preferably 1 to 20, more preferably 2 to 5. The hydrocarbon group R2 has 1 to 40 carbon atoms, preferably 16 to 30, more preferably 18 to ² carbon atoms.
6 is assumed. Further, the hydrocarbon group R ¹ and the hydrocarbon group R
² may be the same or different. In the general formula (I), n is an integer of 1 to 4,
It is preferably 2 to 4, more preferably 3 to 4, and particularly preferably 4.

Specific examples of the specific ester compound include:
Compounds represented by the following formulas (W1) to (W22) can be exemplified.

[0062]

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[0063]

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[0064]

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The content of the release agent is usually from 1 to 30.
%, Preferably 2 to 20% by mass, more preferably 3 to 15% by mass.

In the present invention, the “resin particles containing a release agent” are obtained by dissolving a release agent in a monomer for obtaining a binder resin, and dispersing the obtained monomer solution in an aqueous medium. By subjecting this system to a polymerization treatment, it can be obtained as latex particles.

As a preferred polymerization method for obtaining resin particles containing a release agent, a release agent is contained in a monomer in an aqueous medium in which a surfactant having a concentration equal to or lower than the critical micelle concentration is dissolved. The monomer solution obtained by dissolution is formed into oil droplets (10 to 1000 nm) using mechanical energy to prepare a dispersion, and a water-soluble polymerization initiator is added to the obtained dispersion, A method of radical polymerization (hereinafter, referred to as “mini-emulsion method” in this specification) can be exemplified. Instead of adding the water-soluble polymerization initiator, or together with the addition of the water-soluble polymerization initiator, an oil-soluble polymerization initiator may be added to the monomer solution.

Here, the disperser for dispersing oil droplets by mechanical energy is not particularly limited, and a stirrer “CLEARMIX” equipped with a high-speed rotating rotor (M Technic) (Trade name), an ultrasonic disperser, a mechanical homogenizer, a Menton-Gaulin and a pressure homogenizer. Further, the dispersed particle diameter is 10 to 1
000 nm, preferably 30 to 300 nm.

The binder resin constituting the toner has a molecular weight distribution of 150,000 to 1,000 as measured by GPC.
It is preferable that the resin contains a high molecular weight component having a peak or a shoulder in a region of 0000 and a low molecular weight component having a peak or a shoulder in a region of 1,000 to 20,000. In addition, 50,000 to 1
It is preferable to contain an intermediate molecular weight component having a peak or shoulder in the region of 40,000. As described above, by using the high molecular weight component and the low molecular weight component together, it is possible to achieve both the improvement of the offset resistance and the fixing property (adhesion to the recording material).

Here, as a method of measuring the molecular weight of the resin by GPC, 1 cc of THF is added to 0.5 to 5.0 mg (specifically, 1 mg) of a measurement sample, and the temperature is lowered to room temperature using a magnetic stirrer or the like. And dissolve sufficiently by stirring. Next, a pore size of 0.45 to 0.50 μm
After the treatment with the membrane filter described above, the mixture is injected into GPC. The GPC measurement conditions were as follows: the column was stabilized at 40 ° C., and THF was flowed at a flow rate of 1 cc / min.
Approximately 100 μl of a sample having a concentration of cc is injected and measured. The column is preferably used in combination with a commercially available polystyrene gel column. For example, S manufactured by Showa Denko
HODEX GPC KF-801,802,803,
804, 805, 806, 807 and TSKgel G1000H, G2000H, G30 manufactured by Tosoh Corporation.
00H, G4000H, G5000H, G6000H,
G7000H, a combination of TSK guard column and the like. As the detector, a refractive index detector (IR detector) or a UV detector may be used. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated using a calibration curve created using monodispersed polystyrene standard particles. It is preferable to use about 10 polystyrenes for preparing a calibration curve.

Hereinafter, the constituent materials of the resin particles and the preparation method (polymerization method) will be described. As the polymerizable monomer used to obtain the resin particles, a radical polymerizable monomer is an essential component, and a crosslinking agent can be used as necessary. It is preferable that at least one of the following radical polymerizable monomers having an acidic group or a radical polymerizable monomer having a basic group is contained.

(1) Radical polymerizable monomer: The radical polymerizable monomer is not particularly limited, and a conventionally known radical polymerizable monomer can be used.
In addition, one kind or a combination of two or more kinds can be used so as to satisfy required characteristics. Specifically, aromatic vinyl monomers, (meth) acrylate monomers, vinyl ester monomers, vinyl ether monomers, monoolefin monomers, diolefin monomers And halogenated olefin monomers.

Examples of the aromatic vinyl monomer include, for example,
Styrene, o-methylstyrene, m-methylstyrene,
p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, p-ethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n- Styrene-based monomers such as octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, 2,4-dimethylstyrene, and 3,4-dichlorostyrene, and derivatives thereof. .

The (meth) acrylate monomers include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, and ethyl methacrylate. Butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, ethyl β-hydroxyacrylate, propyl γ-aminoacrylate, stearyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and the like.

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

Examples of the vinyl ether monomer include vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, vinyl phenyl ether and the like. Monoolefin monomers include ethylene, propylene, isobutylene, 1-butene, 1-pentene,
-Methyl-1-pentene and the like.

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

Examples of the halogenated olefin monomer include:
Vinyl chloride, vinylidene chloride, vinyl bromide and the like.

(2) Crosslinking agent: As a crosslinking agent, a radical polymerizable crosslinking agent may be added in order to improve the properties of the toner. Examples of the radical polymerizable crosslinking agent include those having two or more unsaturated bonds such as divinylbenzene, divinylnaphthalene, divinyl ether, diethylene glycol methacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, and diallyl phthalate.

(3) Radical polymerizable monomer having an acidic group or a basic group: Examples of the radical polymerizable monomer having an acidic group or the radical polymerizable monomer having a basic group include a carboxyl group. Amine-containing compounds, sulfonic acid group-containing monomers, amine compounds such as primary amines, secondary amines, tertiary amines, and quaternary ammonium salts can be used. As the radical polymerizable monomer having an acidic group, as a carboxylic acid group-containing monomer, acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, cinnamic acid, maleic acid monobutyl ester, maleic acid monomer Octyl ester and the like. Examples of the sulfonic acid group-containing monomer include styrene sulfonic acid, allyl sulfosuccinic acid, octyl allyl sulfosuccinate, and the like. These may have a structure of an alkali metal salt such as sodium or potassium or an alkaline earth metal salt such as calcium.

Examples of the radical polymerizable monomer having a basic group include amine compounds, such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, and the quaternary of the above four compounds. Ammonium salt, 3-dimethylaminophenyl acrylate, 2-hydroxy-3-methacryloxypropyltrimethylammonium salt, acrylamide, N-butylacrylamide, N, N-dibutylacrylamide,
Piperidylacrylamide, methacrylamide, N-butylmethacrylamide, N-octadecylacrylamide; vinylpyridine, vinylpyrrolidone; vinyl N-methylpyridinium chloride, vinyl N-ethylpyridinium chloride, N, N-diallylmethylammonium chloride, N, N- Diallylethylammonium chloride and the like can be mentioned.

As the radical polymerizable monomer used in the present invention, a radical polymerizable monomer having an acidic group or a radical polymerizable monomer having a basic group is used in an amount of 0.1 to 15% of the whole monomer. The radical polymerizable cross-linking agent is preferably used in an amount of 0.1 to 10% by mass with respect to the total radical polymerizable monomer, although it depends on its properties.

For the purpose of adjusting the molecular weight of the resin particles, a commonly used chain transfer agent can be used. The chain transfer agent is not particularly limited and includes, for example, mercaptans such as octyl mercaptan, dodecyl mercaptan, tert-dodecyl mercaptan, n-octyl-3-mercaptopropionate, terpinolene, carbon tetrabromide and α-methylstyrene. A dimer or the like is used.

The radical polymerization initiator used in the present invention can be appropriately used as long as it is water-soluble. For example, persulfates (potassium persulfate, ammonium persulfate, etc.), azo compounds (4,4'-azobis-4-cyanovaleric acid and its salts, 2,2'-azobis (2-amidinopropane) salts, etc.), peroxides And the like. Further, the radical polymerization initiator can be used as a redox initiator in combination with a reducing agent, if necessary. By using a redox-based initiator, the polymerization activity is increased, the polymerization temperature can be reduced, and a further reduction in the polymerization time can be expected. As the polymerization temperature, any temperature may be selected as long as it is equal to or higher than the lowest radical generation temperature of the polymerization initiator, but for example, a range of 50 ° C to 90 ° C is used. However, by using a polymerization initiator started at room temperature, for example, a combination of hydrogen peroxide and a reducing agent (such as ascorbic acid), polymerization can be performed at room temperature or higher.

In order to carry out polymerization using the above-mentioned radical polymerizable monomer, it is necessary to disperse oil droplets in an aqueous medium using a surfactant. The surfactant that can be used at this time is not particularly limited, but the following ionic surfactants can be mentioned as preferred examples. As the ionic surfactant, a sulfonate (sodium dodecylbenzenesulfonate,
Sodium arylalkyl polyether sulfonate,
3,3-disulfonediphenylurea-4,4-diazo-
Sodium bis-amino-8-naphthol-6-sulfonate, ortho-carboxybenzene-azo-dimethylaniline, 2,2,5,5-tetramethyl-triphenylmethane-4,4-diazo-bis-β-naphthol -6
Sodium sulfonate), sulfate salts (sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, etc.),
Fatty acid salts (sodium oleate, sodium laurate, sodium caprate, sodium caprylate, sodium caproate, potassium stearate, calcium oleate, etc.) are exemplified. Further, a nonionic surfactant can also be used. Specifically, polyethylene oxide, polypropylene oxide, a combination of polypropylene oxide and polyethylene oxide, an ester of polyethylene glycol and higher fatty acid, an alkylphenol polyethylene oxide, an ester of higher fatty acid and polyethylene glycol, an ester of higher fatty acid and polypropylene oxide, a sorbitan ester And the like.

As the colorant constituting the toner, carbon black, magnetic substance, dye, pigment and the like can be used arbitrarily. As the carbon black, channel black, furnace black, acetylene black, thermal black, lamp black and the like can be used. Is used. As the magnetic material, ferromagnetic metals such as iron, nickel and cobalt, alloys containing these metals, compounds of ferromagnetic metals such as ferrite and magnetite, alloys which do not contain ferromagnetic metals but show ferromagnetism by heat treatment, For example, alloys of a type called a Heusler alloy such as manganese-copper-aluminum and manganese-copper-tin, chromium dioxide, and the like can be used.

