JP2003156870A - Electrophotographing device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographing device having a wide fixation temperature area and an improved offset-resistance, wherein the life of a fixing member is prolonged, and an odor at the fixation is reduced. SOLUTION: As for the electrophotographing device, the fixation body and the pressure body are separately provided with an elastic layer coated with a surface mold-released layer, and at least one of the fixation body and the pressure body is provided with a heating means, the elastic layer of the fixation body is constituted of insulating rubber, the surface mold-released layer of the fixation body is a fluororesin-coated layer or has a tube structure, the elastic layer of the pressure body is constituted of conductive or insulating rubber, and the surface mold-released layer of the pressure body has a fluororesin tube structure, the toner contains two or more kinds of metallic salt having different values, and provided that the content of the metallic salt contained the most with reference to the total mass of toner is expressed by (a) (mass%) and the content of the metallic salt contained the next most is expressed by (b) (mass%), the following relations are established; 2.0>=a>=0.1, 1.0>=b>=0.01 and 7.5>=a/b>=1.1.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is applied to copiers, printers, facsimiles, etc. to form an electrostatic latent image on an image bearing member and develop the formed electrostatic latent image with toner to form an image. The present invention relates to an electrophotographic device.

[0002]

2. Description of the Related Art Conventionally, in a copying machine or the like utilizing an electrophotographic process, it is necessary to fix an unfixed toner image formed on a recording sheet to a permanent image. A pressure fixing method or a heat fixing method is known.

As the heating and fixing method, a contact heating type heat roller method, which has good thermal efficiency and safety, and an energy saving type film heating method are adopted.

The heat roller type heat fixing device has a heating roller (fixing roller) as a heating rotator and a pressure roller as a pressure rotator in pressure contact with the heating roller. The transfer material sheet on which the unfixed toner image is formed is introduced into the pressure contact nip portion (fixing nip portion) between the rollers by rotating these rollers. Then, when passing through the pressure contact nip portion, the unfixed image is heat-pressure fixed as a permanent image on the base material by the heat from the heating roller and the pressure at the pressure contact nip portion.

In recent years, the size of copying machines and printers has become smaller, and the pressure rollers used in these machines have also become smaller. As the diameter of the pressure roller is reduced, the elastic layer formed on the outer circumference of the core metal of the pressure roller has been reduced in hardness in order to secure the nip width during fixing. For example, as disclosed in Japanese Patent Publication No. 4-77315, sponge-like silicone rubber has been used for the elastic layer. However, in recent years, it has been considered important to secure not only the nip width but also the nip pressure in order to realize good fixing properties. That is, it has been attempted to set the roller hardness of the pressure roller to an appropriate value and satisfy both the preferable nip width and the nip pressure. For example,
In the pressure roller made of sponge-like silicone rubber covered with a fluororesin tube, by setting the roller hardness to 45 to 60 ° (ASKER-C), which is slightly higher than the conventional one, the nip pressure is secured and the fixability is improved. A heat fixing device having improved heat resistance has been proposed (JP-A-5-1079).
No. 72).

However, although the above-mentioned fixing method using a sponge-like silicone rubber roller has an advantage of being inexpensive and excellent in fixing property, since the fixing load is low, the releasing agent from the toner has a low efficiency and an offset occurs. There was a problem that was easy to do. Further, since the rubber layer becomes thick, the resistance of the roller is extremely increased, and electrostatic offset is likely to occur. In particular, there is a problem that the fixing member is contaminated by a slight offset that is not detected in the image and the life is short. Therefore, the fixing device of the same system has not been applied to high speed printers and high speed copying machines.

Further, in the above fixing method, in order to heat the toner image, a minute amount of components contained in the toner may be released into the atmosphere, which may cause an unpleasant odor to the user. Further, in recent years, with the downsizing of copiers and printers, there are more and more opportunities to use them in offices and the like. In addition, the chances of using it in general households are increasing, and as a result, the odor emitted from the toner is often more unpleasant to the user than ever before.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an electrophotographic apparatus having a wide fixing temperature range, excellent offset resistance, a long fixing member life, and a reduced odor during fixing. It is in.

[0009]

The above objects of the present invention have been achieved by the following constitutions.

1. An unfixed image of toner having an elastic layer covered with a surface release layer, a fixing body and a pressure body that rotate in pressure contact with each other, and a heating unit that heats at least one of the fixing body and the pressure body. In an electrophotographic apparatus for fixing the unfixed image on the recording medium by transporting the recording medium carrying the recording medium between the fixing body and the pressure body to apply heat and pressure, the fixing body has an elastic layer. The surface release layer is made of insulating rubber and has a fluororesin coat layer or a tube structure. In the pressing body, the elastic layer is made of conductive or insulating rubber, and the surface release layer is a fluororesin tube. The toner has a fixing device having a structure, the toner contains two or more kinds of metal salts having different valences, and the content of the most contained metal salt in the toner is a (mass%), the next largest. When the content of the contained metal salt is b (mass%), a and There electrophotographic apparatus which is a relation represented by the formula (1).

2. The metal salt most contained in the a (mass%) of the total toner is an aggregation initiator, and the metal salt most contained after the b (mass%) is an aggregation stopper. The electrophotographic apparatus according to 1 above.

3. 3. The electrophotographic apparatus according to item 1 or 2, wherein the toner is a toner produced by salting out / fusing resin particles.

4. 4. The electrophotographic apparatus according to any one of items 1 to 3, wherein the toner is manufactured through a step of forming particles in an aqueous medium and a deodorizing step.

The inventors of the present invention have made extensive studies in view of the above problems, and as a result, in the fixing device of the electrophotographic apparatus, the elastic layer is formed of insulating rubber and the surface release layer is a fluororesin coating layer or A fixing member having a tube structure and a pressure member having an elastic layer formed of a conductive or insulating rubber and a surface release layer having a fluororesin tube structure are used as toner.
It contains two or more kinds of metal salts having different valences, the content of the most contained metal salt is a (mass%), and the content of the next most contained metal salt is b (mass%). )
In this case, by using a toner in which a and b have the relationship represented by the above formula (1), and further by using a toner produced by salting out / fusing resin particles as the toner, fixing is performed. It has been found that the exudation efficiency of the release agent is high and the fixing rate can be increased even when the load is low, and the present invention has been completed.

The resin particles mentioned here refer to resin particles produced by emulsion polymerization or miniemulsion polymerization as described later. Although details will be described later, the release agent is preferably contained in resin particles, but the toner particles may be formed by salting out / fusing resin particles and release agent particles at the same time. The toner produced by salting out / fusing has uniform and dilute salts in the toner.
It has a feature that the occurrence of electrostatic offset is small, and particularly in the fixing device defined in the present invention, the life of the fixing member is greatly improved.

Generally, the emulsion-polymerized toner has an odor at the time of fixing, and particularly in a fixing device using a fixing roll, the time of contact heating (fixing nip passage time).
It has a long odor, so it often produces odor. Therefore, it has been found that providing a deodorizing step in the toner manufacturing step is an extremely effective means. Although the details of the deodorizing step will be described later, it is effective to add a chemical deodorant such as an enzyme or a plant extract component, or a fragrance / masking agent.

The details of the present invention will be described below. In the electrophotographic apparatus according to claim 1, a fixing member and a pressure member that have an elastic layer covered with a surface release layer and rotate in pressure contact with each other, and a heating unit that heats at least one of the fixing member and the pressure member. And a fixing device for fixing the unfixed image on the recording medium by transporting a recording medium carrying an unfixed image of toner between a fixing body and a pressure body to apply heat and pressure. As the constitution of the fixing body, the elastic layer is formed of an insulating rubber, and the surface release layer is a coating layer of fluororesin or a tube structure, and as the constitution of the pressing body, the elastic layer is a conductive or insulating rubber. One of the characteristics is that the surface release layer is formed of a fluororesin tube structure.

First, an example of the electrophotographic apparatus of the present invention will be described. FIG. 1 is a schematic configuration diagram of an electrophotographic apparatus showing an embodiment of the present invention. Reference numeral 4 denotes a photoconductor, which is a typical example of the electrostatic latent image forming member in the present invention. An organic photoconductor (OPC), which is a photosensitive layer, is formed on the outer peripheral surface of an aluminum drum base, and rotates in the direction of the arrow at a predetermined speed.

In FIG. 1, exposure light is emitted from the semiconductor laser light source 1 based on information read by a document reading device (not shown). This is distributed by the polygon mirror 2 in the direction perpendicular to the paper surface of FIG. 1, and is irradiated onto the surface of the photoconductor through the fθ lens 3 that corrects the image distortion to form an electrostatic latent image. The photoconductor is previously uniformly charged by the charger 5, and starts rotating clockwise in accordance with the timing of image exposure.

The electrostatic latent image on the surface of the photoconductor is developed by the developing device 6, and the formed developed image is transferred by the operation of the transfer device 7 to the base material 8 which is conveyed at a timing. Further, the photoreceptor 4 and the base material 8 are separated by a separator (separation electrode) 9, but the toner development image is transferred and carried on the base material 8 and guided to a fixing device 10 to be fixed.

The toner according to the present invention is preferably used in an image forming method including a step of passing a transfer material on which a toner image is formed between a heating roller and a pressure roller constituting a fixing device to fix the transfer material. To be done.

Next, the fixing device according to the present invention will be described. FIG. 2 is a schematic cross-sectional view showing an example of a heating roller type fixing device having a fixing unit with a heating unit.

The fixing device shown in FIG. 2 includes a fixing body 80 (hereinafter, referred to as a heating roller 80) and a pressure body 70 (hereinafter, referred to as a pressure roller 70) that is in contact with the fixing body 80.
In FIG. 2, T is an undeveloped toner image formed on the base material 8, and T'is a fixed toner image.

The heating roller 80 has an elastic layer 82 made of insulating rubber formed on the surface of a cored bar 81 and contains a heating member 75 made of a linear heater.

The pipe-shaped core metal 81 is made of metal and has an inner diameter of 10 to 70 mm. The metal forming the core metal 81 is not particularly limited, but examples thereof include metals such as iron, aluminum and copper, and alloys thereof.

The core metal 81 has a wall thickness of 0.1 to 15 mm, and is determined in consideration of a balance between a request for energy saving (thinning) and strength (depending on constituent materials). For example,
In order for the core metal made of aluminum to maintain the same strength as the core metal made of iron of 0.57 mm, it is necessary to make the wall thickness 0.8 mm.

The insulating rubber that can be used in the elastic layer 82 is not particularly limited, and for example, the layer thickness is 1 to 3 m.
m, a rubber hardness of 20 to 60 Hs (JIS, A rubber hardness) is preferably a thin insulating rubber, and the material is appropriately selected from silicone rubber, Teflon (R) rubber, chloroprene rubber, urethane rubber, EPDM, etc. Can be used.

A surface release layer 71 is provided on the surface of the elastic layer 82. One of the features of the present invention is that the surface release layer 71 is a fluororesin coat layer or a tube structure. The fluororesin that can be used in the present invention is not particularly limited, but for example, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP),
A fluororesin such as polytetrafluoroethylene (PTFE) can be used. In addition, a primer layer may be provided between the layers as needed.

In FIG. 2, a heating member 75 is provided inside the heating roller 80, and a halogen heater or the like can be preferably used.

The temperature of the heating roller 80 is detected by the temperature sensor 86, and the heater driving circuit controls the lighting of the heating member 75 so that the temperature is adjusted to a preset temperature.

On the other hand, the pressure roller 70 comprises a core metal 83, an elastic layer 84 made of conductive or insulating rubber, and a surface release layer 85 having a fluororesin tube structure, which are arranged in this order. A primer layer may be provided between the layers.

The core metal 83 is the heating roller 80 described above.
It is possible to use the same kind as that of the core metal 81.

As the conductive or insulating rubber used in the elastic layer 84, silicone rubber, Teflon (R) rubber, chloroprene rubber, urethane rubber, EPDM, or the like, or a metal oxide such as carbon or zinc oxide is added thereto. It is possible to use a distributed distribution.

The tube-shaped fluororesin which can be used in the surface release layer 85 is not particularly limited,
For example, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FE
P), polytetrafluoroethylene (PTFE) or the like can be used.

The contact load (total load) between the heating roller 80 and the pressure roller 70 is usually 40 to 350 N,
Preferably 50-300 N, more preferably 50-2
It is 50N. The contact load is defined in consideration of the strength of the heating roller 80 (the wall thickness of the core metal 81), and is 0.3, for example.
In a heating roller having a core metal made of mm iron,
It is preferably set to 250 N or less.

From the viewpoint of offset resistance and fixing property, the nip width is preferably 4 to 10 mm, and the surface pressure of the nip is 0.6 × 10 ^{5 to} 1.5 × 1.
It is preferably 0 ⁵ Pa.

If one example of the fixing conditions of the fixing device shown in FIG. 2 is shown, the fixing temperature (surface temperature of the heating roller 10) is 12
0 to 210 ° C, fixing linear velocity of 80 to 640 mm / s
ec.

Next, FIG. 3 shows an example of a fixing device having heating means for both the fixing body and the pressure body.

