JP2013064826A - Electrostatic charge image developing toner, image formation device and process cartridge - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrostatic charge image developing toner capable of improving a cleaning property of a spherical toner without impeding low-temperature fixability in addition to realizing extended durability of a photoreceptor, and also capable of realizing an electrophotographic system having an excellent image quality with low cost.SOLUTION: A dry electrostatic charge image developing toner includes at least a binder resin and a coloring agent. The toner has projecting portions on a surface thereof. An average length on a long side of the projecting portions is 0.1 μm-0.5 μm. A standard deviation on a long side of the projecting portions is 0.2 or smaller. A coverage factor of a toner surface by the projecting portions is 10%-90%. The toner includes a silicone-oil treated external additive. An entire silicone oil free amount in the toner is 0.2-0.5 mass% with respect to the toner. An addition amount of the external additive is 0.5-4 parts by mass to 100 parts by mass of the toner.

Description

  The present invention relates to a toner for developing a dry electrostatic image for developing an electrostatic latent image formed by electrophotography, electrostatic recording, and electrostatic printing.

  In recent years, color image forming apparatuses using an electrophotographic method have become widespread, and further high definition of printed images has been demanded due to the fact that digitized images can be easily obtained. ing. In an image forming apparatus such as an electronic copying machine, a printer, or a facsimile machine that forms an electrostatic latent image on a latent image carrier and visualizes this with a developer to obtain a recorded image, a dry process using a powdery developer The developing device is widely adopted.

  In order to faithfully reproduce the electrostatic latent image while considering higher resolution and gradation of the image, the improvement on the toner side that visualizes the latent image is to improve the image quality by using a spherical toner. Is already known. However, in order to form a higher-definition image, further spheroidization and particle size reduction have been studied. The toner produced by the pulverization method has limitations in these characteristics, so the so-called polymerized toner produced by the suspension polymerization method, emulsion polymerization method, dispersion polymerization method, etc. that can be spheroidized or reduced in particle size is adopted. (For example, patent document 1 etc.).

  However, in the case of the polymerized toner, there is a problem that the cleaning property is deteriorated due to the spherical shape (through the cleaning blade). That is, the spherical toner has a problem that it is difficult to remove the toner remaining on the photoreceptor, and the charging roller is contaminated and the image quality is lost due to the toner remaining on the photoreceptor. If the amount of the external additive is increased in order to solve this problem, the low-temperature fixability is hindered.

  In recent years, it has been studied to extend the life of functional members so that printing can be performed at low cost, and among them, a technique capable of extending the life of a photoreceptor has been developed. However, it is necessary to overcome the problem of film abrasion due to friction with the cleaning blade in order to extend the life of the photoreceptor.

  The present invention improves electrostatic toner image development that improves the cleaning properties of spherical toner, does not hinder the low-temperature fixability, and further prolongs the life of the photoreceptor, and realizes a good image quality and an inexpensive electrophotographic system. An object of the present invention is to provide a toner for use, an image forming apparatus using the toner, and a process cartridge.

The present invention has the following configuration.
(1) A dry electrostatic charge image developing toner containing at least a binder resin and a colorant,
The toner has a protrusion on the surface,
The average length of the long side of the protrusion is 0.1 μm or more and 0.5 μm or less,
The standard deviation of the length of the long side of the protrusion is 0.2 or less,
The coverage of the toner surface by the protrusions is 10% to 90%,
The toner contains a silicone oil-treated external additive,
The total amount of silicone oil in the toner is 0.2 to 0.5% by mass with respect to the toner,
The toner for developing an electrostatic charge image, wherein an additive amount of the external additive is 0.5 to 4 parts by mass with respect to 100 parts by mass of the toner.
(2) The electrostatic image developing toner according to (1) above, wherein the external additive has a BET specific surface area of 10 to 50 m ² / g.
(3) The toner for developing an electrostatic charge image according to the above (1) or (2), wherein the external additive is silica.
(4) The toner for developing an electrostatic charge image according to any one of (1) to (3) above, wherein the external additive has an average primary particle size of 30 to 150 nm.
(5) The electrostatic charge as described in any one of (1) to (4) above, wherein the amount of silicone oil added to the external additive is ² to 10 mg / m ² per surface area of the external additive. Toner for image developer.
(6) The electrostatic image developing toner according to any one of (1) to (5), wherein the protrusion is made of a resin, and the resin is made of a resin containing styrene.
(7) The ratio of the weight of the resin constituting the protrusion to the total weight of the toner is 1% or more and 20% or less, according to any one of (1) to (6), Toner for developing electrostatic images.
(8) The toner according to (1), wherein the toner is obtained by producing a core particle of the toner and then performing a process of fusing the protrusion on the surface of the core particle. The toner for developing an electrostatic charge image according to any one of to (7).
(9) a latent image carrier that carries a latent image;
Charging means for uniformly charging the surface of the latent image carrier;
Exposure means for exposing the surface of the charged latent image carrier on the basis of image data and writing an electrostatic latent image;
Toner removal means for removing residual toner with a cleaning blade after transfer,
A toner that visualizes the latent image;
Developing means for supplying and developing toner on the electrostatic latent image formed on the surface of the latent image carrier;
Transfer means for transferring the visible image on the surface of the latent image carrier to the transfer target;
Fixing means for fixing a visible image on the transfer target;
An image forming apparatus comprising:
An image forming apparatus, wherein the toner is the toner according to any one of (1) to (8).
(10) a latent image carrier, developing means for developing at least a latent image on the latent image carrier with a developer, toner removing means for removing residual toner on the latent image carrier after transfer with a cleaning blade, In the process cartridge that is configured to be detachably attached to the image forming apparatus,
A process cartridge using the toner according to any one of (1) to (8) above as the toner.

  According to the present invention, electrostatic charge image development that improves the cleaning property of spherical toner, does not impair the low-temperature fixability, extends the life of the photoreceptor, and realizes an electrophotographic system with good image quality and low cost. Toner, an image forming apparatus using the toner, and a process cartridge are provided.

It is a figure which shows the state of the stop layer formed in the cleaning blade front surface. FIG. 6 is a diagram illustrating a method for measuring a toner protrusion in the present invention. It is a figure which shows an example of the image forming apparatus of this invention. It is a figure which shows the soft roller type fixing device of a fluorine-type surface layer agent structure. 1 is a schematic diagram illustrating an example of a multicolor image forming apparatus. 1 is a schematic diagram illustrating an example of a revolver type full-color image forming apparatus. It is a figure which shows an example of a structure of a process cartridge.

The electrostatic image developing toner according to the present invention has a protrusion on the surface, the average length of the long side of the protrusion is 0.1 μm or more and 0.5 μm or less, and the length of the long side of the protrusion is The standard deviation is 0.2 or less, and the coverage of the toner surface by the protrusions is 10% to 90%. The toner contains a silicone oil-treated external additive, and the total amount of silicone oil in the toner is 0.2 to 0.5% by mass with respect to the toner. Is 0.5 to 4 parts by mass with respect to 100 parts by mass of the toner.
The amount of the external additive added is preferably 0.7 to 3.5 parts by mass, and more preferably 1.0 to 3.0 parts by mass with respect to 100 parts by mass of the toner. If the added amount of the external additive is less than 0.5 parts by mass with respect to 100 parts by mass of the toner, the amount of silicone oil supplied to the cleaning blade is small, and problems such as film abrasion occur. On the other hand, when the amount of the external additive added is more than 4 parts by mass with respect to 100 parts by mass of the toner, the amount of the free external additive is increased and the member is contaminated with silicone oil.
By including such a protrusion on the toner surface and including an external additive treated with silicone oil, high-quality image formation can be achieved. This effect is considered to be due to the following reason.

  Due to the production method of the polymerized toner, toner components having relatively low resistance are unevenly distributed in the vicinity of the toner surface. On the other hand, the toner of the present invention can suppress background stains due to low chargeability by providing a protrusion that does not contain a low-resistance component on the toner surface. In addition, since the toner has a high average circularity and the protrusions and recesses are formed on the surface, the contact area between the toner and various members can be reduced, and the adhesion resistance, transferability, and cleaning properties can be improved. . Furthermore, by modifying the surface of the toner without completely covering the surface, it is possible to improve storage at high temperature and high humidity while maintaining low temperature fixability.

In order to achieve these, the following conditions are required for the protrusions. The average length of the long side of the protrusion is from 0.1 μm to 0.5 μm. If the thickness is less than 0.1 μm, the effect of the protruding portion cannot be exhibited, and if it exceeds 0.5 μm, the shape of the protruding portion and the shape of the toner become non-uniform, resulting in problems such as background contamination and a decrease in transfer rate.
The standard deviation of the length of the long side of the protrusion is 0.2 or less. When the standard deviation exceeds 0.2, the size of the protrusions becomes non-uniform, and defects are likely to occur.
The coverage of the toner surface by the protrusions is 10% to 90%, and more preferably 20% to 70%. When the coverage is less than 10%, the effect of the protrusion cannot be exhibited, and when it exceeds 90%, the cleaning property is lowered and the fixing temperature is increased.