As the dye, C.I. I. Solvent Red 1, 49, 52, 58, 63, 111, 1
22, C.I. I. Solvent Yellow 19, 44, 7
7, 79, 81, 82, 93, 98, 1
03, 104, 112, 162, C.I. I. Solvent Blue 25, 36, 60, 70, 93, 95, etc., and mixtures thereof can also be used. Examples of the pigment include C.I. I. Pigment Red 5, 48: 1, 53: 1, 57: 1, 122,
139, 144, 149, 166, 177,
178, 222, C.I. I. Pigment Orange 3
1, 43, C.I. I. Pigment Yellow 14, 1
7, 93, 94, 138, 155, 156,
180, 185, C.I. I. Pigment Green 7,
C. I. Pigment Blue 15: 3, 60 and the like, and mixtures thereof can also be used. Although the number average primary particle diameter varies depending on the type, it is generally about 10 to 2
It is preferably about 00 nm.

The colorant can be used after surface modification. As the surface modifier, a conventionally known one can be used, and specifically, a silane coupling agent, a titanium coupling agent, an aluminum coupling agent and the like can be preferably used.

For the purpose of improving the fluidity, the chargeability and the cleaning property, a so-called external additive can be added to the toner. These external additives are not particularly limited, and various inorganic fine particles, organic fine particles, and lubricants can be used. As the inorganic fine particles, it is preferable to use inorganic oxide particles such as silica, titania, and alumina. Further, it is preferable that these inorganic fine particles have been subjected to a hydrophobic treatment with a silane coupling agent, a titanium coupling agent, or the like. The degree of the hydrophobic treatment is not particularly limited, but a methanol wettability of 40 to 95 is preferable. Methanol wettability is to evaluate the wettability to methanol. In this method, 50 ml of distilled water in a 250 ml beaker is
0.2 g of the inorganic fine particles to be measured is weighed and added. Methanol is slowly dropped from a burette whose tip is immersed in the liquid until the whole of the inorganic fine particles is wet with slow stirring. When the amount of methanol required to completely wet the inorganic fine particles is a (ml), the degree of hydrophobicity is calculated by the following equation.

[0090]

## EQU2 ## Degree of hydrophobicity = [a / (a + 50)] × 100

Further, as the organic fine particles, spherical organic fine particles having a number average primary particle diameter of about 10 to 2000 nm can be used. As this, a homopolymer such as styrene or methyl methacrylate or a copolymer thereof can be used. Examples of the lubricant include salts of zinc, aluminum, copper, magnesium, calcium and the like of stearic acid, salts of zinc, manganese, iron, copper, magnesium and the like of oleic acid, and salts of zinc, copper, magnesium, calcium and the like of palmitic acid. Metal salts of higher fatty acids such as salts of linoleic acid such as zinc and calcium, and salts of ricinoleic acid such as zinc and calcium.

The amount of addition of these external additives is 0.1 to 5.0% by mass in the toner, preferably 0.5 to 4.0%.
% By mass. Various external additives may be used in combination.

Examples of the method for producing the toner of the present invention include (1) a dissolving step of dissolving a release agent in a monomer to prepare a monomer solution, and (2) a monomer solution obtained. Is dispersed in an aqueous medium, (3) a polymerization step of preparing a dispersion (latex) of resin particles containing a release agent by polymerizing the aqueous dispersion of the resulting monomer solution, (4) a salting-out / fusion step of salting out / fusing the obtained resin particles and the colorant particles in an aqueous medium to obtain associated particles (toner particles); A filtration / washing step of filtering and removing a surfactant or the like from the associated particles by filtration from the medium, (6) a drying step of the washed associated particles, and (7) drying the associated particles. An external additive adding step of adding an external additive may be included.

(1) Dissolution step: The method for dissolving the release agent in the monomer is not particularly limited. As the amount of the release agent dissolved in the monomer, the content of the release agent in the finally obtained toner is 1 to 30% by mass, preferably 2 to 20% by mass, and more preferably 3 to 15% by mass. And the amount Incidentally, an oil-soluble polymerization initiator and other oil-soluble components can be added to the monomer solution.

(2) Dispersing step: The method of dispersing the monomer solution in the aqueous medium is not particularly limited, but a method of dispersing with a mechanical energy is preferable. It is preferable to disperse the monomer solution into oil droplets using mechanical energy in an aqueous medium in which a surfactant having a concentration is dissolved (an essential mode in the miniemulsion method). Here, the disperser for performing oil droplet dispersion by mechanical energy is not particularly limited, for example, "Clear Mix", an ultrasonic disperser, a mechanical homogenizer, a Mentongorin and a pressure homogenizer, and the like. Can be mentioned. Further, the dispersed particle diameter is 10 to 1000
nm, preferably 30 to 300 nm.

(3) Polymerization step: In the polymerization step, basically, a conventionally known polymerization method (emulsion polymerization method, suspension polymerization method,
Granulation polymerization such as seed polymerization) can be employed. An example of a preferred polymerization method is a mini-emulsion method, that is, a monomer solution is dispersed in oil droplets using mechanical energy in an aqueous medium in which a surfactant having a concentration equal to or lower than the critical micelle concentration is dissolved. A method in which a water-soluble polymerization initiator is added to the resulting dispersion to cause radical polymerization.

(4) Salting-out / fusion step: In the salting-out / fusion step, a dispersion of colorant particles is added to a dispersion of resin particles obtained by the above-mentioned polymerization step.
The colorant particles are salted out / fused in an aqueous medium. In addition, in the salting-out / fusion step, resin particles and colorant particles may be fused together with internal additive particles such as a charge control agent.

Further, in the salting out / fusing step,
Along with the resin particles containing a release agent, resin particles not containing these can also be fused. Here, as a preferred embodiment, a resin particle having an intermediate molecular weight (MP) containing a release agent, a resin particle having a low molecular weight (LP), a resin particle having a high molecular weight (HP), and a colorant particle are mixed with a salt. Deposition / fusion.

By including the release agent only in the intermediate molecular weight resin particles (MP), excellent offset resistance / fixing properties due to the intermediate molecular weight resin particles (MP) are exhibited, and the high molecular weight resin is obtained. The offset resistance and anti-winding properties provided by the particles (HP) and the suitable fixing properties provided by the low molecular weight resin particles (LP) are not impaired.

The “aqueous medium” in the salting-out / fusion step refers to a medium whose main component (50% by mass or more) is water. Here, examples of the component other than water include an organic solvent soluble in water, such as methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, and tetrahydrofuran.
Of these, alcohol-based organic solvents such as methanol, ethanol, isopropanol, and butanol, which are organic solvents that do not dissolve the resin, are particularly preferable.

The colorant particles used in the salting-out / fusion step can be prepared by dispersing the colorant in an aqueous medium. The colorant dispersion treatment is performed in a state where the surfactant concentration is equal to or higher than the critical micelle concentration (CMC) in water. The dispersing machine used for the dispersion treatment of the colorant is not particularly limited, but preferably, "Clear Mix", an ultrasonic dispersing machine, a mechanical homogenizer, a pressure dispersing machine such as Menton Gorin or a pressure homogenizer, a sand grinder, a getzman mill. And a media type disperser such as a diamond fine mill. Examples of the surfactant used include the same surfactants as described above.

The colorant (particle) may be surface-modified. In the surface modification method of the colorant, the colorant is dispersed in a solvent, the surface modifier is added to the dispersion, and the system is reacted by raising the temperature of the system. After completion of the reaction, the colorant is separated by filtration, washed and filtered repeatedly with the same solvent, and then dried to obtain a colorant (pigment) treated with a surface modifier.
Is obtained.

In the salting-out / fusion method, a salting-out agent comprising an alkali metal salt and / or an alkaline earth metal salt is coagulated in water in which resin particles and colorant particles are present. This is a step in which salting out is advanced by simultaneously heating the resin particles to a temperature equal to or higher than the glass transition point of the resin particles, and simultaneously performing fusion. In this step, an organic solvent that is infinitely soluble in water may be added.

Here, the alkali metal salt and alkaline earth metal salt as salting-out agents include lithium, potassium, sodium and the like as alkali metals, and magnesium, calcium, strontium, barium and the like as alkaline earth metals. And preferably potassium, sodium, magnesium, calcium and barium. Examples of the salt include chloride, bromide, iodine, carbonate, sulfate and the like.

Further, the organic solvent infinitely soluble in water includes methanol, ethanol, 1-propanol,
2-propanol, ethylene glycol, glycerin,
Acetone and the like can be mentioned, and alcohols of methanol, ethanol, 1-propanol and 2-propanol having 3 or less carbon atoms are preferable, and 2-propanol is particularly preferable.

In the salting-out / fusion step, it is preferable to minimize the time for which the salting-out agent is left after the addition of the salting-out agent (the time until the start of heating). That is, it is preferable that the heating of the dispersion of the resin particles and the colorant particles is started as soon as possible after the addition of the salting-out agent, so that the temperature is equal to or higher than the glass transition temperature of the resin particles. Although the reason for this is not clear, the aggregation state of the particles fluctuates depending on the standing time after salting out, and the particle size distribution becomes unstable or the surface properties of the fused toner fluctuate. Occurs.
The time until the start of heating (leaving time) is usually within 30 minutes, preferably within 10 minutes. The temperature at which the salting-out agent is added is not particularly limited, but is preferably equal to or lower than the glass transition temperature of the resin particles.

In the salting out / fusing step, it is necessary to rapidly raise the temperature by heating, and the rate of temperature rise is preferably 1 ° C./min or more. The upper limit of the heating rate is not particularly limited, but is preferably 15 ° C./min or less from the viewpoint of suppressing generation of coarse particles due to rapid salting out / fusion. Furthermore, after the dispersion of the resin particles and the colorant particles reaches the temperature equal to or higher than the glass transition temperature, it is important to maintain the temperature of the dispersion for a certain period of time to continue the salting-out / fusion. . Thereby, the growth of the toner particles (aggregation of the resin particles and the colorant particles) and the fusion (the disappearance of the interface between the particles) can be effectively advanced, and the durability of the finally obtained toner is improved. can do. Further, after stopping the growth of the associated particles, the fusion by heating may be continued.

(5) Filtration / Washing Step: In this filtration / washing step, a filtration treatment for filtering the toner particles from the dispersion liquid of the toner particles obtained in the above step, and a filtration and washing of the toner particles (cake) Cleaning treatment for removing extraneous matter such as a surfactant and a salting-out agent from the aggregate in the form of a liquid. here,
The filtration method is not particularly limited, such as a centrifugal separation method, a reduced pressure filtration method using a Nutsche method, a filtration method using a filter press, or the like.

(6) Drying step: This step is a step of drying the washed toner particles. Dryers used in this step include spray dryers, vacuum freeze dryers, vacuum dryers and the like, stationary shelf dryers, mobile shelf dryers, fluidized bed dryers, rotary dryers It is preferable to use a stirring dryer. The moisture content of the dried toner particles is preferably 5% by mass or less, more preferably 2% by mass or less.