In FIG. 3, a fixing member (heating roller) 80
The configuration and material of the pressurizing member (pressurizing roller) 70 are shown in FIG.
The conditions can be the same as those described in detail above.

In FIG. 3, a heating member 75 'is also provided inside the pressure roller 70, and for example, a halogen heater or the like can be suitably used, and the unfixed toner image T can be obtained.
The base material 8 carrying the is transported between the heating roller 80 and the pressure roller 70 to perform the fixing process.

The surface of the pressure roller 70 is detected by the temperature sensor 86 ', and the heater driving circuit controls the lighting of the heating member 75' so that the temperature is adjusted to a preset temperature.

A cleaning mechanism may be added to each of the fixing devices according to the present invention, if necessary. In this case, as a method of supplying the silicone oil to the upper roller (heating roller) of the fixing section, 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, one having high heat resistance is used, and polydimethyl silicone, polyphenylmethyl silicone, polydiphenyl silicone or the like is used. Since those having a low viscosity have a large outflow amount at the time of use, those having a viscosity at 20 ° C. of 1 to 100 Pa · s are preferably used.

However, the effect of the present invention is particularly remarkable when the step of forming an image is performed by the fixing device which does not supply the silicone oil or the supply amount of the silicone oil is extremely low. Therefore, even when the silicone oil is supplied, the supply amount is preferably 2 mg or less per A4 sheet.

By setting the amount of silicone oil supplied to 2 mg or less per A4 sheet, the amount of silicone oil adhered to the transfer paper (image support) after fixing is reduced, and the ballpoint pen formed by the silicone oil adhered to the transfer paper is reduced. There is no difficulty in filling with an oil-based pen, and the writing ability is not impaired.

Further, it is possible to avoid problems such as deterioration of offset resistance due to deterioration of silicone oil with time, and contamination of optical system and band electrode by silicone oil.

Here, the amount of silicone oil supplied is determined by transferring the transfer paper (A4) to the fixing device (between rollers) heated to a predetermined temperature.
It is calculated by continuously passing 100 sheets of white paper of a size) and measuring the mass change (Δw) of the fixing device before and after passing the paper (Δw / 100).

Next, the toner according to the present invention will be described. In the invention according to claim 1, the toner contains two or more kinds of metal salts having different valences, the content of the most contained metal salt is a (mass%), and the second largest content is contained with respect to the total mass of the toner. An electrophotographic apparatus, wherein when the content of the metal salt is b (mass%), a and b have a relationship represented by the following formula (1).

Formula (1) 2.0 ≧ a ≧ 0.1 1.0 ≧ b ≧ 0.01 7.5 ≧ a / b ≧ 1.1 However, the masses of a and b represent anhydride conversion values.

The valence of the metal salt as used in the present invention means the valence of the constituent metal elements. In the invention according to claim 2, the metal salt most contained in the toner (a) (mass%) is the aggregation initiator, and the metal salt contained abundantly after the b (mass%). Is a coagulation terminator.

The details of the aggregating initiator and the aggregating terminator will be described later, but in order to salt out, aggregate and fuse the composite resin particles and the colorant particles, the composite resin particles and the colorant particles are dispersed. In the dispersion liquid, a coagulant initiator having a critical coagulation concentration or higher is added, and the dispersion liquid is heated to a glass transition temperature (Tg) or higher of the composite resin particles, so that the coagulation initiator can give a desired composite resin particle. A coagulation terminator is used when the particle size is reached.

As a method for measuring the valence of the metal salt according to the present invention, for example, a fluorescent X-ray analyzer "System 3270" is used.
It can be determined by measuring the fluorescent X-ray intensity emitted from the metal species of the metal salt (for example, calcium derived from calcium chloride) using [Rigaku Denki Kogyo KK]. As a specific measuring method, a plurality of toners having a known metal salt content ratio are prepared, 5 g of each toner is pelletized, and the metal salt content ratio (a and b) and fluorescence from the metal species of the metal salt are prepared. The relationship (calibration curve) with the X-ray intensity (peak intensity) is measured. Then, the toner (sample) whose content ratio of the metal salt is to be measured is pelletized in the same manner, and the fluorescent X-ray intensity from the metal species of the coagulant metal salt is measured to determine the content ratio, that is, "the amount of metal salt in the toner. Can be asked.

(Specific Example of Metal Salt) The method of adding the metal salt is not particularly limited.

Preferably, in the process of salting out, aggregating and fusing the resin particles from the dispersion liquid of the resin particles prepared in an aqueous medium, a divalent to tetravalent metal salt is used as a salting-out agent, and salting out is carried out. A salting-out terminator having a smaller valence than the agent can be stopped and used. As means for controlling the concentration in the toner, the metal salt is confined in the toner particles by the addition amount of the metal salt, the pH at the time of addition, the temperature at the time of addition / after the addition, and then the surface salts are removed by the amount of washing water. Preferably.

The toner production temperature is preferably 100 ° C. or lower. Thereby, the metal cross-linking by the metal salt having a high valence is selectively promoted, and the metal cross-linking structure can be weakened by the metal ion having a low valence in the fixing temperature range of 120 ° C. or higher.

In the toner according to the present invention, the metal salt is preferably an inorganic metal salt in order to promote the metal crosslinking efficiently. Specific examples of the metal salt are shown below.

Examples of the divalent metal salt include magnesium chloride, calcium chloride, zinc chloride, copper sulfate, magnesium sulfate and manganese sulfate, and examples of the trivalent metal salt include aluminum chloride and iron chloride. . Examples of the tetravalent metal salt include titanyl sulfate and tin chloride.

Although these are appropriately selected according to the purpose, a divalent or trivalent metal salt is preferable because aggregation proceeds at an appropriate speed and the toner particle size is easily controlled. Particularly preferably, a divalent metal salt is used. As the monovalent metal salt,
Examples include sodium chloride, potassium chloride, and lithium chloride. In addition to metal salts, ammonium salts such as ammonium chloride can be used. Further, as the divalent to trivalent metal salt, the same ones as the aggregation initiator described later can be used.

Table 1 shows the constitution of the metal salt preferred in the present invention.

[0060]

[Table 1]

The invention according to claim 3 is characterized in that the toner is a toner produced by salting out / fusing resin particles, and in the invention according to claim 4, the particles are formed in an aqueous medium. It is characterized by being manufactured through a process and a deodorizing process.

The toner according to the present invention is characterized in that it is a toner produced by salting out / fusing resin particles, but the resin particles are associated (that is, salting out / fusing) to grow. The aqueous medium preferably contains the below-mentioned anionic surfactant. Although the anionic surfactant and the nonionic or cationic surfactant may be used in combination, the particle size can be controlled with high accuracy by including only the anionic surfactant. The anionic surfactant may be brought in from the resin particle dispersion liquid, or may be newly added at the time of association.

First, the deodorizing technique according to the present invention will be described in detail. In the present invention, the deodorizing treatment with the deodorant is performed in any step until the toner particles containing the resin and the colorant in which the particles are formed in the aqueous medium are separated from the aqueous medium.

Examples of deodorants that can be used in the present invention are shown below, but the present invention is not limited thereto.

(Plant extract component) The plant extract component that can be used in the present invention means an extract derived from a plant, an extract component, or a compound having a structure similar to that of the plant extract component, dispersed in water or the like. Refers to something. In the present invention, the deodorant substance related to the plant extract component is preferably a substance that deodorizes a sulfur-based malodorous component, for example, a green tea extract, a plant extract such as persimmon condensed tannin and bamboo extract is preferable,
These have the effect of chemically decomposing hydrogen sulfide, methyl mercaptan, or the like into odorless molecules, or encapsulating (inclusion) these malodorous molecules to deodorize them.

When the deodorant containing the plant extract component of the present invention is produced from green tea, crushed raw leaves of tea leaves are soaked in ethanol, and then the catechins, vitamins, sugars and enzymes thus obtained are obtained. The deodorant containing the plant extract component according to the present invention can be obtained by filtering and concentrating the ethanol extract solution containing the. More specifically, fresh tea leaves are treated with ethanol at 80 ° C or lower, for example, 50 to 70 ° C.
It was produced by extracting with ethanol and the solution contains ethanol-soluble components and water-soluble components contained in fresh tea leaves. In the extraction of fresh tea leaves with ethanol, the ethanol extract contains (-)-
Epicatechin (EC), (−)-epigallocatechin (E
flavanols such as gC), (−)-epicatechin gallate (ECg) and (−)-epigallocatechin gallate (EGCg), enzymes such as oxidoreductase, transferase, hydrolase and isomerase, flavonols Kind, for example,
Flavone, isoflavone, flavonol, flavanone,
Flava reel, auron, antoanidin, chalcone,
It contains substantially the same extract components as green tea extract including dihydrochalcone and the like and glycosides of flavonols, caffeine, amino acids, flavandiols, polysaccharides and proteins, vitamins and the like. Since the raw leaf component of tea leaves varies depending on the weather, temperature, harvest time and place of harvest, it provides a uniform and stable deodorizing duration as a deodorant and enhances the deodorant effect and deodorant effect of the deodorant. Therefore, it is preferable to add 1 to 2% by mass of the solid content of the synthesized and purified vitamin C and vitamin B1 to the ethanol extract.

The deodorant according to the present invention is an alcohol solution such as ethanol containing catechins, vitamins, sugars and enzymes, and may further contain the extraction residue of alcohol of the raw leaves of tea leaves. Therefore, the deodorant according to the present invention can be produced by immersing a crushed product of fresh tea leaves in alcohol to extract the tea leaf components contained in the fresh leaves.

Other specific examples of the deodorant containing a plant extract component include trees such as cypress, Aomori Hiba, beech, cedar, camphor and eucalyptus, herbs, mustard, wasabi, lemon, quince, peppermint, clove, Ceylon Nikkei,
Bamboo, Iriomote thistle rhizome, Yaeyama palm root, and the like, and an extract or an extract component can be obtained by treating these plants by crushing, pressing, boiling, or steam distillation. Specific examples of plant-derived extract components or synthetic compounds having a structure similar to plant extract components include tropolones such as hinokitiol and α
-Pinene, β-pinene, camphor, menthol, limonene, borneol, α-terpinene, γ-terpinene,
Monoterpenes such as α-terpineol, terpinen-4-ol and cineol, sesquiterpenes such as α-casino and t-mullol, polyphenols such as catechin and tannin, and naphthalene derivatives such as 2,3,5-trimethylnaphthalene. , Long-chain fatty alcohols such as citronellol, cinnamaldehyde, citral,
Examples thereof include aldehydes such as perilaldehyde and allyl compounds such as allyl isothiocyanate. Further, a wood vinegar solution obtained by steaming a tree can also be used in the present invention. When the plant-derived extract component or the synthetic product having the same structure as the plant extract component is insoluble in water, it can be dispersed in water by using a dispersant such as a surfactant.

As the commercially available plant extract deodorant, for example, F118 (manufactured by Fine 2 Co., Ltd.), Delsen (manufactured by Yutsune Pharmaceutical Co., Ltd.) and the like are preferably used.

In the present invention, at least one of the plant extract components is preferably a phytoncide.

The phytoncide type deodorant is mainly composed of a phytoncide-containing plant extract and has a molecular weight of 15,000 to 2,300,00 extracted from coniferous trees.
Anionic activator, glycols,
It is manufactured by adding a special activator, a host compound, etc., and its effect is to completely chemically decompose the odorous component by the neutralization inclusion method and change it to another substance. As a commercially available product, Biodash D-200 (manufactured by Daiso) is preferably used.

(Enzyme Deodorant) In the present invention, the polymerizable monomer is polymerized in an aqueous medium, and an enzyme is added before the toner particles containing at least the resin and the colorant are separated from the aqueous medium. It is preferable to treat with a deodorant.

Biological oxidases, especially some of the metal-containing enzymes, have a function of oxidatively decomposing ammonia, amine, hydrogen sulfide, mercaptans, indole, carbonyl compounds and the like. That is, since many of the odor molecules have mobile hydrogen, they are dehydrogenated and oxidized,
Deodorization becomes possible by making it a dimer, making it water-soluble, and making it non-volatile.

Specific examples of the enzyme having a deodorizing effect include:
Enzymes such as tacarase, amylase, protease, lipase, papain, chymopapain and pepsin can be mentioned. The tacarase enzyme contains hematoporphyrin, which binds to apoprotein, iron is in the electronic state of trivalent spin, and the histidine-imidazole nitrogen of the protein is coordinated to the fifth coordination site. In addition, as a commercially available enzyme-based deodorant,
Bio C (manufactured by Consol Corporation) and Bio Dash P-500 (manufactured by Daiso) are preferably used.

(Metal Phthalocyanines and Artificial Enzyme Deodorants Using the Same) In the present invention, a metal phthalocyanine deodorant is used, and an artificial enzyme deodorant containing a metal phthalocyanine is used as a toner. Is preferably produced.

A metal phthalocyanine derivative having a catalytic activity similar to that of the natural enzyme tacarase, preferably a carboxyphthalocyanine iron complex, particularly preferably an octacarboxyphthalocyanine iron iron complex, has the effect of decomposing odor molecules by a reaction mechanism similar to tacarase. Have. The molecular structure of the octacarboxyphthalocyanine iron complex is shown below.