Further, since the toner of the present invention has a specific silicone oil release amount, a strong static layer can be formed. Furthermore, by having the above-mentioned protrusions, it is possible to gradually supply free silicone oil to the cleaning part, to maintain a strong stationary layer through durability, to improve the cleaning property of the spherical toner, and to reduce the amount of external additives Does not interfere with low-temperature fixability.
In addition, the free silicone oil can reduce the frictional force between the photoconductor and the cleaning blade, and can suppress film abrasion on the surface of the photoconductor. Similarly, by having the above protrusion, free silicone oil can be gradually supplied to the cleaning part, and through durability, film abrasion on the surface of the photoreceptor can be suppressed, the life of the photoreceptor can be extended, and good image quality can be achieved. An inexpensive electrophotographic method can be provided.
The total amount of silicone oil released in the toner is 0.2 to 0.5% by mass with respect to the toner. More preferably, it is 0.3-0.5 mass%, More preferably, it is 0.3-0.4 mass%. When the amount is less than 0.2% by mass, a sufficient amount of silicone oil is not supplied to the cleaning unit, the cleaning failure or the frictional force with the photosensitive member does not decrease, and image loss due to film scraping occurs.

(External additive)
In the present invention, inorganic fine particles can be preferably used as the external additive. As the inorganic fine particles, either those having a surface hydrophobized or those not hydrophobized can be used.
<Hydrophobic treatment of inorganic fine particles>
As a method for hydrophobizing the inorganic fine particles used in the present invention, a method of chemically treating with inorganic silicon fine particles reacting or physically adsorbing is used. A preferred method is a method of treating inorganic fine particles produced by vapor phase oxidation of a metal halide compound with an organosilicon compound.

  Examples of organosilicon compounds used in the hydrophobization treatment include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methotrechlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyl Dimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, ρ-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane, dimethylethoxy Silane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyl Rudisiloxane, 1,3-diphenyltetramethyldisiloxane, dimethylpolysiloxane having 2 to 12 siloxane units per molecule and containing hydroxyl groups bonded to one Si at each terminal unit is there.

<Silicone oil>
In the present invention, the inorganic fine particles that have been hydrophobized or not hydrophobized are treated with silicone oil. Silicone oils in this case include dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methyl hydrogen silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, polyether-modified silicone oil, alcohol-modified silicone oil, amino-modified Silicone oil, epoxy-modified silicone oil, epoxy / polyether-modified silicone oil, phenol-modified silicone oil, carboxyl-modified silicone oil, mercapto-modified silicone oil, acrylic, methacryl-modified silicone oil, α-methylstyrene-modified silicone oil, and the like can be used.
These silicone oils are used alone or in a mixture of two or more. The amount of silicone oil added as the external additive is preferably ² to 10 mg / m ² per surface area of the external additive. If it is less than 2 mg / m ² , the target amount of silicone oil will not be released, and problems such as film scraping will occur. On the other hand, when the amount is more than 10 mg / m ² , the member is contaminated by the silicone oil, and problems such as a decrease in charging occur.

<Silicone oil treatment method>
In the silicone oil treatment, the inorganic fine particles that have been sufficiently dehydrated and dried in an oven of several hundred degrees Celsius in advance are uniformly contacted with the silicone oil, and the silicone oil is adhered to the surface of the inorganic fine particles.
In order to attach silicone oil to the inorganic fine particles, the inorganic fine particle powder and the silicone oil are sufficiently mixed with the powder with a mixer such as a rotary blade, or the silicone oil is diluted with a relatively low boiling point solvent capable of diluting the silicone oil. And a method in which inorganic fine particle powder is impregnated in a liquid and the solvent is removed and dried. When the viscosity of the silicone oil is high, the treatment is preferably performed in a liquid.
Thereafter, the inorganic powder to which the silicone oil is adhered is heat-treated in an oven at 100 ° C. to several hundred ° C. to form a siloxane bond between the metal and the silicone oil using the hydroxyl group on the surface of the inorganic powder, It can be further polymerized and crosslinked.

  In advance, a catalyst such as acid, alkali, metal salt, zinc octylate, tin octylate, dibutyltin dilaurate or the like may be included in the silicone oil to promote the reaction. The inorganic fine particles may be treated with a hydrophobizing agent such as a silane coupling agent in advance before the silicone oil treatment. Inorganic powder that has been hydrophobized in advance increases the amount of silicone oil adsorbed.

The effect of free silicone in the present invention will be described.
FIG. 1 is a photograph of a state near a cleaning blade when an image is formed using the toner of the present invention. A blocking layer is formed on the front surface of the cleaning blade with silica treated with silicone oil between the cleaning blade and the toner cleaning blade, and this blocking layer functions to prevent the toner from slipping through. Further, in the present invention, since there is a specific silicone oil release amount, the rubbing force between the photoconductor and the cleaning blade is reduced, so that film abrasion of the surface of the photoconductor can be prevented.

<Free silicone oil>
The free silicone oil defined in the present invention includes those that are not necessarily chemically bonded to the surface of the inorganic fine particles (external additive) and are physically adsorbed on the pores of the fine particle surface.
More specifically, it refers to a component that is easily detached from inorganic fine particles upon contact, and the definition of the measurement method will be described later (see “Measurement Method of Silicone Oil Release”).

<Inorganic fine particles>
Examples of inorganic fine particles used as an external additive in the present invention include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, tin oxide, and silica. Sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride, etc. it can. Of these, silica and titanium oxide are particularly preferable.
The addition amount is 0.1 to 5% by mass, preferably 0.3 to 4% by mass with respect to the toner.
These inorganic fine particles may be used alone or in admixture of two or more when used as an electrophotographic toner.

<Inorganic fine particle diameter>
The average particle size (average primary particle size) of the primary particles of the inorganic fine particles as the external additive is not particularly limited, but is preferably 30 to 150 nm. When the average primary particle size is larger than 150 nm, not only the fluidity of the toner is remarkably lowered but also detachment is likely to occur, such being undesirable. In addition, the surface area of the inorganic fine particles is reduced, the total amount of silicone oil that can be supported is reduced, and the surface of the photoreceptor is not uniformly damaged, which is not preferable. On the other hand, when the thickness is less than 30 nm, it is difficult to release from the toner, and it is difficult to form a blocking layer necessary for cleaning, which is not preferable. The average particle diameter here is a number average particle diameter.

  The particle size of the inorganic fine particles used in the present invention can be measured by a particle size distribution measuring apparatus using dynamic light scattering, for example, DLS-700 manufactured by Otsuka Electronics Co., Ltd. or Coulter N4 manufactured by Coulter Electronics. However, since it is difficult to dissociate the secondary aggregation of the particles after the hydrophobization treatment, it is preferable to directly determine the particle diameter from a photograph obtained by a scanning electron microscope or a transmission electron microscope. More preferably, the external additive on the toner surface is observed with a FE-SEM (field emission scanning electron microscope) at a magnification of 100,000 times. In this case, at least 100 or more inorganic fine particles are observed, and the average value of the major axis is obtained. When the external additive has an aggregate structure on the toner surface, the major axis of the single primary particle constituting the aggregate is determined.

<BET specific surface area of inorganic fine particles>
The BET specific surface area of the external additive (inorganic fine particles) used in the toner of the present invention is preferably 10 to 50 m ² / g.
When the BET specific surface area is less than 10 m ² / g, the total amount of silicone oil that can be supported becomes small, and even if the free amount is set within the range of the present invention, the effect is hardly exhibited. If it exceeds 50 m ² / g, it becomes difficult to form a stop layer necessary for cleaning, and the effect is hardly exhibited.

(Other inorganic fine particles; minimal external additives)
In the present invention, together with a fluidizing agent, one or more kinds of known inorganic fine particles not subjected to surface treatment and / or known inorganic fine particles surface-treated with a hydrophobizing agent other than silicone oil as a minimal external additive. You may use together.
As the hydrophobic treatment agent, for example, a silane coupling agent, a silylating agent, a silane coupling agent having a fluorinated alkyl group, an organic titanate coupling agent, an aluminum coupling agent, and the like are preferable surface treatment agents. . Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.

As the inorganic fine particles used in combination, those having an average particle size smaller than that of the inorganic fine particles treated with silicone oil are preferably used.
The coverage of the toner surface is increased by the small inorganic fine particles, and appropriate fluidity can be imparted to the developer, and the faithful reproducibility and the development amount for the latent image during development can be ensured.
Further, aggregation and solidification of the toner during storage of the developer can be prevented.
The addition amount may be 0.01 to 5% by weight, preferably 0.1 to 2% by weight, based on the toner.

<External method>
The external additive of the present invention is added to and mixed with the toner. For the mixing of the external additive, a general powder mixer is used, but it is preferable to equip a jacket or the like and adjust the internal temperature. In order to change the load history applied to the external additive, the external additive may be added in the middle or gradually. Of course, you may change the rotation speed, rolling speed, time, temperature, etc. of a mixer. A strong load may be given first, then a relatively weak load, and vice versa. Examples of mixing equipment that can be used include a rocking mixer, a Roedige mixer, a Nauter mixer, a Henschel mixer, and the like.

(Toner production method)
The method for producing the toner is not particularly limited, and examples thereof include known wet granulation methods such as a dissolution suspension method, a suspension polymerization method, and an emulsion aggregation method, and a pulverization method. From the viewpoint of easy particle size control and shape control, the dissolution suspension method and the emulsion aggregation method are preferable.
When obtaining core particles (colored particles) as cores by an emulsification method or suspension polymerization method, resin fine particles are added to the system in the step after obtaining core particles as cores by the respective known methods. Resin fine particles are adhered and fused to the core particle surfaces. Heating may be performed to promote adhesion and fusion. In addition, the addition of a metal salt is also effective in promoting adhesion and fusion.