Incidentally, the dried toner particles are
In the case where the aggregates are aggregated by a weak attraction between particles, the aggregates may be crushed. Here, as the crushing device,
A mechanical crusher such as a jet mill, a Henschel mixer, a coffee mill, and a food processor can be used.

(7) Step of adding an external additive: This is a step of adding an external additive to the dried toner particles. The equipment used to add the external additives includes
Various known mixing devices such as a turbular mixer, a Hensiel mixer, a Nauta mixer, and a V-type mixer can be used.

The toner used in the present invention may contain a material capable of imparting various functions as a toner material in addition to the colorant and the release agent. Specific examples include a charge control agent. These components can be added simultaneously with the resin particles and the colorant particles in the above-mentioned salting-out / fusion step, and can be added by various methods such as a method of including in the toner and a method of adding to the resin particles themselves. Similarly, various known charge control agents, which can be dispersed in water, can be used. Specifically, a nigrosine dye,
Examples include metal salts of naphthenic acid or higher fatty acids, alkoxylated amines, quaternary ammonium salt compounds, azo-based metal complexes, salicylic acid metal salts or metal complexes thereof.

As described above, the toner used in the present invention is an associative toner obtained by salting out / fusing resin particles containing a release agent and colorant particles in an aqueous medium. Yes, salting out the resin particles containing the release agent and the colorant particles /
By fusing, the release agent can be present in the toner particles (associative particles) with a fine domain structure, and the dispersion state (dispersion area / dispersion amount) and surface state of the release agent between the toner particles , The transfer of the release agent to the carrier is suppressed, and a stable charging property is obtained. Further, the toner used in the present invention has a shape having irregularities on the surface from the time of its production, and further, an association type obtained by fusing resin particles and colorant particles in an aqueous medium. Since the toner is a toner, the difference in shape and surface property between toner particles is extremely small, and as a result, the surface property tends to be uniform.
For this reason, there is little difference in fixability between toners, and good fixability can be maintained.

The toner used in the present invention has a shape coefficient variation coefficient of 16% or less, and the number of toner particles having a number variation coefficient of 27% or less in the number particle size distribution and the ratio of toner particles having no corners of 50 or less. % Or more, and the proportion of toner particles having a number variation coefficient of 27% or less in the number particle size distribution or toner particles having a shape coefficient in the range of 1.2 to 1.6 is 65 number% or more, and the shape coefficient Is 16% or less.

The shape factor of the toner is represented by the following equation, and indicates the degree of roundness of the toner particles.

[0116]

[Formula 3] Shape factor = {(maximum diameter / 2) ² × π} / projected area

Here, the maximum diameter means the width of a particle at which the distance between the parallel lines becomes maximum when the projected image of the toner particles on the plane is sandwiched between two parallel lines. The projection area refers to the area of the projected image of the toner particles on the plane. In the present invention, this shape factor is determined by a scanning electron microscope.
A photograph in which the toner particles were magnified by a factor of 00 was taken, and then based on the photograph, "SCANNING IMAGE A
The measurement was performed by analyzing a photographic image using "NALYZER" (manufactured by JEOL Ltd.). In this case, the shape factor of the present invention was measured by using the above formula using 100 toner particles.

In the toner used in the present invention, the ratio of the toner particles having the shape factor in the range of 1.2 to 1.6 is preferably at least 65% by number, more preferably at least 70% by number. It is. When the ratio of the toner particles having the shape factor in the range of 1.2 to 1.6 is 65% by number or more, the packing density of the toner particles in the transferred toner layer is increased, and the fixing property is improved.
Offset is less likely to occur. Further, the toner particles are less likely to be crushed, so that contamination of the charging member such as a carrier is reduced, and the charging property of the toner is easily stabilized.

The method for controlling the shape factor is not particularly limited. For example, a method of spraying toner particles in a hot air flow, a method of repeatedly applying mechanical energy by an impact force in a gaseous phase in a gas phase, a method of adding a toner in a solvent that does not dissolve a toner and imparting a swirling flow, etc. There is a method in which toner particles having a shape factor of 1.2 to 1.6 are prepared and added to a normal toner so as to fall within the range of the present invention. Further, there is a method in which the overall shape is controlled at the stage of preparing a so-called polymerization toner, and the toner particles whose shape factor is adjusted to 1.2 to 1.6 are similarly added to a normal toner for adjustment. Among the above methods, a polymerization toner is preferred because it is simple as a production method and has excellent surface uniformity as compared with a pulverized toner.

The variation coefficient of the shape factor of the toner is calculated from the following equation.

[0121]

## EQU4 ## Variation coefficient of shape coefficient = (S ₁ / K) × 100 (%)

[Wherein, S ₁ represents the standard deviation of the shape factor of 100 toner particles, and K represents the average value of the shape factors. ]

In the toner used in the present invention, the coefficient of variation of the shape factor is preferably 16% or less, more preferably 14% or less. When the variation coefficient of the shape factor is 16% or less, the gap of the transferred toner layer (powder layer) is reduced, the fixing property is improved, and the offset is less likely to occur. Further, the charge amount distribution can be made sharper, and the image quality is improved.

In order to uniformly control the shape factor of the toner and the variation coefficient of the shape factor without extremely varying lots, a process of fusing resin particles (polymer particles) containing a release agent and controlling the shape. In the method described above, it is preferable to determine an appropriate process end time while monitoring characteristics of toner particles (colored particles) being formed. Monitoring means that a measuring device is incorporated in-line and process conditions are controlled based on the measurement result. In other words, the measurement of the shape and the like is incorporated in-line, and the shape and the particle size are measured while sequentially sampling in the fusion step when the resin particles are salted out / fused in the aqueous medium with the colorant particles. The reaction is stopped when the shape becomes Although the monitoring method is not particularly limited, a flow type particle image analyzer FPIA-2 is used.
000 (manufactured by Toa Medical Electronics Co., Ltd.) can be used.
This apparatus is suitable because the shape can be monitored by performing image processing in real time while passing the sample liquid. That is, a pump or the like is used from the reaction field to constantly monitor and measure the shape and the like, and stop the reaction when the desired shape and the like are obtained.

The number particle size distribution and the number variation coefficient of the toner used in the present invention are measured with a Coulter Counter TA- or Coulter Multisizer (manufactured by Coulter). In the present invention, a Coulter Multisizer was used, connected to an interface (manufactured by Nikkaki) for outputting a particle size distribution and a personal computer. The aperture used in the Coulter Multisizer is 100 μm,
The particle size distribution and the average particle size were calculated by measuring the volume and the number of toner particles having a size of 2 μm or more. The number particle size distribution represents the relative frequency of the toner particles with respect to the particle size, and the number average particle size represents the median size in the number particle size distribution. The “number variation coefficient in the number particle size distribution” of the toner is calculated from the following equation.

[0126]

## EQU5 ## Number variation coefficient = [S ₂ / D _n ] × 100 (%)

[Wherein, S ₂ represents the standard deviation in the number particle size distribution, and D _n represents the number average particle size (μm). ]

The number variation coefficient of the toner used in the present invention is preferably 27% or less, more preferably 2% or less.
5% or less. When the number variation coefficient is 27% or less, voids in the transferred toner layer (powder layer) are reduced, so that the fixing property is improved, and offset is less likely to occur. Further, the charge amount distribution becomes sharper, the transfer efficiency is increased, and the image quality is improved.

The method for controlling the number variation coefficient of the toner is not particularly limited. For example, a method of classifying toner particles by wind force can be used, but classification in a liquid is effective for further reducing the number variation coefficient. As a method of classifying in a liquid, there is a method of separating and collecting toner particles according to a sedimentation speed difference caused by a difference in toner particle diameter by controlling a rotation speed by using a centrifugal separator.

In the toner particles constituting the toner used in the present invention, the proportion of toner particles having no corners is preferably at least 50% by number, more preferably at least 70% by number. When the ratio of the toner particles having no corners is 50% by number or more, the gap of the transferred toner layer (powder layer) is reduced, the fixing property is improved, and the offset is less likely to occur. In addition, the amount of toner particles that are liable to wear and breakage and toner particles having a portion where charges are concentrated are reduced, the charge amount distribution becomes sharper, the chargeability is stabilized, and good image quality is formed over a long period of time. it can.

Here, “toner particles having no corners” refers to toner particles having substantially no projections on which electric charges are concentrated or projections which are easily worn by stress.
Specifically, the following toner particles are referred to as toner particles having no corners. That is, as shown in FIG.
When the major axis is L, a circle C having a radius (L / 10)
The case where the circle C does not substantially protrude outside the toner particle T when the inside is rolled while being in contact with the periphery line of the toner particle T at one point is referred to as a “toner particle having no corner”. . “Cases that do not substantially protrude” refer to cases where there are no more than one protrusion having a protruding circle. Also,
The “longer diameter of the toner particle” refers to the width of the particle at which the interval between the parallel lines is the largest when the projected image of the toner particle on the plane is sandwiched between two parallel lines. FIGS. 1B and 1C show projected images of the toner particles having corners, respectively.

The ratio of the toner particles having no corners was measured as follows. First, a photograph in which the toner particles were enlarged by a scanning electron microscope was taken, and further enlarged to 15.0.
Obtain a 00x photographic image. Next, the presence or absence of the corners is measured for this photographic image. This measurement was performed for 100 toner particles.

The method for obtaining toner having no corners is not particularly limited. For example, as described above, as a method of controlling the shape coefficient, a method of spraying toner particles into a hot air flow, a method of repeatedly applying mechanical energy by an impact force in a gas phase, or a method of dissolving a toner It can be obtained by adding to a solvent that does not contain and giving a swirling flow. In addition, salting out the resin particles /
In the step of stopping fusion when fusing, the surface of the fused particles has many irregularities and the surface is not smooth, but the conditions in the shape control step, such as the temperature, the number of rotations of the stirring blade, and the stirring time, are appropriate. By doing so, a toner having no corners can be obtained. These conditions vary depending on the physical properties of the resin particles. For example, by setting the rotation speed higher than the glass transition temperature of the resin particles, the surface becomes smooth and a toner having no corners can be formed.

The toner used in the present invention preferably has a number average particle diameter of 3 to 8 μm. In the case where toner particles are formed by a polymerization method, the particle size is determined by the concentration of the coagulant, the amount of the organic solvent added, or the fusing time, and the composition of the polymer itself, in the toner manufacturing method described in detail below. Can be controlled by When the number average particle size is 3 to 8 μm, in the fixing step, toner particles having a large adhesive force that fly and adhere to the heating member to generate offset are reduced, and the transfer efficiency is increased, and the halftone The image quality is improved, and the image quality of fine lines, dots, and the like is improved.

When the particle size of the toner particles is D (μm), the natural logarithm lnD is plotted on the horizontal axis, and the horizontal axis is 0.23.
In the histogram showing the number-based particle size distribution divided into a plurality of classes at intervals, the relative frequency (m1) of the toner particles included in the most frequent class and the toner particles included in the class having the second highest frequency after the most frequent class Is preferably 70% or more with respect to the relative frequency (m2).