[0077]

[Chemical 1]

For example, taking the oxidation mechanism of mercaptan as an example, it is shown by the following chemical reaction. ^{2R-SH + 2OH - → 2R} -S - + 2H 2 O (1) 2R-S - + 2H 2 O + O 2 → R-S-S-R + H 2 O 2 + 2OH - (2) ( provided that, R: CH ₃ or C ₂ H ₅ ) The thiolate anion generated by the reaction of the above formula (1) is coordinated with the metal phthalocyanine together with oxygen to become an active species that is a ternary complex, and then coordinated to this active species as in the above formula (2). The resulting thiolate aonine is deodorized by dimerizing into disulfide. Thus, when metal phthalocyanine is used as a deodorant, 1: reaction speed is fast and decomposition efficiency is good 2: reaction proceeds at room temperature 3: there is no concern about environmental pollution because it is an aqueous reaction 4: cycle Since it is a reaction, it is provided with advantageous conditions for decomposing a bad odor such as a long catalyst life.

Further, in the present invention, an artificial enzyme in which a metal phthalocyanine derivative and a polymer compound are ionically bonded is used as a deodorant. As a specific example of the polymer compound, cyclodextrin is preferably used.

(Microbial deodorant) In the present invention, before the polymerizable monomer is polymerized in an aqueous medium and the toner particles containing at least the resin and the colorant are separated from the aqueous medium,
Treatment with a microbial deodorant is preferred.

As the microbial deodorant according to the present invention, a deodorant using a microbial culture is used. Examples of the microorganism include one or more microorganisms selected from the genus Bacillus, Enterobacter, Streptococcus, Rhizopus, and Aspergillus. Furthermore, microorganisms of the genera Nitrosomonas, Nitrobacter and Pseudomonas are preferably used. The microbial deodorant is 5-10 saccharides per 10 parts by weight of these microorganisms.
A mixture of 0 parts by mass, 0.1 to 50 parts by mass of a water-soluble nitrogen compound and 1000 to 50000 parts by mass of water is heated at a temperature of 2
It is obtained by culturing at 0 to 40 ° C. under an oxygen supply of 0.02 to 2.0 liter / min for 15 to 40 hours, and then drying the supernatant or the culture broth obtained by centrifugation. If necessary, 20 to 300 parts by mass of a porous powder such as sawdust may be added to the culture solution to support microorganisms. A liquid aldehyde, specifically, glutaraldehyde may be used in combination with these microbial deodorants. Mixing with a liquid aldehyde is preferable because its deodorizing effect is further enhanced.

Specific examples of the microorganisms preferably used in the present invention include microorganisms of the genus Bacillus, particularly Bacillus subtilis (B. subti).
lis) [IAM (Institute of App
Lied Microbiology; Abbreviation of the Preservation Facility for Useful Strains of the Institute for Applied Microbiology, University of Tokyo; hereinafter also referred to by this abbreviation) 1168],
tto) [IFO (Institute for Fe
mentation Osaka: Abbreviation for Fermentation Research Institute; hereinafter also referred to by this abbreviation) 3009] is preferable, but in addition to this, Baltis coagulans (B. coagulans) [IAM 1115], Bacillus macerans (B) . Macerans) [IA
M 1243] is also available.

Enterobacter
Examples of microorganisms belonging to the genus er) include E. sakazaki [IAM 12660],
Enterobacter agnerance (E. agglon)
erans) [IAM 12659] and the like can be used.

Streptococcus
ccus) microorganisms include Streptococcus
S. faecalis [IAM 111
9], Streptococcus cremoris (S. crem
oris) [IAM 1150] and Streptococcus lactis [IFO 1254].
6] and the like can be used.

As a microorganism (mold) of the genus Rhizopus, R. formosaensis [IAM 625
0], R. oryzae [I
AM6006] or the like can be used.

Aspergillus
Examples of the microorganism belonging to the genus s) include Aspergillus oryzae [IFO 4176] and Aspergillus niger [IFO 406].
6] and the like can be used.

Nitrosomona (Nitrosomona
As the microorganism of the genus s), Nitrosomonas europaea [IFO 14298] and the like can be used.

Nitrobacte
As the microorganism of the genus r), Nitrobacter agilis [IFO 14297] and the like can be used.

Pseudomona
s) genus, P. caryophili [IFO 1295
0], Pseudomonas Stacelli (P.statz
eri) [IFO 3773] and the like can be used.

The microbial deodorant according to the present invention contains dormant microorganisms, organic acids effective for deodorization, and enzymes that decompose organic substances. That is, microorganisms convert sugars and alcohols into organic acids such as lactic acid, citric acid, and malic acid, and produce enzymes (amylase, protease, lipase, etc.) to decompose malodorous sources (organic substances).

(Plant oil deodorant 1) The material effective in the present invention is a plant essential oil obtained from plants of the Lauraceae family, Apiaceae family, Myrtaceae family, Lamiaceae family, Pinaceae family, Cypress family and Gramineae family.

Specifically, the following plant essential oils can be mentioned. These indicate that, for example, cinnamon oil is an essential oil extracted from cinnamon by a steam distillation method. Also,
The names of the main constituent compounds in this essential oil component are shown in parentheses. These vegetable essential oils may be used alone or in a mixture.
It is also obvious that the main constituent compound itself may be used.

Examples of camphoraceae include cinnamon oil (cinnamic aldehyde, cinnamaldehyde), camphor oil (linalol), Ravensala oil (1,8-cineole, α-terpineol), Ravensara eugenol oil (1,8-cineole). , Eugenol), rosewood oil (linalol, α-terpineol), bay leaf oil (linalool, 1,8-cineole, eugenol), and the like as cariaceae, for example, caraway oil (d-carvone, limonene), anise. Oils (anethole, anisaldehyde), angelica oil (α-pinene, α-ferrandrene), galvanum oil (pinene, γ-casinoal), carrot seed oil (carrotol), cumin oil (cuminal), coriander oil (linalol, decanal) , Desenal, octaner ), Dill oil (epoxymenthane, ferrandrene, carpon), fennel oil (anethole, fencon), lobedi oil (ptylidenephthalide, β-ferrandrene, terpinyl acetate, ocimene), etc. Clove oil (eugenol acetate, eugenol), caypte oil (1,8-cineole, α-terpineol), tea tree oil (terpinenol-4, γ-terpinene), niauli oil (1,8-cineole, viridiflorol),
Nyauri nerolidol oil (nerolidol), myrtle (myrte or gimpica) oil (1,8-cineole, alpha
-Pinene, geranyl acetate), eucalyptus globulus oil (globulol, pinocarpon, 1,8-cineole), eucalyptus tygeriana (eucalyptus lemon) oil (citral, geranyl acetate), eucarismine oil (α
-Terpineol, 1,8-cineole), eucalyptus dives oil (piperidone, ferradren), eucalyptus radiata oil (α-terpineol, 1,8-cineole), eucalyptus triodora oil (citronellal, citronellol) Examples include sage oil (Tsuyon, camphor), patchouli oil (patchouli alcohol, guaien), lavender (high R lavender) oil (linalyl acetate, linalool), rosemary camphor oil (camphor, 1,8-cineole). , Rosemary cineole oil (1,8-cineole), spearmint oil (L-carpon, limonene), thyme geraniol oil (geraniol, geranyl acetate), thyme thymol oil (thymol, p-cymene), thyme tunanol. Oil (Tunanol-4, Te Pinenoru -4), time
Linalool oil (sinalol, linalyl acetate), Thyme saturioides oil (borneol, α-terpineol, carvacrol), pasil oil (methylcavicol)
As the Pinaceae, for example, cedar wood oil (cadinene, atlanton), pine oil (α-pinene, β-pinene, β-caryophyllene, α-terpineol), pine nut oil (α-pinene, β-pinene). , Siberian peach oil (bornyl acetate, camphene), balsam fir oil (β-pinene, bornyl acetate), as a cypress family,
For example, cypress oil (α-pinene, β-pinene, terpinyl acetate, cedrol), Junivar branch oil (α-pinene, β-pinene, tsuyopsene, sabinene),
Juniper berry oil (α-pinene, terpinenol-
(4, Germacron), and as a Gramineae, for example,
Examples thereof include citronella oil (methylisoeugenol, geraniol), palmarosa oil (geraniol, geranyl acetate), vetiver oil (vetibo), lemongrass oil (geranial, neral, geraniol).

(Vegetable oil deodorant 2) Materials effective in the present invention include eugenol, cinnamaldehyde, p-cymene, benzaldehyde, benzyl acetate and benzyl benzoate, and at least one selected from them. The feature is to do.

Eugenol includes, for example, Ravensala eugenol (Lauraceae), pasil eugenol (Lamiaceae) and clove (Lupaceae), cinnamaldehyde for cinnamon (Lauraceae), and p-cymene for thymethymol (Lamiaceae). ), And benzyl benzoate has ylang-ylang (Anemoneaceae).

Incidentally, plant oil means flowers of various plants,
Aromatic and volatile oils obtained from leaves, fruits, branches, roots, etc.

(Amyris Oil Deodorant) The term “amiris oil” as used in the present invention means Amyris Balsamifera of the Rutaceae family in northern South America.
ifera) is a plant essential oil extracted by steam distillation from xylem or seeds. Its main ingredients are casino, kazinen,
It's Cariophyllen.

The method of use in the present invention is to emulsify amylis oil in water using a surfactant. After this emulsion is subjected to a polymerization reaction or a salting-out / fusion reaction, filtration /
Used as a cleaning solution during cleaning. As a result, it reacts with the chain transfer agent remaining on the surface of the colored particles to decompose and deodorize the odorous components by a chemical reaction.

(Macrocyclic lactone, macrocyclic ketone compound)
As the macrocyclic lactone compound used as a fragrance,
For example, 14-tetradecanolide, 15-pentadecanolide, 11 (or 12) -pentadecene-15-olide, 16-hexadecanolide and 9-hexadecene-1.
6-olide and the like can be mentioned.

Examples of the macrocyclic ketone compound used as a fragrance include cyclopentadecanone and 3-
Methyl-cyclopentadecanone, cyclohexadecanone, 5-cyclohexadecen-1-one, 8-cyclohexadecen-1-one, cycloheptadecane, 3-ethyl-cyclopentadecanone, 3-propyl-cyclopentadeca Non-, 9-cycloheptadecen-1-one, cycloheneicosanone, 3-methyl-cycloheneicosanone, 11-cycloheneicosen-1-one and the like can be mentioned.

(Pyruvate) In the present invention, it has been found that a highly safe and effective deodorizing effect can be obtained by using the following pyruvate.

[0102]

[Chemical 2]

Here, R represents a linear, branched or cyclic alkyl group, alkenyl group, aryl group or aralkyl group having 1 to 18 carbon atoms. More specifically, as the alkyl group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, amyl group, isoamyl group, hexyl group, heptyl group, octyl group, nonyl group, 2- Examples thereof include groups such as ethylhexyl group, decyl group, cyclopentyl group, cyclohexyl group, and examples of aryl groups include phenyl group, and substituted phenyl groups such as tolyl group and p-chlorophenyl group. Examples of the aralkyl group include benzyl group, phenethyl group, phenylpropyl group, methylbenzyl group, dimethylbenzyl group, trimethylbenzyl group, p-isopropylbenzyl group and the like. Examples of the aralkyl group include a norbornyl group, a citronellyl group and a geranyl group.

Regarding the use of these compounds, they can be used alone or as a mixture. Pyruvate can be prepared by esterifying pyruvate by a known method, or by oxidizing lactic acid ester.

As for the method of use, first, pyruvic acid esters are emulsified in water using a surfactant. Next, at the time of washing, the amount of pyruvic acid ester is 0.0
It is preferable to add the toner particles to the cleaning liquid of the toner particles so that the content of the toner particles is about 1 to 1% by mass. Repeating this step may increase the effect, and thus may be repeatedly washed.

(Deodorant Dissolved or Dispersed in Water) In the present invention, before the polymerizable monomer is polymerized in an aqueous medium and toner particles containing at least a resin and a colorant are separated from the aqueous medium. In addition, it is preferably treated with a deodorant solution dissolved or dispersed in water. Specifically, it is a toner production step such as a polymerization step, a salting out / fusion step, a solid-liquid separation step, a drying step and an external addition step. Among them, it is particularly preferable to perform the deodorizing treatment in any of the polymerization step to the solid-liquid separation step.

The deodorant solution according to the present invention contains 50% by mass or more of water, and may further contain alcohols, alcohol amines, surfactants, and organic acids such as citric acid.

(Adsorption of Deodorant on Surface of Toner Particles) In the present invention, from the viewpoint of maintaining the deodorizing action even if the odorous component of the toner exudes from the inside of the toner during drying or after the hermetically sealed packaging, the deodorizing action is maintained. The agent is preferably adsorbed on the surface. The method of adsorbing is not particularly limited, but it is preferable to dissolve or disperse the deodorant in an aqueous medium in which the toner is polymerized and salted out and aggregated. In the toner filtration washing step described later, a surfactant, a salting out agent, etc. It is particularly preferable to treat with a high-concentration deodorant solution after removing the adhered substances. The deodorant concentration to be adsorbed is
It is preferably 0.01 to 10 ppm. 0.01
If it is less than ppm, the deodorizing action is not long-lasting, and if it is more than 10 ppm, the charging characteristics are not stable.