(Resin fine particles)
As the resin fine particles in the present invention, those dispersed in an aqueous medium can be used. Examples of the resin constituting the resin fine particles include vinyl resins, polyesters, polyurethanes, polyureas, and epoxy resins. Of these, vinyl resins are preferred because resin fine particles dispersed in an aqueous medium can be easily obtained. As a method for obtaining an aqueous dispersion of vinyl resin fine particles, a known polymerization method such as an emulsion aggregation method, a suspension polymerization method, or a dispersion polymerization method may be used. Among these, the emulsion aggregation method is particularly preferable because particles having a particle size suitable for the present invention can be easily obtained.

(Vinyl resin fine particles)
The vinyl resin fine particles used in the present invention have a vinyl resin obtained by polymerizing a monomer mixture composed of at least a styrene monomer.
In order to use the colored resin particles obtained in the present invention as particles that function by charging, such as toner for developing electrostatic latent images, the surface of the colored resin particles should have a structure that is easily charged. In the monomer mixture, a styrene monomer having an electron orbit such that an electron can stably exist like an aromatic ring structure is 50 to 100% by mass, preferably 80 to 100% by mass, more preferably 95 to 100% by mass. It should be used. When the styrenic monomer is less than 50% by mass, the resulting colored resin particles have poor chargeability, and the application of the colored resin particles is limited.

Here, the styrene monomer refers to an aromatic compound having a vinyl polymerizable functional group. Examples of the polymerizable functional group include a vinyl group, an isopropenyl group, an allyl group, an acryloyl group, and a methacryloyl group.
Specific examples of the styrene monomer include styrene, α-methylstyrene, 4-methylstyrene, 4-ethylstyrene, 4-tert-butylstyrene, 4-methoxystyrene, 4-ethoxystyrene, 4-carboxystyrene, and metal salts thereof. 4-styrenesulfonic acid or a metal salt thereof, 1-vinylnaphthalene, 2-vinylnaphthalene, allylbenzene, phenoxyalkylene glycol acrylate, phenoxyalkylene glycol methacrylate, phenoxy polyalkylene glycol acrylate, phenoxy polyalkylene glycol methacrylate, and the like. Of these, it is preferable to mainly use styrene which is easily available, has excellent reactivity and high chargeability.

  Moreover, although the acid monomer may be used for the vinyl-type resin used for this invention, it is good to use an acid monomer for 0-7 mass% in a monomer mixture, Preferably 0-4 mass%, More preferably, no acid monomer is used. When the acid monomer is used in an amount exceeding 7% by mass, the resulting vinyl resin fine particles have high dispersion stability, and thus such a vinyl resin is contained in a dispersion in which oil droplets are dispersed in an aqueous phase. Even if resin fine particles are added, they are difficult to adhere at room temperature or are easily detached even if they are attached, and they are easily removed in the process of solvent removal, washing, drying, and external addition treatment. Furthermore, when the usage-amount of an acid monomer shall be 4 mass% or less, the change of charging property can be decreased by the environment where the colored resin particle obtained is used.

Here, the acid monomer means a compound having a vinyl polymerizable functional group and an acid group, and examples of the acid group include carboxylic acid, sulfonyl acid, and phosphonic acid.
Examples of the acid monomer include carboxyl group-containing vinyl monomers and salts thereof ((meth) acrylic acid, (anhydrous) maleic acid, monoalkyl maleate, fumaric acid, monoalkyl fumarate, crotonic acid, itaconic acid, itaconic acid mono Alkyl, itaconic acid glycol monoether, citraconic acid, monoalkyl citraconic acid, cinnamic acid, etc.), sulfonic acid group-containing vinyl monomers, vinyl sulfate monoesters and salts thereof, phosphate group-containing vinyl monomers and salts thereof, etc. There is. Among these, (meth) acrylic acid, (anhydrous) maleic acid, monoalkyl maleate, fumaric acid, and monoalkyl fumarate are preferable.

On the other hand, in order to control the compatibility with the core particles, the amount of the monomer having an ethylene oxide (EO) chain such as phenoxyalkylene glycol acrylate, phenoxyalkylene glycol methacrylate, phenoxy polyalkylene glycol acrylate, phenoxy polyalkylene glycol methacrylate, 10 mass% or less of the whole, Preferably it is 5 mass% or less, More preferably, 2 mass% or less is good. If the amount exceeds 10% by mass, the environmental stability of charging is remarkably reduced due to an increase in the polar group on the toner surface, which is not preferable. Moreover, since compatibility with a core particle becomes high too much and the burying rate of a projection part falls easily, it is unpreferable.
In order to control the compatibility with the core particles, a monomer having an ester bond such as 2-acryloyloxyethyl succinate and 2-methacryloyloxyethylphthalic acid may be used at the same time. In this case, the amount used is 10% by mass or less, preferably 5% by mass or less, more preferably 2% by mass or less of the whole monomer. If the amount exceeds 10% by mass, the environmental stability of charging is remarkably reduced due to an increase in the polar group on the toner surface, which is not preferable. Moreover, since compatibility with a core particle becomes high too much and the burying rate of a projection part falls easily, it is unpreferable.

Although it does not specifically limit as a method of obtaining vinyl resin fine particles, The following (a)-(f) is mentioned.
(A) The monomer mixture is reacted by a polymerization reaction such as a suspension polymerization method, an emulsion polymerization method, a seed polymerization method or a dispersion polymerization method to produce a dispersion of vinyl resin fine particles.
(B) The monomer mixture is polymerized in advance, and the resin obtained is pulverized using a mechanical pulverizer or jet pulverizer and then classified to produce resin fine particles.
(C) Resin fine particles are produced by polymerizing the monomer mixture in advance and spraying the resulting resin solution in a solvent in the form of a mist.
(D) polymerizing the monomer mixture in advance, adding a solvent to the resin solution obtained by dissolving the obtained resin in a solvent, or cooling the resin solution previously dissolved in a solvent to precipitate resin fine particles; Resin fine particles are produced by removing the solvent.
(E) A monomer solution is polymerized in advance, and a resin solution obtained by dissolving the obtained resin in a solvent is dispersed in an aqueous medium in the presence of a suitable dispersant, and the solvent is removed by heating or decompression.
(F) A monomer mixture is polymerized in advance, an appropriate emulsifier is dissolved in a resin solution obtained by dissolving the obtained resin in a solvent, and water is added to perform phase inversion emulsification.
Among them, the method (a) is preferable because it is easy to produce and the resin fine particles can be obtained as a dispersion, and can be smoothly applied to the next step.

  In the method (a), when the polymerization reaction is performed, a dispersion stabilizer can be added to the aqueous medium, or the dispersion stability of the resin fine particles obtained by polymerization can be imparted to the monomer that performs the polymerization reaction. It is preferable to add such a monomer (so-called reactive emulsifier) or use these two means in combination to impart dispersion stability of the resulting vinyl resin fine particles. If a dispersion stabilizer or reactive emulsifier is not used, the dispersion state of the particles cannot be maintained, so the vinyl resin cannot be obtained as fine particles, or the dispersion stability of the obtained resin fine particles is low, so that the storage stability Colored resin particles finally obtained because the core particles are easily agglomerated and united because they are agglomerated during storage or because the dispersion stability of the particles in the resin fine particle adhesion process described later decreases. This is not preferable because the uniformity of the particle size, shape, surface, etc. of the resin deteriorates.

  Examples of the dispersion stabilizer include surfactants and inorganic dispersants. Examples of the surfactant include anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates and phosphate esters, and alkylamine salts. Amine salt types such as amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride, etc. Nonionic surfactants such as quaternary ammonium salt type cationic surfactants, fatty acid amide derivatives, polyhydric alcohol derivatives, such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N Amphoteric surfactants such as N- dimethyl ammonium betaine and the like. As the inorganic dispersant, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite and the like are used.

  The weight average molecular weight of the vinyl resin is in the range of 3,000 to 300,000, preferably 4,000 to 100,000, more preferably 5,000 to 50,000. If the weight average molecular weight is less than 3,000, the mechanical strength of the vinyl resin is weak and fragile, so the surface of the colored resin particles easily changes depending on the usage situation depending on the application of the colored resin particles finally obtained. For example, it causes a significant change in chargeability, contamination such as adhesion to peripheral agents, and the occurrence of quality problems associated therewith. On the other hand, if it exceeds 300,000, the molecular ends are reduced, so that the entanglement of the molecular chain with the core particle is reduced and the adhesion to the core particle is lowered, which is not preferable.

  The glass transition temperature (Tg) of the vinyl resin is 45 to 100 ° C, preferably 55 to 90 ° C, more preferably 65 to 80 ° C. When stored in a high-temperature and high-humidity environment, the resin in the protrusions is plasticized by moisture in the atmosphere, which may cause a decrease in the glass transition temperature. During transportation of the toner or toner cartridge, a high temperature and high humidity environment of 40 ° C. and 90% is assumed. The obtained colored resin particles are deformed when placed under a certain pressure, or the colored resin particles stick to each other. There is a possibility that it may not behave as an original particle. For this reason, it is not preferable that the glass transition temperature (Tg) of the said vinyl-type resin is less than 45 degreeC. Moreover, when it is less than 45 degreeC, when using for one-component development, since durability with respect to friction falls, it is unpreferable. On the other hand, if the glass transition temperature exceeds 100 ° C., the fixability is deteriorated.