When the sum (M) of the relative frequency (m1) and the relative frequency (m2) is 70% or more, the dispersion of the particle size distribution of the toner particles becomes narrower. Thus, the occurrence of selective development can be reliably suppressed. In the present invention, the histogram showing the number-based particle size distribution includes a natural logarithm lnD (D: particle size of individual toner particles) in a plurality of classes (0 to 0.23: 0.23 to 0.23) at intervals of 0.23. 0.46: 0.46-0.
69: 0.69-0.92: 0.92-1.15: 1.
15-1.38: 1.38-1.61: 1.61-1.
84: 1.84 to 2.07: 2.07 to 2.30: 2.
30 to 2.53: 2.53 to 2.76...) Is a histogram showing the number-based particle size distribution, which is based on the following conditions. Diameter data is
It is transferred to a computer via the / O unit, and is created by the computer using a particle size distribution analysis program.

[Measurement conditions] (1) Aperture: 100 μm (2) Sample preparation method: Electrolyte [ISOTON R-1
1 (manufactured by Coulter Scientific Japan)
An appropriate amount of a surfactant (neutral detergent) is added to 50 to 100 ml, and the mixture is stirred, and 10 to 20 mg of a measurement sample is added thereto. This system is prepared by subjecting it to a dispersion treatment with an ultrasonic disperser for 1 minute.

FIG. 2 is an explanatory view showing an example of the configuration of a reaction apparatus (stirring apparatus) suitably used for producing a polymerization toner for salting out / fusing resin particles. 2, a stirring tank, 3 a rotating shaft, 7 an upper material inlet, 8 a lower material inlet, and 46 and 56 stirring blades. This reaction device (stirring device) is characterized in that no obstacle such as a baffle plate that forms a turbulent flow is provided in the stirring tank 2. Regarding the configuration of the stirring blades, it is preferable that the upper-stage stirring blades have a multi-stage configuration in which the lower-stage stirring blades are disposed with an intersection angle α that precedes the rotation direction.

The shape of the stirring blade is not particularly limited as long as it does not form a turbulent flow.
As shown in (d) to (d), those formed of continuous surfaces, such as a rectangular plate, are preferable. The stirring blade 5a shown in FIG. 3 (a) has no hole, and the stirring blade 5b shown in FIG. 3 (b) has a large hole 6b in the center, and FIG. 3 (c).
The stirring blade 5c shown in FIG. 5 has a horizontally elongated middle hole 6c (slit), and the stirring blade 5d shown in FIG.
There is d (slit). Further, it may have a curved surface. Further, a three-stage stirring blade may be provided, and in this case, a middle hole formed in the upper stirring blade and a middle hole formed in the lower stirring blade may be different from each other. , May be the same.

According to such a reaction apparatus, by controlling the temperature, the number of revolutions, and the time in the fusing step and the shape control step, a toner having an intended shape coefficient and a uniform shape distribution can be formed. Can be. The reason for this is that when fusion is performed in a place where a laminar flow is formed, strong stress is not applied to the particles that are undergoing aggregation and fusion (association or aggregated particles) and the flow is accelerated in a laminar flow. It is presumed that as a result of the uniform temperature distribution in the stirring tank, the shape distribution of the fused particles becomes uniform. Further, the fused particles gradually become spherical by heating and stirring in the subsequent shape control step, and the shape of the toner particles can be arbitrarily controlled.

The developer according to the present invention includes an image forming method including a step of fixing a recording material on which a toner image is formed by passing the recording material between a heating roller and a pressure roller constituting a fixing device. Image forming method). As a suitable fixing method used in the present invention, a so-called contact heating method can be used. In particular, examples of the contact heating method include a heat and pressure fixing method, a heat roll fixing method, and a pressure contact heat fixing method in which fixing is performed by a rotating pressing member including a fixedly disposed heating element.

FIG. 4 is a sectional view showing an example of a fixing device used in the present invention. This fixing device includes a heating roller 10 and a pressure roller 20 that comes into contact with the heating roller 10. In FIG. 4, T is a toner image formed on a recording material (also referred to as an image support, typically a transfer paper).

The heating roller 10 has a core metal 11 on the surface of which a coating layer 12 made of a fluororesin or an elastic body is formed, and includes a heating member 13 made of a linear heater.

The core metal 11 is made of a metal or an alloy thereof, and has an inner diameter of 10 to 70 mm. The material constituting the metal core 11 is not particularly limited, and examples thereof include metals such as iron, aluminum, and copper, and alloys thereof. The thickness of the core metal 11 is set to 0.1 to 2 mm, and demand for energy saving (thinning)
And strength (depending on the constituent materials). For example, in order to maintain a strength equivalent to that of a 0.57 mm iron core with an aluminum core, the wall thickness must be 0.8 mm.

As the fluororesin constituting the coating layer 12, PTFE (polytetrafluoroethylene) and P
FA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer) and the like can be exemplified. The thickness of the coating layer 12 made of fluororesin is 10 to 50
0 μm, preferably 20 to 200 μm.
If the thickness of the coating layer 12 made of fluororesin is less than 10 μm, the function as the coating layer cannot be sufficiently exhibited, and the durability as a fixing device cannot be secured. On the other hand, there is a problem that the surface of the coating layer having a thickness of more than 500 μm is easily scratched by paper dust, and toner or the like adheres to the scratched portion, thereby causing image stains.

As the elastic body constituting the coating layer 12, it is preferable to use silicone rubber and silicone sponge rubber having good heat resistance such as LTV, RTV and HTV. The thickness of the coating layer 12 made of an elastic body is 0.1 to 30 mm, preferably 0.1 to 20 mm.
It is said. The Asker C hardness of the elastic body constituting the coating layer 12 is less than 80 °, preferably less than 60 °. When the thickness of the coating layer 12 is less than 0.1 mm and when the Asker C hardness of the elastic body constituting the coating layer 12 exceeds 80 °, the fixing nip cannot be increased, and It is difficult to exhibit the effect of soft fixing such as the effect of improving color reproducibility by the toner layer at the interface.

As the heating member 13, for example, a halogen heater can be suitably used. The number of the heating members 13 is not particularly limited, and a configuration in which a plurality of heating members are included and the heat distribution area can be changed according to the size (width) of the transfer paper passing therethrough can be employed. For example, a configuration in which a central region heating halogen heater for heating a central region on the surface of the heating roller, and an end region heating halogen heater for heating an end region on the surface of the heating roller are provided. can do. In the heating roller having such a configuration, for example, when a narrow transfer paper is passed, only the central area heating halogen heater needs to be energized. It is sufficient to energize the halogen heater for heating the region.

The pressure roller 20 has a coating layer 22 made of an elastic material formed on the surface of a metal core 21. Coating layer 22
The elastic body is not particularly limited, and includes various soft rubbers such as urethane rubber and silicone rubber and sponge rubber.
It is preferable to use the silicone rubber and the silicone sponge rubber exemplified as those constituting the first coating layer 12.

The thickness of the coating layer 22 is 0.1 to 30 mm, preferably 0.1 to 20 mm. The Asker C hardness of the elastic body constituting the coating layer 22 is less than 70 °, preferably less than 60 °. Coating layer 22
Is less than 0.1 mm, and the coating layer 22
When the Asker C hardness of the elastic body constituting 70 ° exceeds 70 °, the fixing nip cannot be increased, and for example, soft fixing such as an effect of improving color reproducibility by a smoothed interface toner layer is achieved. It cannot be effective.

The material constituting the core metal 21 is not particularly limited, but examples thereof include metals such as aluminum, iron, and copper or alloys thereof.

The contact load (total load) between the heating roller 10 and the pressure roller 20 is usually 40 to 350 N, preferably 50 to 300 N, and more preferably 50 to 300 N.
２５０250N. This contact load is applied to the heating roller 1
It is defined in consideration of the strength of 0 (thickness of the metal core 11). For example, in the case of a heating roller having a metal core of 0.3 mm, it is preferably 250 N or less.

From the viewpoints of offset resistance and fixability, the nip width is preferably 4 to 10 mm, and the surface pressure of the nip is 0.6 × 10 ⁵ Pa to 1.5.
It is preferably × 10 ⁵ Pa.

An example of the fixing condition by the fixing device shown in FIG. 4 is as follows. Fixing temperature (surface temperature of heating roller 10)
Is 150 to 210 ° C., and the fixing linear velocity is 80 to 640 m.
m / sec.

The fixing device used in the present invention may be provided with a cleaning mechanism as needed. In this case, as a method of supplying the silicone oil to the upper roller (heating roller) of the fixing unit, a method of supplying and cleaning with a pad, a roller, a web, or the like impregnated with the silicone oil can be used. As the silicone oil, those having high heat resistance are used, and polydimethyl silicone, polyphenylmethyl silicone, polydiphenyl silicone and the like are used. Since those with low viscosity have a large outflow during use, the viscosity at 20 ° C. is 1%.
Those having a pressure of １００100 Pa · s are preferably used.

[0155]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples. In the following, “parts” means “parts by mass”.

<Production Example 1 of Core Particles> 22 mol% of Li ₂ CO ₃ and 78 mol% of Fe ₂ O ₃ were mixed in a wet ball mill by a wet ball mill.
After crushing, mixing and drying for an hour, the mixture was temporarily calcined by holding at 900 ° C. for 2 hours. This was again pulverized by a ball mill for 3 hours to form a slurry. A dispersing agent and a binder were added, and primary particles were prepared by granulating and drying with a spray drier, and further baked at 1200 ° C. for 3 hours to obtain ferrite core particles having a volume average particle diameter of 71 μm. This is referred to as “core particle 1”.

<Production Example 2 of Core Particles> Li ₂ CO ₃ was added to 23
Mol%, Mg (OH) ₂ to 7 mol%, the Fe ₂ O ₃ and 70 mol%, the other to the temperature of the main firing was 1250 ° C. in the same manner as the core particles prepared in Example 1, the volume average particle diameter Is 61μ
m ferrite core particles were obtained. This is called “Core Particle 2”
And

<Production Example 3 of Core Particle> 20% Li ₂ CO ₃
Ferrite core particles having a volume average particle size of 52 μm were obtained in the same manner as in Core particle production example 1 except that mol%, MnO was 8 mol%, and Fe ₂ O ₃ was 72 mol%. This is referred to as “core particles 3”.