Further, in a polymerization toner comprising a resin and a colorant formed by polymerizing the above-mentioned radical polymerizable monomer containing each chain transfer agent in an aqueous medium, the radical in the polymerization toner is used. It is preferable that the polymerizable monomer content is 200 ppm or less and the chain transfer agent content is 50 ppm or less. For that purpose, at least a water-soluble polymerization initiator is used in an aqueous medium, and resin particles formed by polymerizing a radical-polymerizable monomer containing a chain transfer agent are melted in an aqueous medium. In the method for producing the legal toner, it is preferable to add the water-soluble polymerization initiator a plurality of times to produce the toner.

In the polymerization toner according to the present invention, it is preferable to use a chain transfer agent having a small odor as the chain transfer agent itself. The chain transfer agents which can be used in the present invention are listed below. Is not limited to these.

Examples of the chain transfer agent that can be used in the present invention include the following general formula (1) or general formula (2).
The compound represented by can be mentioned.

General formula (1) HS-R ₁ -COOR ₂ (In the formula, R ₁ has ₁ to 10 carbon atoms which may have a substituent.
R ₂ is a hydrocarbon group having 2 to 20 carbon atoms which may have a substituent. As preferred compounds of the general formula (1), thioglycolic acid esters and 3-mercaptopropionic acid esters can be mentioned. Specifically, as thioglycolates, ethyl thioglycolate, butyl thioglycolate, thioglycolic acid t
-Butyl, 2-ethylhexyl thioglycolate, octyl thioglycolate, isooctyl thioglycolate, decyl thioglycolate, dodecyl thioglycolate, thioglycolic acid ester of ethylene glycol,
Thioglycolic acid ester of neopentyl glycol,
Trimethylolpropane thioglycolate ester,
Examples thereof include thioglycolic acid ester of pentaerythritol and thioglycolic acid ester of sorbitol. Examples of 3-mercaptopropionic acid esters include ethyl ester, octyl ester, decyl ester, dodecyl ester, pentaerythritol tetrakis ester and ethylene glycol. 3-mercaptopropionic acid ester, neopentyl glycol 3-mercaptopropionic acid ester, trimethylolpropane 3-mercaptopropionic acid ester, pentaerythritol 3-mercaptopropionic acid ester, sorbitol 3-mercaptopropionic acid ester You can

General formula (2) HS-R ₃ (In the formula, R ₃ has 1 to 20 carbon atoms which may have a substituent.
Represents a hydrocarbon group of. ) Preferred are n-octyl mercaptan, 2
-Ethylhexyl mercaptan, n-dodecyl mercaptan, sec-dodecyl mercaptan, t-dodecyl mercaptan and the like can be mentioned.

As another preferable chain transfer agent, a terpene compound can be mentioned. There are some terpene-based compounds that have the same performance as a mercaptan-based compound as a chain transfer agent and that do not generate an odor during fixing by heating. That is, in the toner according to the present invention, it is preferable that among the terpene-based compounds, resin fine particles prepared by a polymerization method using a mono- or sesquiterpene-based compound as a chain transfer agent are used. Further, among the monoterpene compounds, particularly preferable compounds are α-pinene, β-pinene, 3-carene, camphene, limonene, terpinolene, α-terpinene, myrcene, α-terpineol, β-terpineol, linalool, nerol. , Geraniol, and particularly preferred compounds among the sesquiterpene compounds include apple forene and caryophyllene.

The monoterpene compound and sesquiterpene compound chain transfer agent which can be used in the present invention are conventionally known thioglycerin, thioglycolic acid, thioglycolic acid ester, mercaptan compound, carbon tetrachloride, chloroform. Can be used in the same manner as chain transfer agents such as.

In the present invention, the amount of monoterpene compound or sesquiterpene compound used is preferably 0.01 to 5% by mass, more preferably 0.05 to 5% by mass, based on the radical-polymerizable monomer composition. It is 4% by mass. 0.
If the amount is less than 01% by mass, the effect cannot be exhibited.
If the amount exceeds the mass%, the chain transfer agent remains unreacted, which is not preferable.

Other preferred chain transfer agents include:
A mercaptosilane chain transfer agent can be used.

Examples of the mercaptosilane chain transfer agent which can be used in the present invention include mercaptomethyldimethoxysilane, mercaptomethyldiethoxysilane, mercaptomethylethyldimethoxysilane, mercaptomethylethyldiethoxysilane and 2-mercaptoethyldimethoxysilane. Silane, 2-mercaptoethyldiethoxysilane, 2-mercaptoethylethyldimethoxysilane, 2-mercaptoethylethyldiethoxysilane, 3
-Mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-mercaptopropylethyldimethoxysilane, 3-mercaptopropylethyldiethoxysilane, 4-mercaptobutylmethyldimethoxysilane, 4-mercaptobutylmethyldiethoxysilane, 4-mercaptobutylethyldimethoxysilane, 4-mercaptobutylethyldiethoxysilane, 8-mercaptooctylethyldimethoxysilane, 8-mercaptooctylethyldiethoxysilane,
12-mercaptododecylethyldimethoxysilane, 1
2-mercaptododecylethyldiethoxysilane etc. can be mentioned. The amount of the above compound used is preferably 0.01 to 5% by mass based on the total mass of the toner.

As other preferable chain transfer agents, known water-soluble chain transfer agents can be used, and examples thereof include sodium sulfite, sodium bisulfite, potassium bisulfite, sodium pyrosulfite, potassium pyrosulfite, chloromethanol, 2-chloroethanol, 1-chloro-2
-Propanol, 2-chloro-n-propanol, 3-
Chloro-n-propanol, 2-chloro-n-butanol, 3-chloro-n-butanol, 4-chloro-n-butanol, chloropentanol, chlorohexanol,
Chloroheptanol, chlorooctanol, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, chlorodifluoroacetic acid, α-chloropropionic acid, β-chloropropionic acid, p-chlorobenzoic acid, 2-chloro-6-fluorobenzoic acid, α- Bromopropionic acid, β-bromopropionic acid, 2-bromo-n-valeric acid, 5-bromovaleric acid,
11-undecanoic acid, α-bromophenylacetic acid, p-bromophenylacetic acid, 2-bromooctanoic acid, 2-bromopentanoic acid, 2-bromohexanoic acid, 6-bromohexanoic acid, chlorosuccinic acid, chlorofumaric acid, chloromaleic acid Acid, chloromalonic acid, etc. are mentioned.

Next, the method for producing the toner used in the present invention will be described. (Toner Production Method) In the toner production method according to the present invention, the polymerizable monomer is polymerized in an aqueous medium.
There are two characteristics. That is, when forming the resin particles (nucleus particles) or the coating layer (intermediate layer) containing the release agent, the release agent is dissolved in the monomer, and the resulting monomer solution is used as an oil in an aqueous medium. In this method, latex particles are obtained by dispersing in drops, adding a polymerization initiator to this system, and subjecting to a polymerization treatment.

The aqueous medium referred to in the present invention means water 50 to 10
A medium composed of 0 mass% and a water-soluble organic solvent of 0 to 50 mass%. As the water-soluble organic solvent, for example, methanol, ethanol, isopropanol, butanol,
Acetone, methyl ethyl ketone, tetrahydrofuran and the like can be exemplified, and an alcohol-based organic solvent that does not dissolve the obtained resin is preferable.

An example of the method for producing the toner according to the present invention is shown below. The toner manufacturing process mainly includes the following processes.

1: Multi-step polymerization step (I) for obtaining composite resin particles in which a release agent and / or crystalline polyester is contained in a region other than the outermost layer (central portion or intermediate layer) 2: Composite resin particles Salting out / fusing step (II) of salting out and fusing the colorant particles with the colorant particles to filter out the toner particles from the dispersion system of the toner particles, and from the toner particles to the surfactant. Filtering / washing step for removing the like and the like 4: Drying step for drying the washed toner particles, 5: Adding an external additive to the dried toner particles.

Each step will be described in detail below. [Multistage Polymerization Step (I)] The multistage polymerization step (I) is a step of producing composite resin particles by forming a coating layer made of a monomer polymer on the surface of the resin particles by a multistage polymerization method. Is.

In the present invention, it is preferable to employ a multi-step polymerization method of three or more steps from the viewpoint of stability of production and crushing strength of the obtained toner.

The two-step polymerization method and the three-step polymerization method, which are typical examples of the multi-step polymerization method, will be described below.

<Two-Step Polymerization Method> The two-step polymerization method is composed of a central portion (nucleus) formed of a high molecular weight resin containing a release agent and an outer layer (shell) formed of a low molecular weight resin. Is a method for producing composite resin particles. That is, the composite resin particles obtained by the two-step polymerization method are composed of the core and one coating layer.

This method will be described in detail. First, a releasing agent is dissolved in the monomer L to prepare a monomer solution, and the monomer solution is added to an aqueous medium (for example, an aqueous surfactant solution). After the oil droplets are dispersed in the system, the system is polymerized (first stage polymerization).
By doing so, a dispersion liquid of high molecular weight resin particles containing a release agent is prepared.

Then, a polymerization initiator and a monomer L for obtaining a low molecular weight resin are added to the dispersion liquid of the resin particles,
Polymerization of monomer L in the presence of resin particles (second stage polymerization)
Is a method of forming a coating layer made of a low molecular weight resin (polymer of monomer L) on the surface of the resin particles.

<Three-step polymerization method> The three-step polymerization method comprises a central portion (nucleus) formed of a high molecular weight resin, an intermediate layer containing a release agent, and an outer layer (shell) formed of a low molecular weight resin. It is a method for producing composite resin particles. That is, the composite resin particles obtained by the three-step polymerization method are composed of a core and two coating layers.

This method will be described in detail. First, a dispersion liquid of resin particles obtained by a polymerization treatment (first stage polymerization) according to a conventional method is added to an aqueous medium (for example, an aqueous solution of a surfactant). In addition to the addition, a monomer solution obtained by dissolving the release agent in the monomer M is dispersed in the aqueous medium as an oil droplet, and then the system is subjected to a polymerization treatment (second-stage polymerization).
On the surface of the resin particles (core particles), a coating layer (intermediate layer) made of a resin (polymer of the monomer M) containing a release agent is formed to form composite resin particles (high molecular weight resin-intermediate molecular weight resin). )
A dispersion liquid is prepared.

Then, a polymerization initiator and a monomer L for obtaining a low molecular weight resin are added to the obtained dispersion liquid of the composite resin particles, and the monomer L is polymerized in the presence of the composite resin particles. By performing (third stage polymerization), a coating layer made of a low molecular weight resin (polymer of monomer L) is formed on the surface of the composite resin particles. In the above method, by incorporating the second stage polymerization, the release agent can be finely and uniformly dispersed, which is preferable.

A polymerization method suitable for forming resin particles or a coating layer containing a release agent is as follows. An aqueous medium prepared by dissolving a surfactant at a concentration not higher than the critical micelle concentration is used.
A monomer solution in which a release agent is dissolved in a monomer is used to prepare a dispersion liquid by dispersing oil droplets using mechanical energy, and a water-soluble polymerization initiator is added to the obtained dispersion liquid, A method of radical polymerization in oil droplets (hereinafter referred to as "miniemulsion method" in the present invention) can be mentioned, and the effects of the present invention can be more exerted, which is preferable. In the above method, an oil-soluble polymerization initiator may be used instead of the water-soluble polymerization initiator or together with the water-soluble polymerization initiator.

According to the mini-emulsion method of mechanically forming oil droplets, unlike the usual emulsion polymerization method, the releasing agent dissolved in the oil phase is not released and the formed resin particles or A sufficient amount of release agent can be introduced into the coating layer.

Here, the dispersing machine for dispersing oil droplets by mechanical energy is not particularly limited, and for example, a stirrer "CLEARMIX" (M -Technique Co., Ltd.), an ultrasonic disperser, a mechanical homogenizer, a Manton Gaulin, a pressure homogenizer, and the like. The dispersed particle size is 1
0 to 1000 nm, preferably 50 to 1000 n
m, and more preferably 30 to 300 nm.

As another polymerization method for forming the resin particles containing the release agent or the coating layer, an emulsion polymerization method,
Known methods such as a suspension polymerization method and a seed polymerization method can also be adopted. In addition, these polymerization methods include resin particles (core particles) or a coating layer that form composite resin particles,
It can also be employed to obtain a release agent and a crystalline polyester-free material.

The particle size of the composite resin particles obtained in the polymerization step (I) is determined by the electrophoresis light scattering photometer "ELS-80".
0 "(manufactured by Otsuka Electronics Co., Ltd.) is preferably in the range of 10 to 1000 nm in terms of mass average particle size.

Also, the glass transition temperature (T
g) is preferably in the range of 48 to 74 ° C, more preferably 52 to 64 ° C.