(Oil phase preparation process)
As a method of preparing an oil phase in which a resin, a colorant or the like is dissolved or dispersed in an organic solvent, the resin, the colorant, or the like is gradually added to the organic solvent while stirring, and the oil phase can be dissolved or dispersed. That's fine. However, when using a pigment as a colorant or adding a release agent or charge control agent that is difficult to dissolve in an organic solvent, the particles should be made smaller prior to addition to the organic solvent. It is preferable.
As described above, the master batch of the colorant is one of the means, and the same method can be applied to the release agent and the charge control agent.

As another means, it is also possible to obtain a wet master by adding a dispersion aid as required in an organic solvent and dispersing the colorant, the release agent, and the charge control agent in a wet manner.
Further, as another means, if a thing that melts below the boiling point of the organic solvent is dispersed, in the organic solvent, if necessary, a dispersion aid is added and heated with stirring with the dispersoid, Once dissolved, the mixture may be cooled with stirring or shearing to crystallize to produce dispersoid microcrystals.
The colorant, release agent, and charge control agent dispersed using the above means may be further dispersed after being dissolved or dispersed together with the resin in the organic solvent. For dispersion, a known disperser such as a bead mill or a disk mill can be used.

(Core particle production process)
The method for producing a dispersion in which the oil phase obtained in the above-described step is dispersed in an aqueous medium having at least a surfactant and core particles composed of the oil phase are dispersed is not particularly limited. Known equipment such as a low-speed shear type, a high-speed shear type, a friction type, a high-pressure jet type, and an ultrasonic wave can be applied. In order to make the particle size of the dispersion 2 to 20 μm, a high-speed shearing type is preferable. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm.
The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. If the dispersion is performed for more than 5 minutes, particles having an undesirably small diameter may remain, or the dispersion may be overdispersed, resulting in instability of the system and generation of aggregates and coarse particles. It is not preferable.
As temperature at the time of dispersion | distribution, it is 0-40 degreeC normally, Preferably it is 10-30 degreeC. If it exceeds 40 ° C., the molecular motion becomes active, so that the dispersion stability is lowered and aggregates and coarse particles are easily generated, which is not preferable. On the other hand, when the temperature is less than 0 ° C., the viscosity of the dispersion increases, and the shear energy required for dispersion increases, so that the production efficiency decreases.
As the surfactant, the same surfactants as described in the description of the method for producing fine resin particles can be used. However, in order to efficiently disperse oil droplets containing a solvent, a disulfonate having a high HLB is used. preferable.

(Resin fine particle adhesion process)
When the dissolution suspension method is used, the above method may be used, but in the state where the oil phase in which the constituent material of core particles serving as a nucleus is dissolved or dispersed in an organic solvent is dispersed in an aqueous medium, resin fine particles are added. Therefore, it is preferable that the resin fine particles are adhered and fused to the surface of the oil phase droplet because the core particles serving as the core and the resin fine particles can be firmly adhered and fused. It is not preferable to add resin fine particles during the toner core particle preparation process because the projections become coarse and non-uniform.
The core particle dispersion liquid obtained as described above can stably cause core particle droplets to exist while stirring. In this state, the resin fine particle dispersion is charged and adhered onto the core particles. The vinyl resin fine particle dispersion is preferably charged over 30 seconds. If the charging is performed in less than 30 seconds, it is not preferable because the dispersion system changes abruptly to generate aggregated particles or uneven adhesion of vinyl resin fine particles. On the other hand, it is not preferable from the viewpoint of production efficiency to add to the dark cloud for a long time, for example, exceeding 60 minutes.

The vinyl resin fine particle dispersion may be diluted or concentrated to adjust the concentration as appropriate before being added to the core particle dispersion. The concentration of the vinyl resin fine particle dispersion is preferably 5 to 30% by mass, and more preferably 8 to 20% by mass. If it is less than 5% by mass, the change in the concentration of the organic solvent accompanying the introduction of the dispersion is large, and the adhesion of the resin fine particles becomes insufficient. Further, if it exceeds 30% by mass, the resin fine particles are likely to be unevenly distributed in the core particle dispersion, and as a result, the adhesion of the resin fine particles becomes non-uniform.
The vinyl resin fine particles adhere to the core particles (colored particles) with sufficient strength by the method of the present invention because the core particles freely deform when the vinyl resin fine particles adhere to the core particle droplets. In order to achieve this, the interface between the vinyl resin fine particles and the contact surface must be sufficiently formed, and the vinyl resin fine particles are swollen or dissolved by the organic solvent, and the vinyl resin fine particles and the resin in the core particles are likely to adhere to each other. It seems to be. Therefore, in this state, the organic solvent needs to be sufficiently present in the system. Specifically, in the state of the core particle dispersion, it is 50% by mass to 150% by mass, preferably 70% by mass with respect to the solid content (resin, colorant, and if necessary, release agent, charge control agent, etc.). It may be in the range of% to 125% by mass. If it exceeds 150% by mass, the amount of colored resin particles obtained in a single production process is reduced and the production efficiency is low, and if there is a large amount of organic solvent, the dispersion stability is lowered and stable production becomes difficult. .

The temperature at which the vinyl resin fine particles adhere to the core particles is 10 to 60 ° C, preferably 20 to 45 ° C. If the temperature exceeds 60 ° C, the energy required for production increases and the environmental burden on the production increases. In addition, low acid value vinyl resin fine particles may be present on the droplet surface, making dispersion unstable. Since coarse particles may be generated, it is not preferable. On the other hand, when the temperature is lower than 10 ° C., the viscosity of the dispersion is increased, and adhesion of resin fine particles becomes insufficient, which is not preferable.
The ratio of the resin constituting the resin fine particles to the total weight of the toner is 1% to 20%, preferably 3% to 15%, more preferably 5% to 10%. If it is less than 1%, the effect is insufficient, and if it exceeds 20%, excessive resin fine particles adhere weakly to the toner core particles and cause filming and the like.
In addition, there is a method in which the toner particle matrix and resin fine particles are mixed and agitated to mechanically adhere and coat.

<Demelting process>
In order to remove the organic solvent from the obtained colored resin dispersion, it is possible to employ a method in which the entire system is gradually heated while being stirred to completely evaporate and remove the organic solvent in the droplets.
Alternatively, the obtained colored resin dispersion can be sprayed into a dry atmosphere while stirring to completely remove the organic solvent in the droplets. Alternatively, the colored resin dispersion may be decompressed while stirring to evaporate and remove the organic solvent. The latter two means can be used in combination with the first means.
As a dry atmosphere in which the emulsified dispersion is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, or the like, in particular, various air currents heated to a temperature equal to or higher than the boiling point of the highest boiling solvent used is generally used. Sufficient quality can be obtained with a short treatment such as spray dryer, belt dryer or rotary kiln.

<Aging process>
When a modified resin having an isocyanate group at the terminal is added, an aging step may be performed in order to advance the elongation / crosslinking reaction of the isocyanate. The aging time is usually 10 minutes to 40 hours, preferably 2 to 24 hours. The reaction temperature is usually 0 to 65 ° C, preferably 35 to 50 ° C.

<Washing process>
In order to take out only the colored resin particles from these, since the dispersion of the colored resin particles obtained by the above method contains secondary materials such as a dispersant such as a surfactant in addition to the colored resin particles. Wash. Methods for washing the colored resin particles include methods such as a centrifugal separation method, a vacuum filtration method, and a filter press method, but are not particularly limited in the present invention. Either method can give a cake of colored resin particles, but if it cannot be washed sufficiently by a single operation, the obtained cake is again dispersed in an aqueous solvent to form a slurry and colored by any of the above methods. The step of taking out the resin particles may be repeated, and if washing is performed by a vacuum filtration method or a filter press method, an aqueous solvent is passed through the cake and a method of washing away the secondary material that the colored resin particles have embraced is adopted. Also good. As the aqueous solvent used for this washing, water or a mixed solvent obtained by mixing water and alcohol such as methanol or ethanol is used, but water is preferably used in view of cost and environmental load due to wastewater treatment.

<Drying process>
Since the washed colored resin particles contain a large amount of the aqueous medium, only the colored resin particles can be obtained by drying and removing the aqueous medium. Drying methods such as spray dryers, vacuum freeze dryers, vacuum dryers, stationary shelf dryers, mobile shelf dryers, fluidized tank dryers, rotary dryers, and agitation dryers are used as drying methods. be able to. The dried colored resin particles are preferably dried until the water content finally becomes less than 1%. If the colored resin particles after drying are softly agglomerated and inconvenience occurs during use, use a device such as a jet mill, a Henschel mixer, a super mixer, a coffee mill, an auster blender, or a food processor. It may be crushed to loosen the soft agglomeration.

(About toner particle size)
In order to achieve uniform and sufficient charging in the toner of the present invention, the volume average particle size of the toner is preferably in the range of 3 to 9 μm, preferably 4 to 8 μm, more preferably 4 to 7 μm. If it is less than 3 μm, the toner adhesion is relatively increased and the toner operability due to the electric field is lowered, which is not preferable. On the other hand, if it exceeds 9 μm, the image quality such as reproducibility of thin lines is deteriorated.
The ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) of the toner is preferably 1.25 or less, more preferably 1.20 or less, and further preferably 1.17 or less. preferable. If it exceeds 1.25, the uniformity of the particle size of the toner is low, so that the size of the protrusion tends to vary. In addition, the toner having a large particle diameter or a small toner in some cases is consumed over time, and the average particle diameter of the toner remaining in the developing device changes. As a result, various phenomena such as charging failure, extreme increase or decrease in the transport amount, toner clogging, and toner spillage are likely to occur.