<Production Example 1 of Carrier> Structural units in which substituents R ³ and R ⁴ in general formula (II) are a methyl group and a hydroxyl group, respectively, and substituent R ⁵ in general formula (III)
And a structural unit in which R ⁶ is a methyl group together with (I
I) :( III) = 100 parts of a silicone resin contained in a mass ratio of 40:60, 10 parts of a silane coupling agent represented by the above formula (1), and an oxime type represented by the above formula (15) Was mixed with 5 parts of a curing agent and dissolved in a toluene solvent to prepare a toluene solution having a solid content of 15% by mass. Next, after applying a toluene solution by a spray drying method so that the resin coating amount on the core particles 1 becomes 0.5% by mass, baking (curing) is performed at 230 ° C. for 3 hours to form a coating resin layer. , Core particle 1
To obtain a silicone resin carrier in which a silicone resin is coated on the surface. This is referred to as “carrier 1”.

<Example 2 of Carrier Production> Example 1 of Carrier Production
, A silicone resin-coated carrier was obtained in the same manner as in Carrier Production Example 1, except that the amount of resin coating on the core particles 1 was 0.8% by mass. This is called “carrier 2”.

<Carrier Production Example 3> Carrier Production Example 1
In, when forming a resin coating layer on the core particles,
Assuming that the resin coating amount on the core particles 1 is 0.6% by mass, 1
After forming the next coating resin layer, the resin coating amount is further increased by 0.4
A silicone resin-coated carrier was obtained in the same manner as in Carrier Production Example 1, except that the desired coating resin layer was formed as mass%. This is called “carrier 3”.

<Carrier Production Example 4> Carrier Production Example 3
In Carrier Production Example 3, except that the primary coating resin layer was formed with the resin coating amount being 0.4% by mass, and the intended coating resin layer was further formed with the resin coating amount being 0.4% by mass. And a silicone resin-coated carrier was obtained in the same manner. This is called “carrier 4”.

<Carrier Production Example 5> Carrier Production Example 3
In Example 3, except that the addition amount of the silane coupling agent represented by the above formula (1) was set to 20 parts,
In the same manner as in the above, a silicone resin-coated carrier was obtained. This is referred to as “carrier 5”.

<Carrier Manufacturing Example 6> Carrier Manufacturing Example 3
In Carrier Production Example 3, except that the addition amount of the silane coupling agent represented by the above formula (1) was set to 40 parts,
A silicone resin-coated carrier was obtained in the same manner as described above. This is referred to as “carrier 6”.

<Carrier Production Example 7> Carrier Production Example 1
, A silicone resin-coated carrier was obtained in the same manner as in Carrier Production Example 1, except that the silane coupling agent represented by the above formula (1) was not added. This is referred to as “carrier 7”.

<Carrier Production Example 8> Carrier Production Example 3
In the formula, the substituent R in the general formula (II)^ThreeAnd R^Four
Is a structural unit in which each is a methyl group and a hydroxyl group, and
Substituent R in formula (III)^Five And R⁶Are all
(II) :( III) = 30: 7
100 parts of a silicone resin contained at a mass ratio of 0,
30 parts of the silane coupling agent represented by the formula (1)
8 parts of an oxime-type curing agent represented by the formula (17):
To prepare a toluene solution having a solid content of 15% by mass.
Silicon carrier was prepared in the same manner as in Carrier Production Example 3 except that
Thus, a resin-coated carrier was obtained. This is called "Carrier 8"
I do.

<Carrier Manufacturing Example 9> Carrier Manufacturing Example 3
, A silicone resin-coated carrier was obtained in the same manner as in Carrier Production Example 3 except that core particles 2 were used instead of core particles 1. This is referred to as “carrier 9”.

<Carrier Production Example 10> A silicone resin-coated carrier was obtained in the same manner as in Carrier Production Example 3, except that core particles 3 were used in place of core particles 1. This is referred to as “carrier 10”.

<Production Example of Comparative Carrier> A toluene solution was prepared by dissolving a styrene acrylic resin in a toluene solvent, and the core was dried by spray drying so that the resin coating amount on the core particles 1 was 0.8% by mass. By coating the particles 1, a coated resin layer of a styrene acrylic resin was formed to obtain a resin-coated carrier. This is referred to as “comparative carrier 1”.

With respect to each carrier obtained as described above, the specific resistance was measured by setting the applied voltage at the time of measurement to 1000 V in the above-described measuring method. The results are shown in Table 1 below. Table 1 shows the particle size distribution of each carrier.
Are shown together.

[0171]

[Table 1]

<Production of Toner> [Preparation Example HP-1] Stirrer, temperature sensor, cooling pipe,
In a 5000 ml separable flask equipped with a nitrogen introduction device, 7.08 g of an anionic surfactant (sodium dodecyl sulfonate: SDS) was charged with ion-exchanged water 27.
A surfactant solution (aqueous medium) dissolved in 60 g was charged, and the internal temperature was raised to 80 ° C. while stirring at a stirring speed of 230 rpm under a nitrogen stream. 0.42 g of a polymerization initiator (potassium persulfate: KPS) was added to this surfactant solution.
Was dissolved in 200 g of ion-exchanged water, the temperature was adjusted to 75 ° C., and 115.1 g of styrene, n
-Butyl acrylate 42.0 g, methacrylic acid 10.
A 9 g monomer mixture was added dropwise over 1 hour, and the system was heated and stirred at 75 ° C. for 2 hours to prepare a latex (a dispersion of high molecular weight resin particles). This is designated as "latex (HP-1)". The peak molecular weight of the resin particles constituting this latex (HP-1) was 518,000.

[Preparation Example HP-2] Preparation Example HP-2 was repeated except that the reaction temperature was changed to 85 ° C.
A latex (dispersion liquid of resin particles of high molecular weight) was prepared in the same manner as -1. This is called "latex (HP-2)"
And The peak molecular weight of the resin particles constituting the latex (HP-2) was 421,000.

[Preparation Example HP-3] A latex (having a high molecular weight) was prepared in the same manner as in Preparation Example HP-1, except that the amount of the polymerization initiator (KPS) was changed to 0.84 g. A dispersion of resin particles) was prepared. This is designated as "latex (HP-3)". The peak molecular weight of the resin particles constituting the latex (HP-3) is 31.
6,000.

[Preparation Example HP-4] Preparation Example HP-1 was prepared in the same manner as in Preparation Example HP-1, except that the amount of potassium persulfate (KPS) was changed to 0.84 g and the reaction temperature was changed to 90 ° C. A latex (dispersion liquid of high molecular weight resin particles) was prepared in the same manner as described above. This is called "latex (HP-
4) ". The peak molecular weight of the resin particles constituting this latex (HP-4) was 193,000.

[Preparation Example MP-1] In a flask equipped with a stirrer, 72.0 g of a compound represented by the above formula (W19) (hereinafter, referred to as “exemplary compound (19)”) was added.
383.6 g of styrene, n-butyl acrylate 14
0.0 g, 36.4 g of methacrylic acid, and 5.6 g of dodecyl mercaptan were added to a monomer mixture, heated to 80 ° C. and dissolved to prepare a monomer solution. On the other hand, in a 5000 ml separable flask equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introducing device, a surfactant solution (water-based solution) in which 1.6 g of an anionic surfactant (SDS) was dissolved in 2000 g of ion-exchanged water. ), And the internal temperature was raised to 80 ° C. Next, a mechanical dispersing machine "CLEARMIX" having a circulation path (M Technique Co., Ltd.)
The monomer solution (80 ° C.) was mixed and dispersed in the surfactant solution (80 ° C.) to prepare a dispersion of emulsified particles (oil droplets) having a uniform dispersed particle diameter. Next, to this dispersion, an initiator solution obtained by dissolving 19.1 g of a polymerization initiator (KPS) in 240 g of ion-exchanged water and 750 g of ion-exchanged water are added, and the system is heated at 80 ° C. for 3 hours. Polymerization was carried out by stirring to prepare a latex (a dispersion of resin particles having an intermediate molecular weight and containing the exemplified compound (W19)). This is designated as "latex (MP-1)". The peak molecular weight of the resin particles constituting the latex (MP-1) was 103,000.

[Preparation Example MP-2] A latex was prepared in the same manner as in Preparation Example MP-1 except that the amount of dodecyl mercaptan constituting the monomer mixture was changed to 8.3 g. (Dispersion liquid of intermediate molecular weight resin particles containing exemplary compound (W19)) was prepared. This is designated as "latex (MP-2)". The peak molecular weight of the resin particles constituting this latex (MP-2) is 8
It was 1,000.

[Preparation Example MP-3] In Preparation Example MP-1, the amount of Exemplified Compound (W19) added to the monomer mixture was changed to 144.0 g, and n-octyl-3 was used instead of dodecylmercaptan. -Latex (dispersion liquid of intermediate molecular weight resin particles containing Exemplified Compound (W19)) was prepared in the same manner as in Preparation Example MP-1, except that 5.6 g of mercapropionate was used. This is designated as "latex (MP-3)". This latex (MP
The peak molecular weight of the resin particles constituting -3) is 103,0.
00.

[Preparation Example MP-4] In Preparation Example MP-1, the compound of the above formula (W21) was used instead of Exemplified Compound (W19).
A latex (Exemplified Compound (W21)) was prepared in the same manner as in Preparation Example MP-1 except that 72.0 g of a compound represented by the following formula (hereinafter referred to as “Exemplified Compound (W21)”) was added to the monomer mixture. (A dispersion of resin particles having an intermediate molecular weight). This is designated as "latex (MP-4)". The peak molecular weight of the resin particles constituting this latex (MP-4) was 102,000.

[Preparation Example MP-5] In Preparation Example MP-1, the above compound of the formula (W18) was used instead of Exemplified Compound (W19).
A latex (exemplified compound (W18)) was prepared in the same manner as in Preparation Example MP-1 except that 72.0 g of a compound represented by the following formula (hereinafter, referred to as “exemplified compound (W18)”) was added to the monomer mixture. (A dispersion of resin particles having an intermediate molecular weight). This is designated as “latex (MP-5)”. The peak molecular weight of the resin particles constituting the latex (MP-5) was 102,000.

[Preparation Example LP-1] In a flask equipped with a stirrer, a temperature sensor, a cooling tube, and a nitrogen introducing device, 60 g of an anionic surfactant (SDS) was charged with ion-exchanged water 5.
A surfactant solution (aqueous medium) dissolved in 000 g was charged, and the internal temperature was raised to 80 ° C. while stirring at a stirring speed of 230 rpm in a nitrogen stream. To this surfactant solution, 22.8 g of a polymerization initiator (KPS) was added with ion-exchanged water 2
The initiator solution dissolved in 00 g was added and the temperature was raised to 80 ° C.
Styrene 850 g, butyl acrylate 252 g, methacrylic acid 98 g, n-octyl-3-
A monomer mixture comprising 32 g of mercaptopropionate was added dropwise over 1 hour, and this system was heated and stirred at 80 ° C. for 2 hours to prepare a latex (a dispersion of resin particles of low molecular weight). . This is designated as "latex (LP-1)". This latex (LP-
The peak molecular weight of the resin particles constituting 1) is 18,000.
Met.