The softening point of the composite resin particles is 95-14.
It is preferably in the range of 0 ° C. [Salting out / fusion step (II)] This salting out / fusion step (II)
Is an indefinite shape (non-spherical shape) by salting out / fusing the composite resin particles obtained by the multi-step polymerization step (I) and the colorant particles (progressing salting out and fusing at the same time).
This is a step of obtaining the toner particles of.

The term "salting out" as used in the present invention means that the composite resin particles dispersed in an aqueous medium are aggregated by utilizing the action of salt. In addition, fusion means to eliminate the interparticle interface between resin particles aggregated by the salting out. The salting-out / fusion of the present invention refers to the two steps of salting-out and fusion occurring in sequence, or the action of causing them to occur in sequence. In order to perform salting out and fusion at the same time, particles (composite resin particles, colorant particles) are formed under the temperature condition of the glass transition temperature (Tg) of the resin constituting the composite resin particles or higher.
Need to be aggregated.

In this salting out / fusion step (II), internal additive particles (fine particles having a number average primary particle diameter of about 10 to 1000 nm) such as a charge control agent are salted out together with the composite resin particles and the colorant particles. / May be fused. Further, the colorant particles may be surface-modified, and as the surface-modifying agent,
Conventionally known ones can be used.

The colorant particles are subjected to salting-out / fusion treatment in a state of being dispersed in an aqueous medium. The aqueous medium in which the colorant particles are dispersed is preferably an aqueous solution in which the surfactant is dissolved at a concentration equal to or higher than the critical micelle concentration (CMC).

The disperser used for the dispersion treatment of the colorant particles is not particularly limited, but preferably a stirring device "CLEARMIX (CLEAR) equipped with a rotor rotating at a high speed.
MIX) ”(manufactured by M Technique Co., Ltd.), ultrasonic disperser, mechanical homogenizer, manton-goulin, pressure homogenizer such as pressure homogenizer, and medium type disperser such as Getzman mill and diamond fine mill.

In order to salt out / fuse the composite resin particles and the colorant particles, the salting out agent (aggregating agent) having a critical coagulation concentration or more is added to the dispersion liquid in which the composite resin particles and the colorant particles are dispersed. ) Is added and the dispersion is heated to the glass transition temperature (Tg) or higher of the composite resin particles.

The temperature range suitable for salting out / fusing is (Tg + 10) to (Tg + 50 ° C.), and particularly preferably (Tg + 15) to (Tg + 40 ° C.). In addition, an organic solvent infinitely soluble in water may be added in order to effectively carry out the fusion.

[Filtration / Washing Step] In this filtration / washing step, a filtering treatment for filtering the toner particles from the dispersion system of the toner particles obtained in the above-mentioned step and the filtered toner particles (cake-shaped A cleaning process is performed to remove deposits such as surfactants and salting-out agents from the aggregate.

Here, the filtration method is not particularly limited, such as a centrifugation method, a vacuum filtration method using a Nutsche or the like, a filtration method using a filter press or the like.

[Drying Step] In this step, the washed toner particles are dried.

Examples of the dryer used in this step include a spray dryer, a vacuum freeze dryer, a vacuum dryer and the like. A stationary shelf dryer, a mobile shelf dryer, a fluidized bed dryer, a rotary dryer It is preferable to use a dryer or a stirring dryer.

The water content of the dried toner particles is preferably 5% by mass or less, more preferably 2% by mass or less.

The toner particles that have been dried are
When the aggregates are aggregated by the weak attraction between particles, the aggregates may be crushed. Here, as the disintegration processing device,
A mechanical crushing device such as a jet mill, a Henschel mixer, a coffee mill or a food processor can be used.

The toner according to the present invention forms composite resin particles in the absence of a colorant, and adds the dispersion liquid of the colorant particles to the dispersion liquid of the composite resin particles to obtain the composite resin particles and the colorant particles. Is preferably prepared by salting out / fusing.

Thus, by carrying out the preparation of the composite resin particles in a system without the colorant, the polymerization reaction for obtaining the composite resin particles is not hindered. Therefore, the toner according to the present invention does not impair the excellent offset resistance, and does not cause contamination of the fixing device or image contamination due to toner accumulation.

Further, as a result of the polymerization reaction being surely carried out to obtain the composite resin particles, no monomer or oligomer remains in the resulting toner particles, and the image forming method using the toner concerned is improved. No offensive odor is generated in the heat fixing step.

Further, the obtained toner particles have uniform surface characteristics and a sharp charge amount distribution, so that an image having excellent sharpness can be formed for a long period of time. Such a toner having a uniform composition, molecular weight, and surface characteristics among toner particles maintains good adhesiveness (high fixing strength) to an image support in an image forming method including a fixing step by a contact heating method. However, it is possible to improve the anti-offset property and the wrapping prevention property, and it is possible to obtain an image having an appropriate gloss.

Next, each constituent factor used in the toner manufacturing process will be described in detail. (Polymerizable Monomer) As the polymerizable monomer for producing the resin (binder) used in the present invention, a hydrophobic monomer is used as an essential constituent component, and a crosslinkable monomer is added as necessary. Used. Further, as described below, at least 1 monomer having an acidic polar group or a monomer having a basic polar group is used.
It is desirable to include a kind.

(1) Hydrophobic Monomer The hydrophobic monomer constituting the monomer component is not particularly limited, and conventionally known monomers can be used. Further, one kind or a combination of two or more kinds can be used so as to satisfy the required characteristics.

Specifically, a monovinyl aromatic monomer,
(Meth) acrylic acid ester-based monomer, vinyl ester-based monomer, vinyl ether-based monomer, monoolefin-based monomer, diolefin-based monomer, halogenated olefin-based monomer, etc. may be used. it can.

Examples of vinyl aromatic monomers include:
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- Examples thereof include styrene-based monomers such as octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, 2,4-dimethylstyrene, and 3,4-dichlorostyrene, and derivatives thereof. .

As the acrylic monomer, acrylic acid,
Methacrylic acid, methyl acrylate, ethyl acrylate,
Butyl acrylate, 2-ethylhexyl acrylate,
Cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, ethyl β-hydroxyacrylate, γ-aminoacrylate propyl, stearyl methacrylate, methacrylic Examples thereof include dimethylaminoethyl acid salt and diethylaminoethyl methacrylate.

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

Examples of vinyl ether type monomers include vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, vinyl phenyl ether and the like.

Examples of the monoolefin type monomer include ethylene, propylene, isobutylene, 1-butene, 1-pentene, 4-methyl-1-pentene and the like.

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

(2) Crosslinkable Monomer A crosslinkable monomer may be added to improve the characteristics of the resin particles. Examples of the crosslinkable monomer 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) Monomer having acidic polar group As the monomer having an acidic polar group, (a) an α, β-ethylenically unsaturated compound having a carboxyl group (—COOH) and (b) sulfone. An α, β-ethylenically unsaturated compound having a group (—SO ₃ H) can be mentioned.

Examples of the α, β-ethylenically unsaturated compound having a —COO group of (a) include acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, cinnamic acid and monobutyl maleate. Examples thereof include esters, maleic acid monooctyl esters, and metal salts thereof such as Na and Zn.

Examples of the α, β-ethylenically unsaturated compound having a —SO ₃ H group (b) include sulfonated styrene, its Na salt, allylsulfosuccinic acid, octyl allylsulfosuccinate, and its Na salt. be able to.

(4) Monomer Having Basic Polar Group As the monomer having a basic polar group, (i) an amine group or a quaternary ammonium group having 1 to 1 carbon atoms
2, preferably 2 to 8, particularly preferably 2 (meth) acrylic acid ester of an aliphatic alcohol, (ii) (meth)
Acrylic amide or optionally 1 to 18 carbon atoms on N
(Meth) acrylic acid amide mono- or di-substituted by an alkyl group, (iii) a vinyl compound substituted by a heterocyclic group having N as a ring member, and (iv) N, N-diallyl-
Examples thereof include alkylamines and quaternary ammonium salts thereof. Among them, (i) the (meth) acrylic acid ester of an aliphatic alcohol having an amine group or a quaternary ammonium group is preferable as the monomer having a basic polar group.

Examples of the (meth) acrylic acid ester of an aliphatic alcohol having an amine group or a quaternary ammonium group (i) include dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, and the above. Quaternary ammonium salt of 4 compounds, 3-dimethylaminophenyl acrylate, 2-hydroxy-
3-methacryloxypropyl trimethyl ammonium salt etc. can be mentioned.

Examples of the (meth) acrylic acid amide of (ii) or the (meth) acrylic acid amide optionally substituted with mono- or dialkyl on N include acrylamide, N-butylacrylamide, N, N-dibutylacrylamide, piperidylacrylamide, Methacrylamide, N-butylmethacrylamide, N, N-dimethylacrylamide,
N-octadecyl acrylamide etc. can be mentioned.

Examples of the vinyl compound substituted with a heterocyclic group having N as a ring member in (iii) include vinyl pyridine and
Examples thereof include vinylpyrrolidone, vinyl-N-methylpyridinium chloride and vinyl-N-ethylpyridinium chloride.

Examples of N, N-diallyl-alkylamine of (iv) include N, N-diallylmethylammonium chloride, N, N-diallylethylammonium chloride and the like.

(Polymerization Initiator) The radical polymerization initiator used in the present invention can be appropriately used if it is water-soluble. For example, persulfates (eg, potassium persulfate, ammonium persulfate, etc.), azo compounds (eg, 4,4 ′)
-Azobis-4-cyanovaleric acid and its salts, 2,2'-azobis (2-amidinopropane) salt, etc.), peroxide compounds and the like. Furthermore, the above radical polymerization initiator can be used as a redox initiator in combination with a reducing agent, if necessary. The use of a redox type initiator is preferable because the polymerization activity can be increased, the polymerization temperature can be lowered, and the polymerization time can be further shortened.

Any temperature may be selected as the polymerization temperature as long as it is at least the minimum radical generation temperature of the polymerization initiator, but for example, a range of 50 ° C. to 90 ° C. is used. However, it is also possible to polymerize at room temperature or higher by using a combination of a polymerization initiator that starts at room temperature, for example, a combination of hydrogen peroxide and a reducing agent (ascorbic acid, etc.).

(Surfactant) In order to carry out the miniemulsion polymerization using the above-mentioned polymerizable monomer, it is preferable to use a surfactant to disperse oil droplets in an aqueous medium. The surfactant that can be used in this case is not particularly limited, but the following ionic surfactants can be mentioned as examples of suitable compounds.

Examples of the ionic surfactant include sulfonates (sodium dodecylbenzenesulfonate,
Aryl alkyl polyether sodium sulfonate,
3,3-disulfone diphenylurea-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, etc.), sulfate ester salts (sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, etc.),
Examples thereof include fatty acid salts (sodium oleate, sodium laurate, sodium caprate, sodium caprylate, sodium caproate, potassium stearate, calcium oleate, etc.).

Further, nonionic surfactants can also be used. Specifically, for example, polyethylene oxide, polypropylene oxide, a combination of polypropylene oxide and polyethylene oxide, ester of polyethylene glycol and higher fatty acid, alkylphenol polyethylene oxide, ester of higher fatty acid and polyethylene glycol, ester of higher fatty acid and polypropylene oxide, Examples thereof include sorbitan ester.

In the present invention, these surfactants are mainly used as an emulsifier during emulsion polymerization, but they may be used for other steps or for other purposes.

(Molecular Weight Distribution of Resin Particles and Toner) The toner according to the present invention has a peak or shoulder of 100,000 to
1,000,000, and 1,000-50,000
Preferably, the peak or shoulder is 1
0,000-1,000,000, 25,000-1
More preferably it is present at 50,000 and 1,000 to 50,000.

The molecular weight of the resin particles is 100,000 to
A resin containing at least both a high molecular weight component having a peak or shoulder in the region of 1,000,000 and a low molecular weight component having a peak or shoulder in the region of 1,000 to less than 50,000 is preferable. More preferably, it is preferable to use an intermediate molecular weight resin having a peak or a shoulder at the peak molecular weight of 15,000 to 100,000.

The method for measuring the molecular weight of toner or resin is as follows:
Measurement by GPC (gel permeation chromatography) using THF (tetrahydrofuran) as a solvent is good. That is, 1.0 ml of THF is added to 0.5 to 5 mg of the measurement sample, more specifically 1 mg, and stirred at room temperature using a magnetic stirrer or the like to sufficiently dissolve the sample. Then, pore size 0.45-0.50
After processing with a μm membrane filter, it is injected into GPC. The measurement conditions of GPC are as follows: stabilize the column at 40 ° C., flow THF at a flow rate of 1.0 ml per minute, and
About 100 μl of a sample having a concentration of g / ml is injected and measured. The column is preferably used in combination with a commercially available polystyrene gel column. For example, Shodex GPC KF-801, 802, 8 manufactured by Showa Denko KK
03, 804, 805, 806, 807 combinations, Tosoh TSKgel G1000H, G2000H,
G3000H, G4000H, G5000H, G600
0H, G7000H, TSKguard column
And the like. A refractive index detector (IR detector) or a UV detector may be used as the detector. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated using a calibration curve prepared using monodisperse polystyrene standard particles. About 10 points may be used as polystyrene for preparing the calibration curve.