Examples of the measuring device for the particle size distribution of toner particles include Coulter Counter TA-II and Coulter Multisizer II (both manufactured by Coulter). The measurement method is described below.
First, 0.1 to 5 ml of a surfactant (preferably alkyl benzene sulfonate) is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution. Here, the electrolytic solution is a solution prepared by preparing a 1% NaCl aqueous solution using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the measurement device is used to measure the volume and number of toner particles or toner using a 100 μm aperture as an aperture. Volume distribution and number distribution are calculated. From the obtained distribution, the volume average particle diameter (D4) and the number average particle diameter (D1) of the toner can be obtained.

  As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 Less than 35 to 8.00 μm; less than 8.00 to less than 10.08 μm; less than 10.08 to less than 12.70 μm; less than 12.70 to less than 16.00 μm; less than 16.00 to less than 20.20 μm; Uses 13 channels of less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm, and targets particles having a particle size of 2.00 μm to less than 40.30 μm.

(About toner shape)
The average circularity of the toner should be 0.930 or more, preferably 0.950 or more, more preferably 0.970 or more. If the average circularity is less than 0.930, the external additive accumulates in the recess. This is not preferable because it is difficult to supply silicone oil. Further, since the toner fluidity is low, problems in development are likely to occur, and transfer efficiency is also lowered.
The average circularity of the toner is measured by a flow type particle image analyzer FPIA-2000. As a specific measuring method, 0.1 to 0.5 ml of a surfactant, preferably alkylbenzene sulfonate, is added as a dispersant to 100 to 150 ml of water from which impure solids have been previously removed, and further measurement is performed. Add about 0.1-0.5g of sample. The suspension in which the sample is dispersed is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the shape and distribution of the toner are measured by the above apparatus with a dispersion concentration of 3,000 to 10,000 / μl. can get.
In the case of a toner manufactured by a wet granulation method, the ionic toner constituent material is unevenly distributed in the vicinity of the surface, so that the toner surface layer has a relatively low resistance. However, there is a problem in that the charge retention is poor, that is, the toner charge amount is easily attenuated. In order to improve this, for example, a method of supporting a surface modifying material on the toner surface can be mentioned.

(Measurement of particle size of vinyl resin fine particles)
The particle size of the resin fine particles was measured using UPA-150EX (manufactured by Nikkiso Co., Ltd.).
The particle size of the resin fine particles is 50 to 200 nm, preferably 80 to 160 nm, and more preferably 100 to 140 nm. If it is less than 50 nm, it is difficult to form a sufficiently large protrusion on the toner surface, and if it exceeds 200 nm, the protrusion tends to be non-uniform. The ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) is preferably 1.25 or less, more preferably 1.20 or less, and even more preferably 1.17 or less. If it exceeds 1.25, the uniformity of the particle size of the resin fine particles is low, so that the size of the protrusions tends to vary.

(Molecular weight measurement (GPC))
The molecular weight of the resin was measured by GPC (gel permeation chromatography) under the following conditions.
・ Equipment: GPC-150C (manufactured by Waters)
Column: KF801-807 (manufactured by Shodex)
・ Temperature: 40 ℃
-Solvent: THF (tetrahydrofuran)
Flow rate: 1.0 mL / min Sample: 0.1 mL of a sample having a concentration of 0.05 to 0.6% was injected.

  The number average molecular weight and weight average molecular weight of the resin were calculated from the molecular weight distribution of the resin measured under the above conditions, using a molecular weight calibration curve prepared with a monodisperse polystyrene standard sample. Standard polystyrene samples for creating a calibration curve include Showdex STANDARD Std. NoS-7300, S-210, S-390, S-875, S-1980, S-10.9, S-629, S manufactured by Showa Denko KK -3.0, S-0.580, and toluene were used. An RI (refractive index) detector was used as the detector.

(Glass transition temperature (Tg) measurement (DSC))
As an apparatus for measuring Tg, a TG-DSC system TAS-100 manufactured by Rigaku Corporation was used.
First, about 10 mg of a sample is placed in an aluminum sample container, which is placed on a holder unit and set in an electric furnace. First, after heating from room temperature to 150 ° C. at a temperature rising rate of 10 ° C./min, the sample was allowed to stand at 150 ° C. for 10 min, the sample was cooled to room temperature and left for 10 min, and the temperature rising rate was again increased to 150 ° C. under a nitrogen atmosphere. DSC measurement was performed by heating at min. Tg was calculated from the contact point between the tangent line of the endothermic curve near the Tg and the base line using the analysis system in the TAS-100 system.

(Solid concentration measurement)
Measurement of the solid content concentration of the oil phase was performed as follows.
On an aluminum pan (about 1 to 3 g) whose mass has been accurately weighed in advance, about 2 g of the oil phase is placed within 30 seconds, and the mass of the placed oil phase is accurately weighed. This is placed in an oven at 150 ° C. for 1 hour to evaporate the solvent, then taken out of the oven, allowed to cool, and the mass of the aluminum dish and the oil phase solids is measured with an electronic balance. Calculate the mass of the oil phase solid by subtracting the mass of the aluminum pan from the total mass of the aluminum pan and the oil phase solid content, and calculate the solid content concentration of the oil phase by dividing by the mass of the oil phase on which it is placed. . The ratio of the amount of the solvent to the solid content in the oil phase is a value obtained by dividing a value obtained by subtracting the mass of the oil phase solid content from the mass of the oil phase (mass of the solvent) by the mass of the oil phase solid content.

<Acid value measurement>
The acid value of the resin is measured according to JIS K1557-1970. A specific measurement method is shown below.
About 2 g of the pulverized sample is precisely weighed (W (g)).
A sample is put into a 200 ml Erlenmeyer flask, 100 ml of a mixed solution of toluene / ethanol (2: 1) is added and dissolved for 5 hours, and then a phenolphthalein solution is added as an indicator.
The solution is titrated with a burette using a 0.1 N potassium hydroxide alcohol solution. The amount of the KOH solution at this time is S (ml). A blank test is performed, and the amount of the KOH solution at this time is defined as B (ml).
The acid value is calculated by the following formula.
Acid value = [(SB) × f × 5.61] / W
(F: Factor of KOH solution)

(Long sides of the protrusion and coverage)
The toner is observed with a scanning electron microscope (SEM), and the length of the long side of the protrusion and the coverage of the protrusion with respect to the toner are determined from the obtained SEM image.
Hereinafter, a method of calculating the long side of the protrusion and the coverage described in the embodiment will be described with reference to FIG.
<Coverage>
First, the shortest length of two parallel lines in contact with the toner is obtained, and the respective contacts are designated as A and B. From the area of a circle whose diameter is the length of the line segment AO with the midpoint O of the line segment AB as the center, and the area of the protrusion included in the circle, the coverage of the protrusions with respect to the toner was calculated. With respect to the coverage, the coverage was calculated for the 100 or more toner particles by the above method and averaged.
<Average length of long side>
The average length of the long side was determined by measuring the length of the long side of 100 or more protrusions with respect to one or more toner particles.
Image analysis type particle size distribution measurement software “Mac-View” (manufactured by Mountec Co., Ltd.) was used to measure the area of the protrusion, the long side of the protrusion, and the circularity. There is no restriction | limiting in particular as a measuring method of the length of the long side of a projection part, and the area of a projection part, According to the objective, it can select suitably.

The average length of the long sides of the protrusions is 0.1 μm or more and 0.5 μm or less, preferably 0.3 μm or less. When the thickness exceeds 0.5 μm, the protrusions on the surface become sparse, the surface area becomes small, and the external additive that is firmly supported decreases, which is not preferable.
The standard deviation of the average length of the long sides of the protrusions is 0.2 or less, preferably 0.1 or less. If the standard deviation exceeds 0.2, the size of the protrusions on the surface becomes non-uniform, and an increase in surface area cannot be expected, which is not preferable.

  The coverage of the toner surface by the protrusions is 10% to 90%, preferably 20% to 70%, more preferably 40% to 80%, and still more preferably 50 to 70%. When the coverage is less than 10% or more than 90%, it is not preferable because the external additive that is firmly supported decreases.

(Measurement method of silicone oil release)
The amount of free silicone oil in the toner (silicone oil free amount) is measured by a quantitative method comprising the following procedures (1) to (3).
(1) Extraction of free silicone oil The sample toner is immersed in chloroform, stirred and allowed to stand.
Chloroform is newly added to the solid after the supernatant is removed by heart separation, and the mixture is stirred and left standing.
Repeat this procedure to remove free silicone oil from the sample.
(2) Quantification of carbon content Quantification of carbon content in a sample from which free silicone oil has been removed is measured with a CHN elemental analyzer (CHN coder MT-5 type (manufactured by Yanaco)).
(3) Determination of free amount of silicone oil The free amount of silicone oil is determined by the following formula (1).
Silicone oil release amount = (C0−C1) / C × 100 × 40/12 (mass%)
... (1)
here,
C: Carbon content (mass%) in the treatment agent silicone oil
C0: Carbon content (% by mass) in the sample before the extraction operation
C1: Carbon content (% by mass) in the sample after the extraction operation
Coefficient 40/12: Conversion coefficient from the amount of C in the structure of polydimethylsiloxane to the total amount The structural formula of polydimethylsiloxane is shown below.