[Production Example 1Bk] 90 g of sodium n-dodecyl sulfate was dissolved in 1600 ml of ion-exchanged water with stirring. While stirring this solution, 200 g of carbon black “Mogal L” (manufactured by Cabot Corporation) was gradually added.
Next, by performing a dispersion treatment using a stirrer “CLEARMIX” (manufactured by M Technique Co., Ltd.) equipped with a high-speed rotating rotor, a dispersion of colorant particles (hereinafter, referred to as
It is referred to as "colorant dispersion (Bk)". ) Was prepared. The particle size of the colorant particles in the colorant dispersion (Bk)
When measured using an electrophoretic light scattering photometer “ELS-800” (manufactured by Otsuka Electronics Co., Ltd.), the weight average particle diameter was 101.
nm.

The latex obtained in Preparation Example HP-1 (H
P-1) 3000 g, 2500 g of the latex (MP-1) obtained in Preparation Example MP-1, 6000 g of the latex (LP-1) obtained in Preparation Example LP-1, 2,000 g of ion-exchanged water, and coloring 1800 g of the agent dispersion liquid (Bk) was stirred in a reaction vessel equipped with a temperature sensor, a cooling pipe, a nitrogen introducing device, and a stirring device. After adjusting the internal temperature to 30 ° C., a 5N aqueous sodium hydroxide solution was added to the solution to adjust the pH to 11.0. Next, an aqueous solution in which 526 g of magnesium chloride hexahydrate was dissolved in 720 ml of ion-exchanged water was added over 10 minutes at 30 ° C. with stirring. After leaving for 3 minutes, the temperature was raised and the system was
The temperature was raised to 90 ° C. over a period of minutes (heating rate = 10 ° C. /
Minutes). In that state, "Coulter counter TA-II"
The particle size of the associated particles is measured at
At this point, particle growth was stopped by adding an aqueous solution in which 1150 g of sodium chloride was dissolved in 7000 ml of ion-exchanged water, and the mixture was heated and agitated for 2 hours at a liquid temperature of 85 ° C. as a maturing treatment to fuse. Was continued. Thereafter, the mixture was cooled to 30 ° C. under the condition of 8 ° C./min, the pH was adjusted to 2.0 by adding hydrochloric acid, and the stirring was stopped.
The formed associated particles were filtered, washed repeatedly with ion-exchanged water, and then dried with warm air at 40 ° C. to obtain colored particles. The colored particles thus obtained are referred to as “colored particles 1B”.
k ”.

[Production Examples 2Bk to 11Bk] Production Example 1Bk except that at least one of the type of latex used (the amount used was the same), the aging temperature and the aging time was changed according to the formulation shown in Table 2 below. In the same manner as in the above, colored particles containing a release agent were obtained. The colored particles thus obtained are referred to as “colored particles 2Bk” to “colored particles 11Bk”.

[Comparative Production Example 1BK] 140 g of an exemplary compound (W19) dissolved by heating in a surfactant solution (85 ° C.) obtained by dissolving 0.5 g of an anionic surfactant (SDS) in 400 g of ion-exchanged water. Was ultrasonically dispersed. This dispersion is referred to as “release agent dispersion”. This release agent dispersion and the latex (HP-1) obtained in Preparation Example HP-1
3000 g, 6000 g of the latex (LP-1) obtained in Preparation Example LP-1, and 2000 g of ion-exchanged water
And 1800 g of the colorant dispersion liquid (Bk) were placed in a reaction vessel equipped with a temperature sensor, a cooling pipe, a nitrogen introducing device, and a stirring device and stirred, and the aging time was changed to 4 hours. In the same manner as in the above, colored particles containing a release agent were obtained. The colored particles thus obtained are referred to as “comparative colored particles 1bk”.

[0186]

[Table 2]

[Production Example 1Y] 90 g of sodium n-dodecyl sulfate was dissolved by stirring in 1600 ml of ion-exchanged water.
While stirring this solution, 200 g of a dye (CI Solvent Yellow 93) was gradually added, and then a stirring device “CLEARMIX” equipped with a high-speed rotating rotor.
A dispersion of colorant particles (hereinafter, referred to as “colorant dispersion (Y)”) was prepared by performing a dispersion treatment using (manufactured by M Technique Co., Ltd.). When the particle size of the colorant particles in this colorant dispersion liquid (Y) was measured using an electrophoretic light scattering photometer “ELS-800” (manufactured by Otsuka Electronics Co., Ltd.), the weight average particle size was 98 nm. .

The latex obtained in Preparation Example HP-1 (H
P-1) 3000 g, 2500 g of the latex (MP-1) obtained in Preparation Example MP-1, 6000 g of the latex (LP-1) obtained in Preparation Example LP-1, 2,000 g of ion-exchanged water, and coloring 1800 g of the agent dispersion liquid (Y) was stirred in a reaction vessel equipped with a temperature sensor, a cooling pipe, a nitrogen introducing device, and a stirring device. After adjusting the internal temperature to 30 ° C., a 5N aqueous sodium hydroxide solution was added to the solution to adjust the pH to 11.0. Next, an aqueous solution in which 526 g of magnesium chloride hexahydrate was dissolved in 720 ml of ion-exchanged water was added over 10 minutes at 30 ° C. with stirring. After leaving for 3 minutes, the temperature was raised and the system was
The temperature was raised to 90 ° C. over a period of minutes (heating rate = 10 ° C. /
Minutes). In that state, "Coulter counter TA-II"
The particle size of the associated particles is measured at
At the time when the particle size reached m, an aqueous solution in which 1150 g of sodium chloride was dissolved in 7000 ml of ion-exchanged water was added to stop the particle growth, and the mixture was heated and stirred at a liquid temperature of 85 ° C. for 4 hours as a ripening treatment to fuse. Was continued. Thereafter, the mixture was cooled to 30 ° C. under the condition of 8 ° C./min, the pH was adjusted to 2.0 by adding hydrochloric acid, and the stirring was stopped.
The formed associated particles were filtered, washed repeatedly with ion-exchanged water, and then dried with warm air at 40 ° C. to obtain colored particles. The colored particles thus obtained are referred to as “colored particles 1”.
Y ".

Comparative Production Example 1y 140 g of an exemplary compound (W19) dissolved by heating in a surfactant solution (85 ° C.) in which 0.5 g of an anionic surfactant (SDS) was dissolved in 400 g of ion-exchanged water. Was ultrasonically dispersed. This dispersion is referred to as “release agent dispersion”. This release agent dispersion,
Latex (HP-1) 30 obtained in Preparation Example HP-1
00g and the latex obtained in Preparation Example LP-1 (LP
-1) Production Example 1Y except that 6000 g, 2,000 g of ion-exchanged water, and 1300 g of the colorant dispersion (Y) were stirred in a reaction vessel equipped with a temperature sensor, a cooling pipe, a nitrogen introduction device, and a stirring device. In the same manner as in the above, colored particles containing a release agent were obtained. The colored particles thus obtained are referred to as “comparative colored particles 1y”.

[Production Example 1M] 90 g of sodium n-dodecyl sulfate was dissolved in 1600 ml of ion-exchanged water with stirring.
While stirring the solution, 200 g of a pigment (CI Pigment Red 122) was gradually added, and then a stirring device “CLEARMIX” equipped with a high-speed rotating rotor.
A dispersion of colorant particles (hereinafter referred to as “colorant dispersion (M)”) was prepared by performing a dispersion treatment using (manufactured by M Technique Co., Ltd.). When the particle size of the colorant particles in the colorant dispersion liquid (M) was measured using an electrophoretic light scattering photometer “ELS-800” (manufactured by Otsuka Electronics Co., Ltd.), the weight average particle size was 115 nm. .

The latex obtained in Preparation Example HP-1 (H
P-1) 3000 g, 2500 g of the latex (MP-1) obtained in Preparation Example MP-1, 6000 g of the latex (LP-1) obtained in Preparation Example LP-1, 2,000 g of ion-exchanged water, and coloring 1800 g of the agent dispersion liquid (M) was stirred in a reaction vessel equipped with a temperature sensor, a cooling pipe, a nitrogen introducing device, and a stirring device. After adjusting the internal temperature to 30 ° C., a 5N aqueous sodium hydroxide solution was added to the solution to adjust the pH to 11.0. Next, an aqueous solution in which 526 g of magnesium chloride hexahydrate was dissolved in 720 ml of ion-exchanged water was added over 10 minutes at 30 ° C. with stirring. After leaving for 3 minutes, the temperature was raised and the system was
The temperature was raised to 90 ° C. over a period of minutes (heating rate = 10 ° C. /
Minutes). In that state, "Coulter counter TA-II"
The particle size of the associated particles is measured at
At the time when the particle size reached m, an aqueous solution in which 1150 g of sodium chloride was dissolved in 7000 ml of ion-exchanged water was added to stop the particle growth, and the mixture was heated and stirred at a liquid temperature of 85 ° C. for 4 hours as a ripening treatment to fuse. Was continued. Thereafter, the mixture was cooled to 30 ° C. under the condition of 8 ° C./min, the pH was adjusted to 2.0 by adding hydrochloric acid, and the stirring was stopped.
The formed associated particles were filtered, washed repeatedly with ion-exchanged water, and then dried with warm air at 40 ° C. to obtain colored particles. The colored particles thus obtained are referred to as “colored particles 1”.
M ”.

[Comparative Production Example 1m] 140 g of an exemplary compound (W19) dissolved by heating in a surfactant solution (85 ° C) obtained by dissolving 5.0 g of an anionic surfactant (SDS) in 4000 g of ion-exchanged water. Was ultrasonically dispersed. This dispersion is referred to as “release agent dispersion”. This release agent dispersion and the latex (HP-1) obtained in Preparation Example HP-1
3000 g, 6000 g of the latex (LP-1) obtained in Preparation Example LP-1, and 2000 g of ion-exchanged water
And 1300 g of the colorant dispersion liquid (M) were placed in a reaction vessel equipped with a temperature sensor, a cooling pipe, a nitrogen introducing device, and a stirring device, and were stirred in the same manner as in Production Example 1M except that the release agent was contained. Colored particles were obtained. The colored particles thus obtained are referred to as “colored comparative particles 1 m”.

[Production Example 1C] 90 g of sodium n-dodecyl sulfate was dissolved in 1600 ml of ion-exchanged water with stirring.
While stirring this solution, 200 g of a pigment (CI Pigment Blue 15: 3) was gradually added, and then a stirring device “CLEARMIX” equipped with a high-speed rotating rotor.
A dispersion of colorant particles (hereinafter, referred to as “colorant dispersion (C)”) was prepared by performing a dispersion treatment using (manufactured by M Technique Co., Ltd.). When the particle size of the colorant particles in the colorant dispersion liquid (C) was measured using an electrophoretic light scattering photometer “ELS-800” (manufactured by Otsuka Electronics Co., Ltd.), the weight average particle size was 105 nm. .