(Aggregating Agent) The aggregating agent (aggregating initiator, aggregation stopping agent) used in the present invention is preferably selected from metal salts.

Examples of the metal salt include monovalent metal salts such as salts of alkali metals such as sodium, potassium and lithium, divalent metal salts such as salts of alkaline earth metals such as calcium and magnesium and manganese and copper. Valuable metal salt, iron,
Examples include trivalent metal salts such as aluminum.

Specific examples of these metal salts are shown below.
Specific examples of metal salts of monovalent metals include sodium chloride,
Examples of potassium chloride, lithium chloride, and metal salts of divalent metals include calcium chloride, zinc chloride, copper sulfate, magnesium sulfate, and manganese sulfate. Examples of the trivalent metal salt include aluminum chloride and iron chloride. These are appropriately selected according to the purpose. Generally, the divalent metal salt has a smaller critical aggregation concentration (coagulation value or coagulation point) than the monovalent metal salt, and the trivalent metal salt has a smaller critical aggregation concentration.

The critical aggregation concentration referred to in the present invention is an index relating to the stability of the dispersion in the aqueous dispersion, and indicates the concentration at the point where aggregation occurs when a flocculant is added. This critical coagulation concentration greatly changes depending on the latex itself and the dispersant. For example, Seizo Okamura et al., Polymer Chemistry 17,601
(1960) and the like, and the value can be known by following these descriptions. Also, as another method,
It is also possible to add a desired salt to the target particle dispersion liquid while changing the concentration, measure the ζ potential of the dispersion liquid, and set the salt concentration at the point where the ζ potential starts to change to the critical aggregation concentration.

In the present invention, the polymer fine particle dispersion is treated with a metal salt so as to have a concentration higher than the critical aggregation concentration. At this time, of course, directly add the metal salt,
Whether to add as an aqueous solution is arbitrarily selected according to the purpose. When it is added as an aqueous solution, the added metal salt needs to have a critical coagulation concentration of the polymer particles or more with respect to the volume of the polymer particle dispersion and the total volume of the metal salt aqueous solution.

The concentration of the metal salt as the aggregating agent in the present invention may be the critical coagulation concentration or more, but is preferably 1.2 times or more, more preferably 1.5 times or more the critical coagulation concentration.

(Colorant) The toner according to the present invention is obtained by salting out / fusing the above composite resin particles and the colorant particles.

Examples of the colorant (colorant particles to be subjected to salting out / fusion with the composite resin particles) constituting the toner according to the present invention include various inorganic pigments, organic pigments and dyes. As the inorganic pigment, conventionally known ones can be used. Specific inorganic pigments are exemplified below.

Examples of black pigments include furnace black, channel black, acetylene black,
Carbon black such as thermal black and lamp black, and magnetic powder such as magnetite and ferrite are also used.

These inorganic pigments can be used alone or in combination of two or more as desired. Further, the amount of the pigment added is 2 to 20% by mass, preferably 3 to 15% by mass, based on the polymer.

When used as a magnetic toner, the above-mentioned magnetite can be added. In this case, from the viewpoint of imparting a predetermined magnetic characteristic, 20 to 6 is contained in the toner.
It is preferable to add 0% by mass.

Known organic pigments and dyes can be used. Specific organic pigments and dyes are exemplified below.

As a magenta or red pigment,
For example, C.I. I. Pigment Red 2, C.I. I. Pigment Red 3, C.I. I. Pigment Red 5, C.I. I.
Pigment Red 6, C.I. I. Pigment Red 7,
C. I. Pigment Red 15, C.I. I. Pigment Red 16, C.I. I. Pigment Red 48: 1, C.I.
I. Pigment Red 53: 1, C.I. I. Pigment Red 57: 1, C.I. I. Pigment Red 122, C.I.
I. Pigment Red 123, C.I. I. Pigment Red 139, C.I. I. Pigment Red 144, C.I. I.
Pigment Red 149, C.I. I. Pigment Red 1
66, C.I. I. Pigment Red 177, C.I. I. Pigment Red 178, C.I. I. Pigment Red 222
Etc.

Examples of the orange or yellow pigment include C.I. I. Pigment Orange 31, C.I.
I. Pigment Orange 43, C.I. I. Pigment Yellow 12, C.I. I. Pigment Yellow 13, C.I. I.
Pigment Yellow 14, C.I. I. Pigment Yellow 15, C.I. I. Pigment Yellow 17, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 9
4, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 180, C.I. I. Pigment Yellow 1
85, C.I. I. Pigment Yellow 155, C.I. I. Pigment Yellow 156 and the like.

As a pigment for green or cyan,
For example, C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 2, C.I. I. Pigment Blue 1
5: 3, C.I. I. Pigment Blue 16, C.I. I. Pigment Blue 60, C.I. I. Pigment Green 7 and the like.

Examples of dyes include C.I. I. Solvent Red 1, 49, 52, 58, 63,
111, 122, C.I. I. Solvent yellow 1
9, the same 44, the same 77, the same 79, the same 81, the same 82, the same 9
3, ibid 98, ibid 103, ibid 104, ibid 112, ibid 16
2, C.I. I. Solvent Blue 25, 36, 60,
No. 70, No. 93, No. 95 and the like can be used, and a mixture thereof can also be used.

These organic pigments and dyes can be used alone or in combination of two or more as desired.
The amount of pigment added is 2 to 20% by mass based on the polymer.
And preferably 3 to 15 mass% is selected.

The colorant (colorant particles) constituting the toner according to the present invention may be surface-modified. 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 or the like can be preferably used. As the silane coupling agent, for example, methyltrimethoxysilane, phenyltrimethoxysilane,
Alkoxysilanes such as methylphenyldimethoxysilane and diphenyldimethoxysilane, siloxanes such as hexamethyldisiloxane, γ-chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxy. Examples thereof include silane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane and γ-ureidopropyltriethoxysilane. As the titanium coupling agent, for example, TTS, 9S, 38S, 41B, 46B, 55, 1 marketed under the trade name "Planeact" manufactured by Ajinomoto Co., Inc.
38S, 238S, etc., commercial products A-1, B manufactured by Nippon Soda Co., Ltd.
-1, TOT, TST, TAA, TAT, TLA, TO
G, TBSTA, A-10, TBT, B-2, B-4,
B-7, B-10, TBSTA-400, TTS, TO
A-30, TSDMA, TTAB, TTOP and the like can be mentioned. As the aluminum coupling agent, for example,
Examples include "Planeact AL-M" manufactured by Ajinomoto Co., Inc.

The amount of these surface modifiers added is preferably 0.01 to 20% by mass, more preferably 0.1 to 5% by mass, based on the colorant.

As a method of modifying the surface of the colorant particles, a method of adding a surface modifier to the dispersion liquid of the colorant particles and heating the system to react them can be mentioned.

The surface-modified colorant particles are collected by filtration, washed with the same solvent and filtered, and then dried.

(Release Agent) The toner used in the present invention is
It is preferable that the toner is obtained by fusing resin particles containing a release agent in an aqueous medium. Thus, by salting out / fusing the resin particles in which the release agent is included in the resin particles with the colorant particles in the aqueous medium, a toner in which the release agent is finely dispersed can be obtained.

In the toner according to the present invention, the release agent is
Low molecular weight polypropylene (number average molecular weight = 1500-9
000) and low molecular weight polyethylene are preferable, and ester compounds represented by the following formulas are particularly preferable.

R ^1- (OCO-R ² ) _{n In the} formula, n is an integer of 1 to 4, preferably 2 to 4, more preferably 3 to 4, and particularly preferably 4. R ¹ , R
² represents a hydrocarbon group which may have a substituent. R ¹
Has 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms, and more preferably 2 to 5 carbon atoms. R ² has 1 to 40 carbon atoms, preferably 16 to 30 carbon atoms, and more preferably 18 to 26 carbon atoms.

Next, examples of typical compounds are shown below.

[0208]

[Chemical 3]

[0209]

[Chemical 4]

The addition amount of the above compound is 1 to 30% by mass, preferably 2 to 20% by mass, and more preferably 3 to 15% by mass, based on the whole toner.

The toner according to the present invention is preferably prepared by encapsulating the above-mentioned releasing agent in resin particles by a mini-emulsion polymerization method, and salting out and fusing with the toner particles.

(Charge control agent) To the toner, a material capable of imparting various functions as a toner material may be added in addition to the colorant and the release agent. Specific examples include charge control agents. These components can be added by various methods such as a method of adding the resin particles and the colorant particles at the same time as the salting-out / fusing step and incorporating them into the toner, a method of adding them to the resin particles themselves.

As the charge control agent, various known ones and those which can be dispersed in water can be used. Specific examples thereof include nigrosine dyes, naphthenic acid or higher fatty acid metal salts, alkoxylated amines, quaternary ammonium salt compounds, azo metal complexes, salicylic acid metal salts or metal complexes thereof.

(External Additive) A so-called external additive may be added to the toner according to the present invention for the purpose of improving fluidity and cleaning property. 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 which can be used as the external additive, conventionally known ones can be mentioned. Specifically, silica fine particles, titanium fine particles, alumina fine particles and the like can be preferably used. These inorganic fine particles are preferably hydrophobic.

Specific examples of the silica fine particles include commercially available products R-805, R-976 and R- manufactured by Nippon Aerosil Co., Ltd.
974, R-972, R-812, R-809, HVK-2150, H-200 manufactured by Hoechst Co., Ltd., and commercial products TS-720, TS-530, TS manufactured by Cabot Co., Ltd.
-610, H-5, MS-5, etc. are mentioned.

Specific examples of titanium fine particles include, for example,
Commercial products T-805 and T-60 manufactured by Nippon Aerosil Co., Ltd.
4. Commercial products MT-100S, MT-1 manufactured by Teika Co., Ltd.
00B, MT-500BS, MT-600, MT-60
0SS, JA-1, commercial product TA- manufactured by Fuji Titanium Co., Ltd.
300SI, TA-500, TAF-130, TAF-
510, TAF-510T, commercial products IT-S, IT-OA, IT-OB, IT-OC manufactured by Idemitsu Kosan Co., Ltd. and the like can be mentioned.

Specific examples of the alumina fine particles include commercially available products RFY-C and C- manufactured by Nippon Aerosil Co., Ltd.
604, a commercial product TTO-55 manufactured by Ishihara Sangyo Co., Ltd., and the like.

Examples of organic fine particles that can be used as an external additive include spherical fine particles having a number average primary particle diameter of about 10 to 2000 nm. Examples of the constituent material of such organic fine particles include polystyrene, polymethylmethacrylate, and styrene-methylmethacrylate copolymer.

Examples of the lubricant that can be used as an external additive include metal salts of higher fatty acids. Specific examples of such metal salts of higher fatty acids include zinc stearate, aluminum stearate, copper stearate, magnesium stearate, calcium stearate, and other stearic acid metal salts; zinc oleate, manganese oleate, iron oleate, and olein. Oleic acid metal salts such as copper acid and magnesium oleate; Metal palmitate salts such as zinc palmitate, copper palmitate, magnesium palmitate and calcium palmitate; Metal linoleate salts such as zinc linoleate and calcium linoleate; Ricinol Examples thereof include metal salts of ricinoleic acid such as zinc acid salt and calcium ricinoleate.

The addition amount of the external additive is preferably about 0.1 to 5% by mass with respect to the toner.

<Step of Adding External Additive> This step is a step of adding the external additive to the dried toner particles.

The equipment used for adding the external additive includes a Turbuler mixer, a Hensiel mixer,
Various known mixing devices such as a Nauta mixer and a V-type mixer can be mentioned.

(Toner Particles) The toner according to the present invention preferably has a number average particle diameter of 3 to 10 μm, more preferably 3 to 8 μm. This particle size is
In the toner production method, it can be controlled by the concentration of the aggregating agent (salting out agent), the addition amount of the organic solvent, the fusing time, and the composition of the polymer.

When the number average particle diameter is 3 to 10 μm, the number of toner fine particles having large adhesiveness that fly and adhere to the heating member to cause offset is reduced in the fixing step, and the transfer efficiency is increased. The image quality of halftone is improved, and the image quality of thin lines and dots is improved.

The number average particle size of the toner is, Coulter Counter TA-II, Coulter Multisizer, SLAD
1100 (a laser diffraction particle size measuring device manufactured by Shimadzu Corporation) can be used for the measurement.

In the present invention, a Coulter Multisizer was used, and an interface (manufactured by Nikkaki Co., Ltd.) for outputting the particle size distribution and a personal computer were connected and used. As the aperture in the Coulter Multisizer, a 100 μm aperture was used, and the volume distribution of the toner of 2 μm or more (for example, 2 to 40 μm) was measured to calculate the particle size distribution and the average particle size.

<Range of preferable shape factor of toner particles>
The toner according to the present invention has a shape factor of 1.0 to 1.6 with 65% by number or more, preferably 1.2 to 1.6 with 65% by number or more, particularly preferably 1.2 to 1 No. 0.6 is 70% by number or more.