<Image forming apparatus>
The image forming apparatus of the present invention forms an image using the toner of the present invention. The toner of the present invention can be used as either a one-component developer or a two-component developer, but is preferably used as a one-component developer. The image forming apparatus of the present invention preferably has an endless intermediate transfer unit. Furthermore, the image forming apparatus of the present invention preferably includes a photosensitive member and a cleaning unit that cleans the toner remaining on the photosensitive member and / or the intermediate transfer unit. At this time, the cleaning means may or may not have a cleaning blade. The image forming apparatus of the present invention preferably includes a fixing unit that fixes an image using a roller having a heating device or a belt having a heating device. Further, the image forming apparatus of the present invention preferably has a fixing unit that does not require oil application to the fixing member. Furthermore, it is preferable to include other means appropriately selected as necessary, for example, static elimination means, recycling means, control means, and the like.

  In the image forming apparatus of the present invention, the photosensitive member and the constituent elements such as the developing unit and the cleaning unit may be configured as a process cartridge, and the process cartridge may be configured to be detachable from the image forming apparatus body. Further, at least one of a charging unit, an exposure unit, a developing unit, a transfer unit, a separating unit, and a cleaning unit is supported together with a photosensitive member to form a process cartridge, and a single unit that is detachable from the main body of the image forming apparatus. It is good also as a structure which can be attached or detached using guide means, such as a rail of a forming apparatus main body.

FIG. 3 shows an example of the image forming apparatus of the present invention. In this image forming apparatus, a latent image carrier (1) that is driven to rotate in the clockwise direction in FIG. 3 is housed in a main body housing (not shown), and around the latent image carrier (1). In addition, a charging device (2), an exposure device (3), a developing means (4) having the toner (T) of the present invention, a cleaning unit (5), an intermediate transfer member (6), a support roller (7), a transfer roller (8) A neutralizing means (not shown) is provided.
The image forming apparatus includes a paper feed cassette (not shown) that stores a plurality of recording papers (P) as an example of a recording medium, and the recording paper (P) in the paper feed cassette is a paper feed (not shown). After the timing is adjusted by a pair of registration rollers (not shown) one by one by a roller, the sheet is fed between a transfer roller (8) as a transfer means and an intermediate transfer body (6).

  In this image forming apparatus, the latent image carrier (1) is rotated clockwise in FIG. 3 to uniformly charge the latent image carrier (1) with the charging device (2), and then the exposure device ( 3) to irradiate the laser modulated with the image data to form an electrostatic latent image on the latent image carrier (1), and to the developing means (4) on the latent image carrier (1) on which the electrostatic latent image is formed. ) To attach toner and develop. Next, a transfer bias is applied from the latent image carrier (1) on which the toner image is formed by the developing means (4) to the intermediate transfer member (6) to transfer the toner image onto the intermediate transfer member (6). By transferring the recording paper (P) between the intermediate transfer body (6) and the transfer roller (8), the toner image is transferred to the recording paper (P). Further, the recording paper (P) on which the toner image is transferred is conveyed to a fixing means (not shown).

  The fixing unit includes a fixing roller heated to a predetermined fixing temperature by a built-in heater and a pressure roller pressed against the fixing roller with a predetermined pressure, and heats the recording paper conveyed from the transfer roller (8). After pressurizing and fixing the toner image on the recording paper on the recording paper, it is discharged onto a paper discharge tray (not shown).

  On the other hand, the image forming apparatus further rotates the latent image carrier (1) on which the toner image is transferred onto the recording paper by the transfer roller (8), and the cleaning unit (5) applies the surface to the surface of the latent image carrier (1). After the remaining toner is scraped off and removed, the charge is removed by a charge removal device (not shown). The image forming apparatus uniformly charges the latent image carrier (1) neutralized by the static eliminator with the charging device (2), and then performs the next image formation in the same manner as described above.

Hereinafter, each member suitably used for the image forming apparatus of the present invention will be described in detail.
The material, shape, structure, size and the like of the latent image carrier (1) are not particularly limited and may be appropriately selected from known ones. The shape may be a drum shape or a belt shape. Examples of the material include inorganic photoreceptors such as amorphous silicon and selenium, and organic photoreceptors such as polysilane and phthalopolymethine. Among these, amorphous silicon and organic photoreceptors are preferable from the viewpoint of long life.

  The electrostatic latent image can be formed on the latent image carrier (1) by, for example, charging the surface of the latent image carrier (1) and then exposing it like an image. It can be performed by latent image forming means. The electrostatic latent image forming means includes, for example, a charging device (2) for charging the surface of the latent image carrier (1) and an exposure device (3) for exposing the surface of the latent image carrier (1) imagewise. At least.

The charging can be performed, for example, by applying a voltage to the surface of the latent image carrier (1) using the charging device (2).
The charging device (2) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the charging device (2) includes a conductive or semiconductive roller, brush, film, rubber blade, etc. And non-contact chargers using corona discharge such as corotron and scorotron.

The shape of the charging device (2) may be a magnetic brush, a fur brush or the like in addition to the roller, and can be selected according to the specifications and form of the electrophotographic apparatus. In the case of using a magnetic brush, the magnetic brush is composed of, for example, various ferrite particles such as Zn-Cu ferrite as a charging member, and a non-magnetic conductive sleeve for supporting the same, and a magnet roll included therein. . In addition, when using a brush, for example, as a material of the fur brush, a fur treated with carbon, copper sulfide, metal or metal oxide is used, and this is wound around a metal or other conductive core. It is configured by pasting.
The charging device (2) is not limited to the contact type charger as described above, but an image forming apparatus in which ozone generated from the charger is reduced is obtained. Therefore, a contact type charger is used. It is preferable.

  The exposure can be performed, for example, by exposing the surface of the photoreceptor imagewise using the exposure apparatus (3). The exposure device (3) is not particularly limited as long as the surface of the latent image carrier (1) charged by the charging device (2) can be exposed like an image to be formed. For example, various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system may be used.

  The development can be performed, for example, by developing the electrostatic latent image using the toner of the present invention, and can be performed by the developing means (4). The developing means (4) is not particularly limited as long as it can be developed using the toner of the present invention, for example, and can be appropriately selected from known ones, for example, containing the toner of the present invention, Preferable examples include those having at least a developing unit that can apply toner to the electrostatic latent image in a contact or non-contact manner.

  The developing means (4) carries toner on its peripheral surface, rotates in contact with the latent image carrier (1), and supplies toner to the electrostatic latent image formed on the latent image carrier (1). The developing roller (40) that performs development and a thin layer forming member (41) that contacts the peripheral surface of the developing roller (40) and thins the toner on the developing roller (40) are preferable.

  As the developing roller (40), either a metal roller or an elastic roller is preferably used. There is no restriction | limiting in particular as a metal roller, Although it can select suitably according to the objective, For example, an aluminum roller etc. are mentioned. By performing a blasting process on the metal roller, it is possible to produce the developing roller (40) having an arbitrary surface friction coefficient relatively easily. Specifically, by treating the aluminum roller with glass bead blasting, the roller surface can be roughened, and an appropriate toner adhesion amount can be obtained on the developing roller.

  As the elastic roller, a roller coated with an elastic rubber layer is used, and a surface coat layer made of a material that is easily charged to a polarity opposite to that of the toner is provided on the surface. The elastic rubber layer is set to a hardness of 60 degrees or less according to JIS-A in order to prevent toner deterioration due to pressure concentration at the contact portion with the thin layer forming member (41). The surface roughness (Ra) is set to 0.3 to 2.0 μm, and a necessary amount of toner is held on the surface. Further, since the developing roller (40) is applied with a developing bias for forming an electric field with the latent image carrier (1), the elastic rubber layer is set to a resistance value of 103 to 1010Ω. . The developing roller (40) rotates in the clockwise direction, and conveys the toner held on the surface to a position facing the thin layer forming member (41) and the latent image carrier (1).

  The thin layer forming member (41) is provided at a position lower than the contact position between the supply roller (42) and the developing roller (40). The thin layer forming member (41) is made of a metal leaf spring material such as stainless steel (SUS) or phosphor bronze, and the free end is brought into contact with the surface of the developing roller (40) with a pressing force of 10 to 40 N / m. Therefore, the toner that has passed under the pressure is thinned and charged by frictional charging. Further, a regulating bias having a value offset in the same direction as the charging polarity of the toner with respect to the developing bias is applied to the thin layer forming member (41) in order to assist frictional charging.

There is no restriction | limiting in particular as a rubber elastic body which comprises the surface of a developing roller (40), Although it can select suitably according to the objective, For example, a styrene-butadiene-type copolymer rubber, an acrylonitrile-butadiene-type copolymer weight Examples include coalesced rubber, acrylic rubber, epichlorohydrin rubber, urethane rubber, silicone rubber, or a blend of two or more thereof. Among these, a blend rubber of epichlorohydrin rubber and acrylonitrile-butadiene copolymer rubber is particularly preferable.
The developing roller (40) is manufactured, for example, by covering the outer periphery of the conductive shaft with a rubber elastic body. The conductive shaft is made of a metal such as stainless steel (SUS), for example.

The transfer can be performed, for example, by charging the latent image carrier (1), and can be performed by a transfer roller. The transfer roller includes a primary transfer unit that transfers a toner image onto an intermediate transfer member (6) to form a transfer image, and a secondary transfer unit (transfer) that transfers the transfer image onto a recording paper (P). An embodiment having a roller (8) is preferred. At this time, two or more colors, preferably full color toners are used as toners, and a primary transfer means for forming a composite transfer image by transferring the toner image onto the intermediate transfer member (6), and recording the composite transfer image An embodiment having secondary transfer means for transferring onto the paper (P) is more preferable.
The intermediate transfer member (6) is not particularly limited, and can be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.