The latex obtained in Preparation Example HP-1 (H
P-1) 3000 g, 2500 g of the latex (MP-1) obtained in Preparation Example MP-1, 6000 g of the latex (LP-1) obtained in Preparation Example LP-1, 2,000 g of ion-exchanged water, and coloring 1300 g of the agent dispersion liquid (M) was stirred in a reaction vessel equipped with a temperature sensor, a cooling pipe, a nitrogen introducing device, and a stirring device. After adjusting the internal temperature to 30 ° C., a 5N aqueous sodium hydroxide solution was added to the solution to adjust the pH to 11.0. Next, an aqueous solution in which 526 g of magnesium chloride hexahydrate was dissolved in 720 ml of ion-exchanged water was added over 10 minutes at 30 ° C. with stirring. After leaving for 3 minutes, the temperature was raised and the system was
The temperature was raised to 90 ° C. over a period of minutes (heating rate = 10 ° C. /
Minutes). In that state, "Coulter counter TA-II"
The particle size of the associated particles is measured at
At the time when the particle size reached m, an aqueous solution in which 1150 g of sodium chloride was dissolved in 7000 ml of ion-exchanged water was added to stop the particle growth, and the mixture was heated and stirred at a liquid temperature of 85 ° C. for 4 hours as a ripening treatment to fuse. Was continued. Thereafter, the mixture was cooled to 30 ° C. under the condition of 8 ° C./min, the pH was adjusted to 2.0 by adding hydrochloric acid, and the stirring was stopped.
The formed associated particles were filtered, washed repeatedly with ion-exchanged water, and then dried with warm air at 40 ° C. to obtain colored particles. The colored particles thus obtained are referred to as “colored particles 1”.
C ".

Comparative Production Example 1c 140 g of an exemplary compound (W19) dissolved by heating in a surfactant solution (85 ° C.) in which 5.0 g of an anionic surfactant (SDS) was dissolved in 4000 g of ion-exchanged water. Was ultrasonically dispersed. This dispersion is referred to as “release agent dispersion”. This release agent dispersion and the latex (HP-1) obtained in Preparation Example HP-1
3000 g, 6000 g of the latex (LP-1) obtained in Preparation Example LP-1, and 2000 g of ion-exchanged water
And 1300 g of the colorant dispersion liquid (C) were placed in a reaction vessel equipped with a temperature sensor, a cooling pipe, a nitrogen introducing device, and a stirring device, and were stirred in the same manner as in Production Example 1C except that the release agent was contained. Colored particles were obtained. The colored particles thus obtained are referred to as “comparative colored particles 1c”.

[0196]

[Table 3]

The colored particles 1Bk obtained as described above
-11Bk, comparative colored particles 1bk, colored particles 1Y, colored particles 1M, colored particles 1C, comparative colored particles 1y, comparative colored particles 1m, and comparative colored particles 1c, respectively.
Shape characteristics and particle size distribution characteristics were measured. The results are shown in Table 4 below.

[0198]

[Table 4]

To each of the colored particles and the comparative colored particles, hydrophobic silica (number average primary particle diameter = 10 nm, degree of hydrophobicity = 63) was added at a ratio of 1.0% by mass, and hydrophobic silica was added. Titanium oxide (number average primary particle size = 25n
m, degree of hydrophobicity = 60) at a ratio of 1.2% by mass, and mixed with a Henschel mixer. The shape and particle size of these toner particles do not change depending on the addition of hydrophobic silica and hydrophobic titanium oxide.

Next, according to the formulation shown in Table 5 below, each of the colored particles to which the hydrophobic silica and the hydrophobic titanium oxide were added was mixed with the above-mentioned carriers 1 to 10 and the comparative carrier 1, and the toner concentration was 5%. A% by weight developer was prepared.

[0201]

[Table 5]

<Examples 1 to 20 and Comparative Examples 1 and 2> The developers 1Bk to 11B of the present invention obtained as described above.
Digital copying machine “7075” (manufactured by Konica Corporation) having a toner recycling system in which toner collected by cleaning is returned to the developing device again by an appropriate recycling system and reused for each of k and comparative developer 1bk. In a high-temperature and high-humidity environment at a temperature of 32 ° C. and a relative humidity of 85%, an actual photographing test was performed to print 200,000 sheets of an original having a pixel rate of 5% by intermittent printing of five sheets. The image density and the fog density of the image and the image formed on the 200,000th sheet were evaluated. Table 6 shows the results. Further, for each developer, the initial charge amount and the charge amount after printing 200,000 sheets are measured to determine the difference,
The change in the charge amount due to the number of printed sheets was evaluated. The results are shown in Table 6 below.

(1) Image Density and Fog Density The image density was measured for the solid black portion of the fixed image using a Macbeth reflection densitometer “RD-918”, and evaluated in terms of absolute density. The fog density is measured by measuring the image density of a white background portion of a fixed image with a Macbeth reflection densitometer “RD-918”,
It was evaluated by the relative concentration to 0).

(2) Charge Amount The initial charge amount and the charge amount after printing of 200,000 sheets were measured, and the fluctuation width of the charge amount depending on the number of printed sheets was evaluated. The charge amount was measured by placing 1 g of the developer in a stainless steel meshed cell and applying a nitrogen gas pressure of 0.2 kg / cm.
^This was performed by blowing for 6 seconds at ² and measuring the charge of the remaining carrier. If the variation between the initial charge amount and the charge amount after printing 200,000 sheets is less than 6 μC / g, there is no practical problem. If the variation amount of the charge amount is 6 to 10 μC / g, the toner It is expected to cause scattering and fogging. If the fluctuation width of the charge amount exceeds 10 μC / g, toner scattering and fogging occur, which is not practical.

Here, the cleaning of the photoreceptor employs a blade system. As the fixing device, a pressure fixing type heat fixing device as shown in FIG. 4 was used. The specific configuration of the fixing device is as follows. A cylindrical shape made of aluminum alloy with a built-in heater in the center (inner diameter = 4
The surface of a metal core having a thickness of 0 mm, a thickness of 1.0 mm, and a total width of 310 mm) is covered with a tube of PFA (tetrafluoroethylene-perfluoroalkylvinyl ether copolymer) (thickness: 120 μm) to form a heating roller ( Constituting the upper roller, a cylindrical shape made of iron (inner diameter = 4)
A surface of a core metal having a thickness of 0 mm and a thickness of 2.0 mm was sponge-like silicone rubber (Asker C hardness 48 °, thickness 2 m).
Pressing roller (lower roller) by coating with m)
And the heating roller and the pressure roller are connected to one another.
The nip having a width of 5.8 mm was formed by contact with a total load of 50N. Using this fixing device, the printing linear velocity was set to 250 mm / sec. In addition, as a cleaning mechanism of the fixing device, polydiphenyl silicone (20
(A viscosity of 10 Pa · s at 10 ° C.) was used. The fixing temperature was controlled by the surface temperature of the heating roller (set temperature: 175 ° C.). The amount of silicone oil applied was 0.1 mg / A4.

[0206]

[Table 6]

<Example 21 and Comparative Examples 3 and 4> According to the combinations shown in Table 7 below, the color developer of the present invention and the color developer for comparison were used, and a color copying machine of an intermediate transfer system was used. In a normal temperature and high humidity environment at a temperature of 25 ° C. and a relative humidity of 80%, an actual photographing test was performed to continuously print 50,000 sheets of a document having a full-color pixel ratio of 25%. The color difference was evaluated for the image formed on the tenth sheet. Table 7 shows the results. The evaluation of the color difference was performed by comparing the color of the solid image portion of the secondary color (red, blue, green) in each of the first formed image and the 50,000-th formed image with “Macbeth Color-E”.
ye7000 ", and the color difference was calculated using the CMC (2: 1) color difference equation. If the color difference obtained by the CMC (2: 1) color difference equation is 5 or less, it can be said that the change in the tint of the formed image is acceptable.

Here, the color copier is Y / M / C / B
k is arranged around the stacked photoreceptor, and after developing each color on the photoreceptor, transferring each color onto the intermediate transfer body, forming a color toner image on the intermediate transfer body, and then using the recording material. It has an intermediate transfer member for transferring to a certain transfer paper. The photoconductor was cleaned by a blade cleaning method. As the fixing method, a pressure fixing type heat fixing device as shown in FIG. 4 was used. The specific configuration is as follows. A cylindrical shape made of aluminum alloy with a built-in heater in the center (inner diameter = 40 mm, wall thickness =
1.0 mm, total width = 310 mm)
A (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer) tube (thickness: 120 μm)
heating roller by coating with m) (upper roller)
And a cylindrical shape made of iron (inner diameter = 40 mm, wall thickness =
2.0 mm) with a sponge-like silicone rubber (Asker C hardness 48 °, thickness 2 mm) to form a pressure roller (lower roller), and the heating roller and the pressure roller Was brought into contact with a total load of 150 N to form a 5.8 mm wide nip. Using this fixing device, the linear velocity of printing is set to 250 mm / sec.
c. In addition, as a cleaning mechanism of the fixing device, polydiphenyl silicone (having a viscosity of 10
a · s) was used. The fixing temperature was controlled by the surface temperature of the heating roller (set temperature: 175 ° C.). The amount of silicone oil applied was 0.6 mg / A4.

[0209]

[Table 7]

As described above, it was confirmed that the developers of Examples 1 to 20 of the present invention can stably form high-quality images free of image stains over a long period of time. On the other hand, in the comparative developer 1bk in Comparative Example 1, although the image density was not significantly reduced in the image on the 200,000th sheet, fog was slightly increased, and the comparative developer in Comparative Example 2 With the agent 2bk, the image density of the image on the 200,000th sheet is remarkably reduced, and fogging is frequently generated. In particular, in Comparative Example 1, when the number of sheets exceeded 40,000 sheets, a stain of the fixing offset began to be generated on the back surface of the first sheet after the pause, and the toner was transferred to the transfer sheet in a state where the paper was rubbed. It is not practical due to the appearance of dirt.

Further, it was confirmed that the color developer of the present invention in Example 21 can stably form a high-quality color image with little color difference over a long period of time. On the other hand, in the comparative color developers of Comparative Examples 3 and 4, the color difference was large, and the formed color image was inferior in color reproducibility. In particular, in Comparative Example 3, when the number of sheets exceeds 10,000, a stain of the fixing offset occurs on the back surface of the first sheet after the pause, and the toner is transferred to the transfer paper in a state where the paper is rubbed. It is not practical due to the appearance of dirt.

[0212]

According to the developer of the present invention, a high-quality image free from image contamination can be stably formed for a long period of time. According to the image forming method of the present invention, a high-quality image free from image contamination can be stably formed for a long period of time.