The shape factor of the toner according to the present invention is represented by the following formula and represents the degree of roundness of toner particles.

Shape factor = ((maximum diameter / 2) 2 × π) / projected area Here, the maximum diameter means that when a projected image of a toner particle on a plane is sandwiched by two parallel lines, the parallel line Refers to the width of the particles at which the interval is maximum. The projected area means the area of the projected image of the toner particles on the plane. In the present invention, this shape factor is obtained by taking a photograph of the toner particles magnified 2000 times with a scanning electron microscope, and then based on the photograph, "SCANNING IMAGE ANALYZE
R ”(manufactured by JEOL Ltd.) was used to measure the photographic image. At this time, the shape factor of the present invention was measured by the above calculation formula using 100 toner particles.

In the toner according to the present invention, when the particle diameter of the toner particles is D (μm), the natural logarithm lnD is plotted on the abscissa, and this abscissa is divided into a plurality of classes at intervals of 0.23. In the histogram showing the particle size distribution of, the sum 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 next most frequent class ( It is preferable that the toner M) is 70% or more.

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 narrow, so that the toner is used in the image forming step. As a result, the occurrence of selective development can be reliably suppressed.

In the present invention, the histogram showing the number-based particle size distribution has a natural logarithm lnD (D: particle size of each toner particle) at a plurality of grades (0 to 0) at intervals of 0.23.
0.23: 0.23 to 0.46: 0.46 to 0.69:
0.69 to 0.92: 0.92 to 1.15: 1.15
1.38: 1.38 to 1.61: 1.61 to 1.84:
1.84-2.07: 2.07-2.30: 2.30-
2.53: 2.53 to 2.76 ...), which is a histogram showing a number-based particle size distribution, and the histogram shows particle size data of a sample measured by a Coulter Multisizer according to the following conditions. Is transferred to a computer via an I / O unit and is created by the particle size distribution analysis program in the computer.

[Measurement conditions] 1: Aperture: 100 μm 2: Sample preparation method: Electrolyte solution [ISOTON R-11
(Made by Coulter Scientific Japan)] 5
An appropriate amount of a surfactant (neutral detergent) is added to 0 to 100 ml and stirred, and 10 to 20 mg of a measurement sample is added thereto. This system is prepared by subjecting it to an ultrasonic disperser for 1 minute.

(Developer) The toner according to the present invention may be used as a one-component developer or a two-component developer.

When used as a one-component developer, 0.1 to 0.5 μm is contained in a non-magnetic one-component developer or toner.
A magnetic one-component developer containing a certain amount of magnetic particles can be used, and any one can be used.

Also, it can be used as a two-component developer by mixing with a carrier. In this case, as the carrier magnetic particles, metals such as iron, ferrite and magnetite,
Conventionally known materials such as alloys of these metals with metals such as aluminum and lead can be used. Ferrite particles are particularly preferable. The volume average particle diameter of the magnetic particles is 15 to 100 μm, and more preferably 25 to 8 μm.
0 μm is preferable.

The volume average particle size of the carrier is typically measured by a laser diffraction type particle size distribution measuring device “HELOS” equipped with a wet disperser (SYMPATIC (SYMP).
(Made by ATEC)).

The carrier is preferably one in which magnetic particles are further coated with a resin, or a so-called resin dispersion type carrier in which magnetic particles are dispersed in a resin. The resin composition for coating is not particularly limited, but, for example, an olefin resin, a styrene resin, a styrene-acrylic resin, a silicone resin, an ester resin, a fluorine-containing polymer resin, or the like is used. The resin for forming the resin-dispersed carrier is not particularly limited, and known ones can be used. For example, styrene-acrylic resin, polyester resin, fluorine resin, phenol resin, etc. are used. be able to.

[0240]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these embodiments.

<< Preparation of Various Deodorants >> Deodorants 1 to 4 were prepared according to the following method.

<Deodorant 1: Deodorant for plant extract component> 10 g of a commercially available deodorant for plant extract component F118 (manufactured by Fine 2 Co., Ltd.) was dissolved in 2 kg of ion-exchanged water at 40 ° C. Deodorant 1 was prepared.

<Deodorant 2: Enzyme-based deodorant> Bio-Dash P-500 (manufactured by Daiso) 5 which is a commercially available deodorant
g was dissolved in 2 kg of ion-exchanged water at 40 ° C. to prepare deodorant 2.

<Deodorant 3: Enzyme-based deodorant containing a plant extract component> Commercially available deodorant Bio-C (enzyme-based deodorant manufactured by Consol Corporation and containing a plant extract component) 5 g Was dissolved in 2 kg of ion-exchanged water at 40 ° C. to prepare deodorant 3.

<Deodorant 4: Amiris Oil Deodorant> 2 g of amiris oil is ion-exchanged water 20 containing a surfactant.
Dispersion was carried out at 0 m to prepare deodorant 4 which was an emulsion.

<< Preparation of Toner and Developer >> (Preparation of Resin Particles) [Preparation of Resin Particles 1HML] <1: Preparation of Core Particles (First Stage Polymerization)> Stirrer, Temperature Sensor, Cooling Tube, Nitrogen Introducing Device 5000m with attached
In a separable flask of 1, the anionic surfactant A
_{(C 10 H 21 (OCH 2} CH 2) 2 OSO 4 Na) 7.08g
Was charged in 3010 g of ion-exchanged water, and a surfactant solution (aqueous medium) was charged, and the internal temperature was raised to 80 ° C. while stirring at a stirring rate of 230 rpm under a nitrogen stream.

9.2 g of a polymerization initiator (potassium persulfate: KPS) was added to this surfactant solution in 200 g of deionized water.
Was added to the initiator solution and the temperature was raised to 75 ° C., and then 70.1 g of styrene and 1-n-butyl acrylate were added.
A monomer mixture solution consisting of 9.9 g and methacrylic acid 10.9 g was added dropwise over 1 hour, and this system was heated at 75 ° C. for 2 hours with stirring to perform polymerization (first stage polymerization), Resin particles (dispersion liquid of resin particles composed of high molecular weight resin) were prepared. This is designated as resin particle (1H).

<2: Formation of Intermediate Layer (Second Stage Polymerization)> In a flask equipped with a stirrer, styrene 10 was added.
5.6 g, n-butyl acrylate 30.0 g, methacrylic acid 15.4 g, and n-octyl-3-mercaptopropionic acid ester 5.6 g were added to the monomer mixture solution containing the above-mentioned exemplified compound 19) as a release agent. Add 98.0g,
Monomer solution 1 was prepared by heating and dissolving at 90 ° C. Then, a surfactant solution prepared by dissolving 1.6 g of the anionic surfactant A in 2700 ml of deionized water is heated to 98 ° C., and the surfactant solution is mixed with the resin particles (1H ) Is added as a solid content, and then a mechanical disperser having a circulation path "CLEARMIX" (manufactured by M Technique Co., Ltd.)
Thus, the prepared monomer solution 1 was mixed and dispersed to prepare an emulsion containing emulsion particles having a uniform dispersed particle diameter (284 nm).

Then, a polymerization initiator (KP
S) 5.1 g of a solution of an initiator dissolved in 240 ml of ion-exchanged water and 750 ml of ion-exchanged water were added, and this system was heated and stirred at 98 ° C for 12 hours to perform polymerization (second-stage polymerization). , Resin particles (dispersion liquid of composite resin particles having a structure in which the surface of resin particles made of a high molecular weight resin is covered with an intermediate molecular weight resin) were obtained. Let this be a resin particle (1HM).

The above resin particles (1HM) were dried and observed by a scanning electron microscope. As a result, particles (400 compound which was not surrounded by latex) as a main component (400)
˜1000 nm) was observed.

<3: Formation of Outer Layer (Third Stage Polymerization)> A polymerization initiator (KPS) was added to the resin particles (1HM) prepared above.
An initiator solution prepared by dissolving 7.4 g in 200 ml of ion-exchanged water was added, and styrene 300 was added under the temperature condition of 80 ° C.
g, n-butyl acrylate 95 g, methacrylic acid 3
A monomer mixture solution consisting of 5.4 g and 10.4 g of n-octyl-3-mercaptopropionic acid ester was added dropwise over 1 hour. After completion of the dropping, polymerization (third stage polymerization) was carried out by heating and stirring for 2 hours, followed by cooling to 28 ° C. to obtain resin particles (a central portion made of a high molecular weight resin and an intermediate layer made of an intermediate molecular weight resin). , An outer layer made of a low molecular weight resin, and an exemplary compound 19) as a release agent in the intermediate layer.
A dispersion liquid of composite resin particles containing is obtained. The resin particles are referred to as resin particles (1HML).

The composite resin particles constituting this resin particle (1HML) are 138,000, 78,000 and 1.
Has a peak molecular weight of 4,500, and
The mass average particle diameter of the composite resin particles was 124 nm.

[Preparation of Resin Particles (2HML)] In the preparation of the above resin particles (1HML), the addition amount of methacrylic acid in the formation of the intermediate layer (second-stage polymerization) was changed from 15.4 g to 10.5 g, and the outer layer was further added. Formation (third stage polymerization), the amount of methacrylic acid added was 35.4 g to 18.5 g.
In the same manner except that the resin particles (a central portion made of a high molecular weight resin, an intermediate layer made of an intermediate molecular weight resin,
A dispersion liquid of composite resin particles having an outer layer made of a low molecular weight resin was prepared. This resin particle is referred to as “resin particle (2HM
L) ”.

The composite resin particles constituting this resin particle (2HML) are 118,000, 80,000 and 1
Has a peak molecular weight of 3,500, and
The mass average particle diameter of the composite resin particles was 110 nm.

(Preparation of Toner) [Preparation of Toner Particles] <Preparation of Toner Particles 1 to 4> Anionic Surfactant B
59.0 g of (sodium dodecyl sulfate) was stirred and dissolved in 1600 ml of ion-exchanged water. While stirring this solution, 420.0 g of carbon black "Regal 330" (manufactured by Cabot) is gradually added, and then dispersed by using "Clearmix" (manufactured by M Technique) to color A dispersion liquid of agent particles (hereinafter referred to as colorant dispersion liquid 1) was prepared. This colorant dispersion 1
The particle diameter of the colorant particles in was measured using an electrophoretic light scattering photometer "ELS-800" (manufactured by Otsuka Electronics Co., Ltd.), and the mass average particle diameter was 98 nm.

The resin particles (1HML) prepared above were mixed with 42
0.7g (as solid content) and 900g of deionized water
And 166 g of the colorant dispersion liquid 1 prepared above were placed in a reaction vessel (four-necked flask) equipped with a temperature sensor, a cooling pipe, a nitrogen introducing device, and a stirring device and stirred. After adjusting the temperature in the container to 30 ° C., a 5 mol / L sodium hydroxide aqueous solution was added to this solution to adjust the pH to 9.0.

Then, an aqueous solution prepared by dissolving each flocculant in 1000 ml of ion-exchanged water in the combinations shown in Table 2 was added under stirring at 30 ° C. for 10 minutes. After standing for 3 minutes, the temperature starts to be raised, and this aqueous solution is used for 9 minutes over 9 minutes.
The temperature was raised to 0 ° C., and particle growth was started. In that state,
The particle size of the associated particles was measured with "Coulter Counter TA-II", and when the volume average particle size reached 4.0 µm,
An aqueous solution prepared by dissolving the stopper described in Table 2 in 1000 ml of ion-exchanged water was added to stop grain growth. further,
As the aging treatment, the fusion was continued by heating and stirring at a liquid temperature of 98 ° C. for 2 hours. Then, it cooled to 30 degreeC on condition of 8 degree-C / min. Then, hydrochloric acid was added to adjust the pH to 2.0, and stirring was stopped. The associated particles thus formed were filtered through a Nutsche and repeatedly washed with ion-exchanged water at 45 ° C., and then the deodorants prepared in the combinations shown in Table 2 were each poured onto the Nutche and filtered, and then at 40 ° C. The toner particles 1 to 4 of the present invention having the constitution shown in Table 2 were prepared by drying with the warm air of No. 2.

<Preparation of Toner Particles 5 to 7> In the preparation of the above toner particles 1 to 4, resin particles (2HML) were used in place of the resin particles (1HML), and as shown in Table 2, an aggregating agent and a stopping agent were used. Toner particles 5 to 7 were prepared by changing the type and amount of the agent and the type of deodorant.

<Preparation of Comparative Toner Particles 1> 55 parts by mass of a polymer of styrene and acrylic acid having a maximum value in the molecular weight of 3,000, styrene and butyl acrylate,
20 parts by mass of a polymer composed of acrylic acid having a maximum value at a molecular weight of 100,000 and 25 parts by mass of a polymer composed of styrene and butyl acrylate having a maximum value at a molecular weight of 650,000 are uniformly dispersed in xylene. Blended. Xylene was distilled off under reduced pressure to obtain Binder Resin 1.

100 parts by mass of binder resin 1, 10 parts by mass of carbon black and 4 parts by mass of polypropylene wax were melt-kneaded by a twin-screw kneader and then pulverized by a jet mill. Then, a toner composition having a volume average particle diameter of 8.5 μm was obtained with an air classifier. To 100 parts by mass of this toner composition, 1 part by mass of hydrophobic silica was added and mixed with a dry mixer to obtain comparative toner particles 1.