  The transfer means (primary transfer means, secondary transfer means) preferably has at least a transfer device that peels and charges the toner image formed on the latent image carrier (1) to the recording paper (P) side. . There may be one transfer means, or two or more transfer means. Examples of the transfer means include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.

  The recording paper (P) is typically plain paper, but is not particularly limited as long as it can transfer an unfixed image after development, and can be appropriately selected according to the purpose. A PET base for OHP can also be used.

For example, the fixing can be performed on the toner image transferred to the recording paper (P) by using a fixing unit, and is performed each time the toner image of each color is transferred to the recording paper (P). Alternatively, it may be performed at the same time in a state where toner images of respective colors are laminated.
The fixing unit is not particularly limited and may be appropriately selected depending on the intended purpose. However, a known heating and pressing unit is preferable. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt. In addition, as for the heating temperature by a heating-pressing means, 80-200 degreeC is preferable.

It may be a soft roller type fixing device having a fluorine surface layer composition as shown in FIG.
This is because the heating roller (9) has an elastic body layer (11) made of silicone rubber and a PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer) surface layer (12) on an aluminum core bar (10). The heater (13) is provided inside the aluminum cored bar. The pressure roller (14) has an elastic layer (16) made of silicone rubber and a PFA surface layer (17) on an aluminum cored bar (15). The recording paper (P) on which the unfixed image (18) is printed is passed as shown.

  In the present invention, for example, a known optical fixing device may be used together with or instead of the fixing unit depending on the purpose.

  The neutralization can be performed, for example, by applying a neutralization bias to the latent image carrier, and can be suitably performed by a neutralization unit. The neutralizing means is not particularly limited as long as it can apply a neutralizing bias to the latent image carrier, and can be appropriately selected from known static eliminators. For example, a neutralizing lamp is preferable. It is done.

  Cleaning can be suitably performed, for example, by removing the toner remaining on the photoreceptor by a cleaning means. The cleaning means is not particularly limited and may be any one selected from known cleaners as long as it can remove the toner remaining on the photosensitive member. For example, a magnetic brush cleaner, an electrostatic brush cleaner, or a magnetic roller can be selected. A cleaner, a blade cleaner, a brush cleaner, a web cleaner and the like are preferable.

  The recycling can be suitably performed, for example, by transporting the toner removed by the cleaning unit to the developing unit by the recycling unit. There is no restriction | limiting in particular as a recycle means, A well-known conveyance means etc. are mentioned.

Control can be suitably performed by controlling each means by a control means, for example. The control means is not particularly limited as long as each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.
According to the image forming apparatus and the process cartridge of the present invention, it is possible to provide a good image by using toner for developing an electrostatic latent image that has excellent fixability and is free from deterioration such as cracking due to stress in the development process. be able to.

<Multicolor image forming apparatus>
FIG. 5 is a schematic view showing an example of a multicolor image forming apparatus to which the present invention is applied. FIG. 5 shows a tandem type full-color image forming apparatus.

  In FIG. 5, the image forming apparatus stores a latent image carrier (1) that is driven to rotate clockwise in the figure in a main body housing (not shown), and around the latent image carrier (1), A charging device (2), an exposure device (3), a developing means (4), an intermediate transfer member (6), a support roller (7), a transfer roller (8) and the like are arranged. Although not shown, the image forming apparatus includes a paper feeding cassette that stores a plurality of recording papers. The recording paper (P) in the paper feeding cassette is fed to a pair of registration rollers (not shown) one by one by a paper feeding roller (not shown). After the timing adjustment, the sheet is fed between the intermediate transfer member (6) and the transfer roller (8) and fixed by the fixing means (19).

  The image forming apparatus rotates the latent image carrier (1) clockwise in FIG. 5 to uniformly charge the latent image carrier (1) with the charging device (2), and then exposes the exposure device (3). The laser beam modulated by the image data is irradiated to form an electrostatic latent image on the latent image carrier (1), and the latent image carrier (1) on which the electrostatic latent image is formed is developed by the developing means (4). Develop with toner attached. The image forming apparatus transfers the toner image formed by attaching the toner to the latent image carrier with the developing means (4) from the latent image carrier (1) to the intermediate transfer member. This is performed for each of the four colors of cyan (C), magenta (M), yellow (Y), and black (K) to form a full-color toner image.

Next, FIG. 6 is a schematic view showing an example of a revolver type full-color image forming apparatus.
In this image forming apparatus, a plurality of color toners are successively developed on one latent image carrier (1) by switching the operation of the developing means. Then, the color toner image on the intermediate transfer body (6) is transferred to the recording paper (P) by the transfer roller (8), the recording paper (P) to which the toner image is transferred is conveyed to the fixing unit, and the fixed image is transferred. obtain.

On the other hand, the image forming apparatus further rotates the latent image carrier (1) on which the toner image is transferred to the recording paper (P) by the intermediate transfer member (6), and the latent image carrier (1) by the cleaning unit (5). ) The toner remaining on the surface is removed by scraping with a blade, and then the charge is removed by the charge removing unit. The image forming apparatus uniformly charges the latent image carrier (1) neutralized by the neutralization unit with the charging device (2), and then performs the next image formation as described above. The cleaning unit (5) is not limited to scraping off the residual toner on the latent image carrier (1) with a blade. For example, the cleaning unit (5) scrapes off the residual toner on the latent image carrier (1) with a fur brush. It may be a thing.
In the image forming apparatus of the present invention, since the toner of the present invention is used as the developer, a good image can be obtained.

<Process cartridge>
The process cartridge of the present invention can develop an electrostatic latent image carrier carrying an electrostatic latent image and the electrostatic latent image carried on the electrostatic latent image carrier using the toner of the present invention. A developing means for forming a visual image, and further comprising other means such as a charging means, a developing means, a transfer means, a cleaning means, and a static elimination means, which are appropriately selected as necessary. The image forming apparatus main body is detachable.

  The developing means includes a developer container that contains the toner or developer of the present invention, and a developer carrier that carries and transports the toner or developer contained in the developer container. And a layer thickness regulating member for regulating the thickness of the toner layer to be carried. The process cartridge of the present invention can be detachably provided in various electrophotographic apparatuses, facsimiles, and printers, and is preferably detachably provided in the image forming apparatus of the present invention described later.

  For example, as shown in FIG. 7, the process cartridge includes a latent image carrier (1), and includes a charging device (2), a developing means (4), a transfer roller (8), and a cleaning unit (5). In addition, other means are provided as necessary. In FIG. 7, (L) shows exposure from the exposure apparatus, and (P) shows recording paper. As the latent image carrier (1), the same one as the image forming apparatus can be used. An arbitrary charging member is used for the charging device (2).

  Next, the image forming process using the process cartridge shown in the figure will be described. The latent image carrier (1) is charged by the charging device (2) while being rotated in the direction of the arrow, and exposure by the exposure means (not shown) ( L), an electrostatic latent image corresponding to the exposure image is formed on the surface. The electrostatic latent image is developed with toner by the developing means (4), and the toner development is transferred onto the recording paper (P) by the transfer roller (8) and printed out. Next, the surface of the latent image carrier after the image transfer is cleaned by the cleaning unit (5), further neutralized by a neutralizing unit (not shown), and the above operation is repeated again.

  Examples are shown below, but the scope of the present invention is not limited by these Examples. Moreover, the part in an Example shows a mass part and% about a density | concentration shows the mass%.

<Method for producing resin dispersion 1>
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 0.7 part of sodium dodecyl sulfate and 498 parts of ion-exchanged water were added and dissolved by heating to 80 ° C. with stirring. A solution obtained by dissolving 2.6 parts in 104 parts of ion-exchanged water was added, and 15 minutes later, a monomer mixture of 200 parts of styrene monomer and 4.2 parts of n-octanethiol was dropped over 90 minutes, Thereafter, the polymerization reaction was carried out at 80 ° C. for another 60 minutes.
Then, it cooled and white [resin dispersion 1] with a volume average particle diameter of 135 nm was obtained. The obtained [Resin Dispersion 1] was placed in a 2 ml petri dish, and the dried solid obtained by evaporating the dispersion medium was measured. As a result, the number average molecular weight was 8,300, the weight average molecular weight was 16,900, and Tg was 83 ° C. It was.

<Method for producing resin dispersion 2>
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introducing tube, 1.1 parts of sodium dodecyl sulfate and 498 parts of ion-exchanged water were added and dissolved by heating to 80 ° C. with stirring, and then potassium persulfate. A solution obtained by dissolving 2.6 parts in 104 parts of ion-exchanged water was added, and 15 minutes later, a monomer mixture of 200 parts of styrene monomer and 4.2 parts of n-octanethiol was dropped over 90 minutes, Thereafter, the polymerization reaction was carried out at 80 ° C. for another 60 minutes.
Then, it cooled and white [resin dispersion 2] with a volume average particle diameter of 93 nm was obtained. The obtained [Resin Dispersion 2] was placed in a 2 ml petri dish, and the dried product obtained by evaporating the dispersion medium was measured. As a result, the number average molecular weight was 8100, the weight average molecular weight was 16100, and Tg was 81 ° C. It was.