[Brief description of the drawings]

FIG. 1A is an explanatory diagram showing a projected image of a toner particle having no corner, and FIGS. 1B and 1C are explanatory diagrams showing a projected image of a toner particle having a corner.

FIG. 2 is an explanatory diagram showing an example of a configuration of a reaction device used for forming a laminar flow.

FIG. 3 is an explanatory diagram showing a specific example of a shape of a stirring blade.

FIG. 4 is an explanatory cross-sectional view illustrating a configuration example of a fixing device.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Heat exchange jacket 2 Stirring tank 3 Rotating shaft 7 Upper material input port 8 Lower material input port 46, 56 Stirrer blades 5a, 5b, 5c, 5d Stirrer blades 6b, 6c, 6d Inside hole (slit) α intersection angle Reference Signs List 10 heating roller 11 core metal 12 coating layer 13 heating member 20 pressure roller 21 core metal 22 coating layer T toner image

 ──────────────────────────────────────────────────の Continuing from the front page (72) Inventor Hiroshi Yamazaki 2970 Ishikawacho, Hachioji-shi, Tokyo Konica Corporation (72) Inventor Hiroyuki Yamada 2970 Ishikawacho, Hachioji-shi, Tokyo Konica Corporation (72) Inventor Yoshiaki Kobayashi 2970 Ishikawa-cho, Hachioji-shi, Tokyo Konica Corporation F term (reference) 2H005 AA06 AA15 AB06 BA06 CA12 CA14 CA30 EA05 EA10 2H033 AA01 AA09 AA39 BA08 BA24 BA58 BB01 BB17 BB28

Claims (28)

[Claims] 1. An electrostatic image developer comprising a toner containing at least a resin, a release agent and a colorant, and a carrier, wherein the toner is formed by coloring resin particles containing a release agent in a binder resin. Obtained by salting out / fusing the agent particles and
The release agent comprises a crystalline ester compound represented by the following general formula (I), and the carrier comprises a core particle made of a magnetic material, a structural unit represented by the following general formula (II) and a carrier represented by the following general formula: An electrostatic image developer comprising a coating resin layer formed of a silicone resin having the structural unit represented by (III). Embedded image Embedded image 2. An electrostatic image developer comprising a toner containing at least a resin, a release agent and a colorant, and the carrier according to claim 1, wherein the toner contains a release agent in a binder resin. The resin particles and the colorant particles are obtained by salting out / fusion, and the release agent comprises a crystalline ester compound represented by the general formula (I), and The coefficient of variation of the shape factor is 16% or less;
An electrostatic image developer comprising toner particles having a number variation coefficient of 27% or less in a number particle size distribution. 3. The electrostatic charge image developer according to claim 2, wherein the toner is a toner in which the proportion of toner particles having a shape factor in the range of 1.2 to 1.6 is 65% by number or more. 4. The percentage of toner particles having no corners is 50% by number.
The electrostatic image developer according to claim 2, wherein the toner is the toner described above. 5. The number average particle diameter of the toner particles is 3 to 8 μm.
The electrostatic image developer according to any one of claims 2 to 4, wherein the toner is: 6. When the particle size of the toner particles is D (μm), the natural logarithm lnD is set on the horizontal axis, and the horizontal axis is the number-based particle size distribution obtained by dividing the class into a plurality of classes at intervals of 0.23. In the histogram shown, the sum (M) of the relative frequency (m1) of the toner particles included in the most frequent class and the relative frequency (m2) of the toner particles included in the class having the next highest frequency after the most frequent class is 70. The toner according to any one of claims 2 to 5, wherein the toner is not less than%. 7. An electrostatic image developer comprising a toner containing at least a resin, a release agent and a colorant, and the carrier according to claim 1, wherein the toner contains a release agent in a binder resin. It is obtained by salting out / fusing the resin particles and the colorant particles containing,
The release agent comprises the crystalline ester compound represented by the general formula (I), the ratio of the toner particles having no corners is 50% by number or more, and the number variation coefficient in the number particle size distribution is 27%. % Or less of toner particles. 8. The electrostatic image developer according to claim 7, wherein the toner is a toner in which the ratio of toner particles having a shape coefficient in the range of 1.2 to 1.6 is 65% by number or more. 9. The toner particles have a number average particle size of 3 to 8 μm.
The electrostatic image developer according to claim 7, wherein the toner is: 10. When the particle diameter of the toner particles is D (μm), the natural logarithm lnD is plotted on the horizontal axis, and the horizontal axis is 0.23.
In the histogram showing the number-based particle size distribution obtained by dividing into a plurality of classes at intervals, the relative frequency (m1) of the toner particles included in the most frequent class and the class having the next highest frequency after the most frequent class are included. The electrostatic image developer according to any one of claims 7 to 9, wherein the toner (M) has a sum (M) of 70% or more with respect to the relative frequency (m2) of the toner particles. 11. An electrostatic image developer comprising a toner containing at least a resin, a release agent and a colorant, and the carrier according to claim 1, wherein the toner contains a release agent in a binder resin. It is obtained by salting out / fusing the resin particles and the colorant particles containing,
The release agent comprises the crystalline ester compound represented by the general formula (I), and has a shape factor of 1.2.
An electrostatic image developer comprising a toner particle having a ratio of 65% by number or more and a shape coefficient variation coefficient of 16% or less in a range of from 1.6 to 1.6. 12. The toner according to claim 11, wherein the ratio of toner particles having no corners is 50% by number or more.
3. The electrostatic image developer according to item 1. 13. The number average particle diameter of the toner particles is 3 to 8 μm.
The electrostatic image developer according to claim 11, wherein the toner is m. 14. When the particle diameter of the toner particles is D (μm), the natural logarithm lnD is plotted on the horizontal axis, and the horizontal axis is 0.23.
In the histogram showing the number-based particle size distribution obtained by dividing into a plurality of classes at intervals, the relative frequency (m1) of the toner particles included in the most frequent class and the class having the next highest frequency after the most frequent class are included. 14. The electrostatic image developer according to claim 11, wherein the toner has a sum (M) of 70% or more with respect to the relative frequency (m2) of the toner particles. 15. A recording material on which a toner image developed by an electrostatic image developer comprising at least a toner containing a resin, a release agent and a colorant and a carrier is formed.
In an image forming method including a step of fixing by passing between a heating roller and a pressure roller, the toner salt-outs / fuses resin particles containing a release agent and colorant particles in a binder resin. Is obtained by letting
The release agent comprises a crystalline ester compound represented by the following general formula (I), and the carrier comprises a core particle made of a magnetic material, a structural unit represented by the following general formula (II) and a carrier represented by the following general formula An image forming method comprising: forming a coating resin layer with a silicone resin having the structural unit represented by (III). Embedded image Embedded image 16. A recording material on which a toner image developed by an electrostatic image developer comprising at least a toner containing a resin, a release agent and a colorant and the carrier according to claim 15 is formed. In an image forming method including a step of fixing by passing between a heating roller and a pressure roller, the toner salt-outs / fuses resin particles containing a release agent and colorant particles in a binder resin. Is obtained by letting
The release agent comprises the crystalline ester compound represented by the general formula (I), and the coefficient of variation of the shape coefficient is 16% or less, and the number variation coefficient in the number particle size distribution is 27% or less. An image forming method comprising certain toner particles. 17. The image forming method according to claim 16, wherein a toner having a ratio of toner particles having a shape factor in a range of 1.2 to 1.6 is 65% by number or more. 18. A toner according to claim 1, wherein the ratio of toner particles having no corners is 50% by number or more.
The image forming method according to claim 6 or claim 17. 19. The number average particle diameter of the toner particles is 3 to 8 μm.
19. The image forming method according to claim 16, wherein a toner of m is used. 20. Assuming that the particle diameter of the toner particles is D (μm), the natural logarithm lnD is the horizontal axis, and the horizontal axis is 0.23.
In the histogram showing the number-based particle size distribution obtained by dividing into a plurality of classes at intervals, the relative frequency (m1) of the toner particles included in the most frequent class and the class having the next highest frequency after the most frequent class are included. 20. The image forming method according to claim 16, wherein a toner whose sum (M) with the relative frequency (m2) of the toner particles is 70% or more is used. 21. A recording material on which a toner image developed by an electrostatic image developer comprising a toner containing at least a resin, a release agent and a colorant and the carrier according to claim 15 is formed. In an image forming method including a step of fixing by passing between a heating roller and a pressure roller, the toner salt-outs / fuses resin particles containing a release agent and colorant particles in a binder resin. Is obtained by letting
The release agent comprises the crystalline ester compound represented by the general formula (I), the ratio of the toner particles having no corners is 50% by number or more, and the number variation coefficient in the number particle size distribution is 27%. % Of the toner particles. 22. The image forming method according to claim 21, wherein a toner having a shape factor in a range of 1.2 to 1.6 and having a toner particle ratio of 65% by number or more is used. 23. The number average particle diameter of the toner particles is 3 to 8 μm.
The image forming method according to claim 21, wherein a toner having a value of m is used. 24. Assuming that the particle size of the toner particles is D (μm), the natural logarithm lnD is set on the horizontal axis, and the horizontal axis is set to 0.23.
In the histogram showing the number-based particle size distribution obtained by dividing into a plurality of classes at intervals, the relative frequency (m1) of the toner particles included in the most frequent class and the class having the next highest frequency after the most frequent class are included. The image forming method according to any one of claims 21 to 23, wherein a toner having a sum (M) of 70% or more with respect to the relative frequency (m2) of the toner particles is used. 25. A recording material on which a toner image developed by an electrostatic image developer comprising a toner containing at least a resin, a release agent and a colorant and the carrier according to claim 15 is formed. In an image forming method including a step of fixing by passing between a heating roller and a pressure roller, the toner salt-outs / fuses resin particles containing a release agent and colorant particles in a binder resin. Is obtained by letting
The release agent comprises the crystalline ester compound represented by the general formula (I), and has a shape factor of 1.2.
An image forming method comprising: toner particles having a ratio of 65% by number or more and toner particles having a shape coefficient variation coefficient of 16% or less. 26. A toner according to claim 2, wherein the toner has a ratio of toner particles having no corners of 50% by number or more.
6. The image forming method according to 5. 27. The number average particle diameter of the toner particles is 3 to 8 μm.
27. The image forming method according to claim 25, wherein a toner having a value of m is used. 28. When the particle diameter of the toner particles is D (μm), the natural logarithm lnD is plotted on the horizontal axis, and the horizontal axis is 0.23.
In the histogram showing the number-based particle size distribution obtained by dividing into a plurality of classes at intervals, the relative frequency (m1) of the toner particles included in the most frequent class and the class having the next highest frequency after the most frequent class are included. 28. The image forming method according to claim 25, wherein a toner whose sum (M) with the relative frequency (m2) of the toner particles is 70% or more is used.