The molecular weight distribution of this comparative toner particle 1 was measured by gel permeation chromatography. As a result, the molecular weight was 3,000 in the chromatogram.
Had a main peak, one peak at a molecular weight of 500,000, and a shoulder near a molecular weight of 130,000. Low molecular weight component (LP) is 63% by mass, intermediate molecular weight component (MP) is 20% by mass, and high molecular weight component (HP) is 17% by mass.
Mass%, [MPratio + 2 × HPrati
o] was 54% by mass. Further, as a result of measuring the glass transition point of this comparative toner particle 1, the glass transition point was 55.
It was ℃.

The glass transition temperature is measured by DSC.
The glass transition point was defined as the intersection between the baseline and the slope of the endothermic peak. Specifically, using a differential scanning calorimeter, the temperature is raised to 100 ° C., left at that temperature for 3 minutes, and then cooled to room temperature at a falling temperature of 10 ° C./min. Then, when this sample was measured at a temperature rising rate of 10 ° C./min, an extension line of the baseline below the glass transition point,
The intersection with the tangent line showing the maximum slope from the rising portion of the peak to the apex of the peak was measured as the glass transition point. As a measuring device, DS manufactured by Perkin Elmer
C-7 was used.

[0263]

[Table 2]

(Measurement of metal salts a and b in each toner particle)
The contents of the metal salts a and b defined in claim 1 were measured for each of the prepared toners, and the results are shown in Table 3.

The content of the metal salts a and b in each toner was measured by a fluorescent X-ray analyzer "System 3270 type".
(Manufactured by Rigaku Denki Kogyo Co., Ltd.), the fluorescent X-ray intensity emitted from the inorganic salt metal species (eg, calcium derived from calcium chloride) and the corresponding fluorescent X-ray intensity of the base were determined.

[0266]

[Table 3]

(Preparation of Developer) As a developer, a silicone-coated carrier having a volume average particle diameter of 60 μm was used and mixed with each toner so that the toner concentration was 6%.

<Image formation and evaluation of formed image> (Image formation) (Production of pressure roller) Pressure rollers 1 to 3 were produced according to the method described below.

<Production of Pressure Roller 1> For 100 parts by mass of a mixture of diorganopolysiloxane, a polymerization catalyst and AIBN, a glass balloon (Glass Bubbles K15: average particle size 100 μm, as an inorganic minute hollow body, True specific gravity of 0.15 g / ml, Sumitomo 3M) 5 parts by mass,
This is heated to a rubber length of 225 mm and a rubber thickness of 2.5 m.
A sponge-like silicone rubber having an m and an outer diameter of 20 mm was obtained. Note that the glass balloons are observed with a microscope, and half of the sum of the major axis and the minor axis of each glass balloon is defined as the particle size,
The particle diameters of 0 glass balloons were averaged to obtain the average particle diameter. The true specific gravity means the powder density excluding air, and was measured using an air comparison pycnometer according to ASTM D2840.

Since the mass of the polymerization catalyst and AIBN and the mass change accompanying the reaction can be ignored, in this case, 5 parts by mass of the glass balloon was added to 100 parts by mass of the sponge-like silicone rubber. The sponge-like silicone rubber thus obtained was coated with and adhered to a PFA tube having a thickness of 30 μm to prepare a pressure roller 1. The foaming ratio of the sponge-like silicone rubber is approximately 150%, and the thermal conductivity measured using a rapid thermal conductivity meter QTM-D3 manufactured by Kyoto Electronics Co., Ltd. is 1.2 × 10 ⁻³ (W / cm · ℃). The roller hardness is 52 ° (JIS-S-605
According to 0), the surface hardness of the pressure roller was directly measured.
Specifically, it was measured with an ASKER-C type rubber hardness meter manufactured by Kobunshi Keiki Co., Ltd. under a load of 600 g.

<Production of Pressure Roller 2> As an inorganic minute hollow body, glass balloon (Glass Bubbles K1: average particle diameter 120 μm, true specific gravity 0.10 g / ml, manufactured by Sumitomo 3M Ltd.)
A pressure roller 2 was produced in the same manner as the pressure roller 1 except that 8 parts by mass was used. The expansion ratio is about 130%,
The heat conductivity was 9.7 × 10 ⁻⁴ (W / cm · ° C.).
The roller hardness was 55 ° (ASKER-C).

<Production of Pressure Roller 3> A core metal is inserted into a polyimide tube having a thickness of 20 μm to be used as a release layer, and a raw material 100 of hydrogen foaming type sponge silicone rubber is prepared.
A mixture of 10 parts by mass of a glass balloon (Glass Bubbles K15: average particle size 100 μm, true specific gravity 0.15 g / ml, manufactured by Sumitomo 3M Co., Ltd.) as an inorganic micro hollow body was used between the core metal and the tube. It has a surface length of 225 mm and a rubber thickness of about 2.5 mm.
A pressure roller 3 having an outer diameter of 20 mm was produced. The outer peripheral surface of the polyimide tube is previously coated with a fluororesin coating having a thickness of 10 μm. In addition, the inner peripheral surface is pre-treated with a primer, and at the same time when the sponge-like silicone rubber is formed,
A release layer made of polyimide coated with fluororesin is adhered.

The expansion ratio of the sponge-like silicone rubber is
It is about 400%, and the heat conduction is 5.5 × 10 ^-4 (W
/Cm.degree. C.). The roller hardness is 53 °
(ASKER-C).

(Production of Heating Roller 1) As the heating roller 1, an aluminum cored bar having an outer diameter of 30 mm and a thickness of 1.5 mm was used.
An elastic layer is made of silicon rubber, and PFA is 15μ on it.
What was m-coated was used.

(Production of Heating Roller 2) As the heating roller 2, an aluminum cored bar having an outer diameter of 30 mm and a thickness of 1.5 mm was used.
An elastic layer made of silicon rubber was coated on the elastic layer with a PFA having a tube structure having a thickness of 15 μm.

(Image formation) Image formation was carried out by combining the toners prepared as described above with the pressure rollers and heating rollers prepared above, as shown in Table 4.

As the image forming apparatus, a heating roll type fixing device having the heating means shown in FIG. 3 in the fixing body and the pressure body was used.

The fixing device shown in FIG. 3 includes a heating roller 80.
A ceramic heater is provided as a heating member 75 inside the, and the surface temperature of the heating roller 80 is 170 ° C.
Fixing speed 220mm / sec, nip width 10m
set to m. The unfixed toner image is introduced into and passed through the nip # area formed by the heating roller 80 and the pressure roller 70, and each toner image printed on the base material is fixed by heat and pressure, and the fixing state is obtained. The following evaluation was performed. The toner density of the unfixed toner image was 1.5 mg / cm ² .

[Evaluation of Formed Image] <Measurement of Fixable Temperature Range> The temperature of the fixing roll is 120 ° C.
A fixed image was prepared by changing the temperature in the range of up to 240 ° C in steps of 10 ° C. In outputting the fixed image, A4 size plain paper (basis weight: 64 g / m ² ) was used.

The fixing strength of the obtained fixed image was measured by a method in accordance with the mending tape peeling method described in Section 1.4 of Chapter 9, “Basics and Applications of Electrophotographic Technology: The Electrophotographic Society of Japan”. Was evaluated. Specifically, after forming a 2.54 cm square solid fixed image in which the amount of each toner attached is 0.6 mg / cm ² , the image density before and after peeling with a Scotch mending tape (Sumitomo 3M) is measured. Then
The residual rate of the image density was measured as the fixing rate. A reflection densitometer RD-918 manufactured by Macbeth was used for measuring the image density, and the fixing temperature at which the fixing rate was 95% or more was defined as the fixable temperature.

The fixable temperature measured by the above method was ranked in the fixable temperature range according to the following criteria.

A (excellent): Fixable temperature range is 100 ° C or higher B (Good): Fixable temperature range is 70 ° C or higher and lower than 100 ° C C (Practical): Fixable temperature range is 40 ° C or higher 70 ° C
Less than D (defective): Fixable temperature range is less than 40 ° C. <Evaluation of offset resistance> After 1,000 sheets of continuous printing on each A4 size transfer sheet using each toner, a blank sheet is printed to offset the sheet. The white paper stain and the toner stain on the surface of the fixing member were visually observed. As the transfer paper, high-quality paper 200 g / m ² thick paper was used, and the width was 0.3 mm and the length was 150 mm, which was parallel to the paper traveling direction (heat roller circumferential direction).
Was formed, and the offset property was evaluated according to the criteria described below.

⊚: Neither image offset nor toner stain on the heating roller is observed. ◯: No image offset is confirmed, but toner stain is observed on the heating roller. ×: Image offset is clearly confirmed. It was judged that ◯ is acceptable and × is impractical.

<Evaluation of Fixing Member Life> Continuous printing is performed under the conditions described above, and toner sticks to the surface of the endless belt or the heating roller until cleaning becomes impossible.
Alternatively, the number of sheets at which an image defect started to be detected due to peeling of the release layer on the endless belt or the heating roller surface was used as a measure of the life of the fixing member.

<Evaluation of odor during fixing> The exhaust filter was removed, and an electrophotographic apparatus having the fixing unit shown in FIG. 3 was used to continuously print 1000 sheets of a chart having an image area of 7% with each toner. With respect to the fixing odor, the odor was determined by 20 general panelists according to the following criteria.

[0286] ◎: Almost no odor ◯: Slight odor is observed, but there is no particular discomfort X: An offensive odor is observed Table 4 shows the results obtained as described above.

[0287]

[Table 4]

As is clear from Table 4, the elastic layer as the fixing member is made of insulating rubber, the surface release layer is the fluororesin coating layer, and the elastic layer as the pressing member is conductive or insulating rubber. A fixing device having a fluororesin tube structure formed as the surface release layer is used, and a toner containing two or more kinds of metal salts having different valences and each metal salt content has a specific relationship is used. Thus, it can be seen that the fixing temperature range and the offset resistance are excellent, the fixing member has a long life, and odor is hardly generated at the time of fixing, as compared with the comparative example.

[0289]

According to the present invention, it is possible to provide an electrophotographic apparatus having a wide fixing temperature range, excellent offset resistance, a long fixing member life, and a reduced odor during fixing.

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram of an electrophotographic apparatus showing an embodiment of the present invention.

FIG. 2 is a schematic cross-sectional view showing an example of a fixing device having a fixing member and heating means according to the present invention.

FIG. 3 is a schematic view showing an example of a fixing device having a fixing member and a pressure member each having heating means according to the present invention.

[Explanation of symbols]

1 Semiconductor laser light source 4 photoconductor 5 charger 6 developer 7 Transfer device 8 base materials 10 Fixing device 11 Cleaning device 12 Pre-charge exposure (PCL) 13 Cleaning blade 70 Pressure roller 71,85 Surface release layer 75, 75 'heating member 80 heating roller 81, 83 core metal 82, 84 elastic layer 86,86 'Temperature sensor T undeveloped toner image T'Fixed toner image

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Shiro Hirano             2970 Ishikawa-cho, Hachioji-shi, Tokyo Konica stock             In the company F-term (reference) 2H005 AA06 AB03 AB06 AB09 CB08                       CB10 CB20 EA07 FB01                 2H033 AA09 AA23 AA32 BA25 BA30                       BA42 BA43 BA58 BB03 BB05                       BB06 BB13 BB15 BB29 BB33                       BB34

Claims (4)

[Claims] 1. An elastic layer coated with a surface release layer,
A recording medium having a fixing body and a pressure body that rotate in pressure contact with each other, and a heating unit that heats at least one of the fixing body and the pressure body, and a recording medium carrying an unfixed image of toner is formed between the fixing body and the pressure body. In an electrophotographic apparatus in which the unfixed image is fixed on a recording medium by being conveyed and heated and pressed, the fixing member has an elastic layer made of insulating rubber and a surface release layer made of fluororesin. Of the coating layer or tube structure, wherein the pressurizing body has an elastic layer formed of conductive or insulating rubber,
The toner has a fixing device in which the surface release layer has a fluororesin tube structure, the toner contains two or more kinds of metal salts having different valences, and the content of the most contained metal salt is (Mass%), where b (mass%) is the content of the metal salt contained next, a and b have a relationship represented by the following formula (1). Formula (1) 2.0 ≧ a ≧ 0.1 1.0 ≧ b ≧ 0.01 7.5 ≧ a / b ≧ 1.1 However, the masses of a and b represent anhydride conversion values. 2. The metal salt most contained in the a (mass%) of the total toner mass is an aggregation initiator, and the metal salt most contained after the b (mass%) is an aggregation stopper. The electrophotographic apparatus according to claim 1, wherein the electrophotographic apparatus is provided. 3. The electrophotographic apparatus according to claim 1, wherein the toner is a toner produced by salting out / fusing resin particles. 4. The electrophotography according to claim 1, wherein the toner is manufactured through a step of forming particles in an aqueous medium and a deodorizing step. apparatus.