<Method for producing resin dispersion 3>
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 0.7 part of sodium dodecyl sulfate and 498 parts of ion-exchanged water were added and dissolved by heating to 80 ° C. with stirring, and then potassium persulfate. A solution prepared by dissolving 2.5 parts in 101 parts of ion-exchanged water was added, and 15 minutes later, a monomer mixture of 169 parts of styrene monomer, 30 parts of butyl acrylate and 1 part of divinylbenzene was added dropwise over 90 minutes. Thereafter, the polymerization reaction was continued at 80 ° C. for a further 60 minutes.
Then, it cooled and the white [resin dispersion 3] with a volume average particle diameter of 100 nm was obtained. The obtained [Resin dispersion 3] was placed in a 2 ml petri dish and the dried solid obtained by evaporating the dispersion medium was measured. The number average molecular weight was 31,300, the weight average molecular weight was 88300, and Tg was 75 ° C.

Production method of polymerized toner <Synthesis of polyester 1>
229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propion oxide 3-mole adduct, 208 parts of terephthalic acid, 46 parts of adipic acid and dibutyltin oxide 2 parts were added and reacted at 230 ° C. under normal pressure for 8 hours. Next, after reacting under reduced pressure of 10 to 15 mmHg for 5 hours, 44 parts of trimellitic anhydride was added to the reaction vessel and reacted at 180 ° C. for 2 hours under normal pressure to synthesize [Polyester 1]. . The obtained [Polyester 1] had a number average molecular weight of 2,500, a weight average molecular weight of 6,700, a glass transition temperature of 43 ° C., and an acid value of 25 mgKOH / g.

<Synthesis of polyester 2>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 264 parts of bisphenol A ethylene oxide 2-mole adduct, 523 parts of bisphenol A propylene oxide 2-mole adduct, 123 parts of terephthalic acid, 173 parts of adipic acid and dibutyl 1 part of tin oxide was added and reacted for 8 hours at 230 ° C. under normal pressure, and further reacted for 8 hours under reduced pressure of 10 to 15 mmHg. Thereafter, 26 parts of trimellitic anhydride was added to the reaction vessel and reacted at 180 ° C. and normal pressure for 2 hours to obtain [Polyester 2]. [Polyester 2] had a number average molecular weight of 4000, a weight average molecular weight of 47000, Tg of 65 ° C., and an acid value of 12.

-Synthesis of isocyanate-modified polyester 1-
In a reaction vessel equipped with a condenser and a nitrogen introducing tube, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, 22 parts of trimellitic anhydride and 2 parts of dibutyltin oxide was charged and reacted at 230 ° C. for 8 hours under normal pressure. Next, it was reacted for 5 hours under a reduced pressure of 10 to 15 mmHg to synthesize [Intermediate Polyester 1]. The obtained [Intermediate polyester 1] has a number average molecular weight of 2,200, a weight average molecular weight of 9,700, a glass transition temperature of 54 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 52 mgKOH / g. there were.
Next, 410 parts of [Intermediate polyester 1], 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Modified polyester 1] was obtained.

-Preparation of master batch-
Carbon black (Regal 400R manufactured by Cabot Corporation): 40 parts, Binder resin: Polyester resin (Sanyo Kasei RS-801 Acid value 10, Mw 20,000, Tg 64 ° C.): 60 parts, Water: 30 parts are mixed in a Henschel mixer. Thus, a mixture in which water was soaked into the pigment aggregate was obtained. This was kneaded for 45 minutes with two rolls set at a roll surface temperature of 130 ° C. and pulverized to a size of 1 mm with a pulverizer to obtain [Masterbatch 1].

Example 1
<Oil phase preparation process>
In a container equipped with a stir bar and a thermometer, 545 parts of [Polyester 1], 181 parts of [paraffin wax (melting point 74 ° C.)] and 1450 parts of ethyl acetate are charged, and the temperature is raised to 80 ° C. with stirring and remains at 80 ° C. After holding for 5 hours, it was cooled to 30 ° C. in 1 hour. Next, 500 parts of [Masterbatch 1] and 100 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 1].
[Raw material solution 1] 1500 parts are transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), liquid feeding speed is 1 kg / hr, disk peripheral speed is 6 m / sec, and 0.5 mm zirconia beads are 80% by volume. The pigment and WAX were dispersed under the conditions of filling and 3 passes. Next, 655 parts of a 66% ethyl acetate solution of [Polyester 1] was added, followed by one pass with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 1].
[Pigment / WAX Dispersion 1] 976 parts were mixed for 1 minute at 5,000 rpm with a TK homomixer (made by Tokushu Kika), and then 88 parts of [Isocyanate-modified polyester 1] were added to a TK Homomixer (made by Tokushu Kika). ) At 5,000 rpm for 1 minute to obtain [Oil Phase 1]. It was 52.0 mass% when solid content of the obtained [oil phase 1] was measured, and the quantity of ethyl acetate with respect to solid content was 92 mass%.

<Preparation of aqueous phase>
970 parts of ion-exchanged water, 40 parts of a 25% by weight aqueous dispersion of organic resin fine particles for dispersion stabilization (styrene copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate), dodecyl When 95 parts of a 48.5% aqueous solution of sodium diphenyl ether disulfonate and 98 parts of ethyl acetate were mixed and stirred, the pH reached 6.2. A 10% aqueous sodium hydroxide solution was added dropwise thereto to adjust the pH to 9.5 to obtain [Aqueous Phase 1].

<Core particle production process>
Add 1200 parts of [Aqueous Phase 1] to [Oil Phase 1] obtained above, and cool in a water bath to suppress temperature rise due to shear heat of the mixer. While adjusting so as to be, adjust at a rotation speed of 8,000 to 15,000 rpm using a TK homomixer, mix for 2 minutes, and then adjust at a rotation speed of 130 to 350 rpm with a three-one motor with an anchor blade attached. The mixture was stirred for 10 minutes to obtain [Core Particle Slurry 1] in which oil phase droplets serving as core particles were dispersed in an aqueous phase.

<Formation of protrusions>
Ion exchange with 106 parts of [Resin dispersion 1] at a liquid temperature of 22 ° C. while stirring the [core particle slurry 1] with a three-one motor with an anchor blade attached at a rotational speed of 130 to 350 rpm. A mixture of 71 parts of water (solid content concentration 15%) was added dropwise over 3 minutes. After dropping, the number of rotations was adjusted to 200 to 450 rpm, and stirring was continued for 30 minutes to obtain [Composite Particle Slurry 1]. When 1 ml of [Composite Particle Slurry 1] was taken and diluted to 10 ml and centrifuged, the supernatant was transparent.

<Desolvent>
[Composite particle slurry 1] was put into a container equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 8 hours while stirring to obtain [Dispersion slurry 1]. When [Dispersion Slurry 1] was placed on a small amount of slide glass and the state was observed with an optical microscope at a magnification of 200 times with a cover glass in between, uniform core particles were observed. Further, when 1 ml of [Dispersion Slurry 1] was taken and diluted to 10 ml and centrifuged, the supernatant was transparent.

<Washing and drying process>
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(2): 900 parts of ion-exchanged water was added to the filter cake of (1), ultrasonic vibration was applied, and the mixture was mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure. This operation was repeated so that the electric conductivity of the reslurry liquid was 10 μC / cm or less.
(3): 10% hydrochloric acid was added so that the reslurry solution of (2) had a pH of 4, and the mixture was directly filtered with a three-one motor for 30 minutes.
(4): 100 parts of ion-exchanged water was added to the filter cake of (3), mixed with a TK homomixer (10 minutes at 12,000 rpm) and then filtered. This operation was repeated so that the reslurry liquid had an electric conductivity of 10 μC / cm or less to obtain [Filter Cake 1].
[Filtration cake 1] was dried at 45 ° C. for 48 hours in a circulating drier, and sieved with an opening of 75 μm mesh to obtain [Toner Base 1]. When the obtained [Toner Base 1] was observed with a scanning electron microscope, the vinyl resin fine particles were uniformly attached to the surface of the core particles.
[Toner base 1] [Toner 1] was obtained by mixing 100 parts of the external additive of Table 1 with a Henschel mixer and removing coarse particles and aggregates by passing through a sieve having an opening of 60 μm. .

(Example 2)
Except that [Resin Dispersion 1] in Example 1 was changed to [Resin Dispersion 2], [Toner Base 2] was prepared in the same manner, except that [Toner Base 2] was used (Example 1). [Toner 2] was obtained in the same manner as above.

(Example 3)
[Toner Base 3] was prepared in the same manner except that [Resin Dispersion 1] in Example 1 was changed to [Resin Dispersion 3] (Example 1) except that [Toner Base 3] was used. In the same manner, [Toner 3] was obtained.

Example 4
<Preparation of aqueous phase>
970 parts of ion-exchanged water, 29 parts of a 25 wt% aqueous dispersion of organic resin fine particles (styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt) for dispersion stabilization, dodecyl diphenyl ether When 95 parts of a 48.5% aqueous solution of sodium disulfonate and 98 parts of ethyl acetate were mixed and stirred, the pH was 6.2. A 10% aqueous sodium hydroxide solution was added dropwise thereto to adjust the pH to 9.1 to obtain [Aqueous Phase 2].

<Preparation of pigment / WAX dispersion (oil phase)>
A container equipped with a stir bar and a thermometer was charged with 175 parts of [Polyester 1], 430 parts of [Polyester 2], 153 parts of [Paraffin wax (HNP9)] and 1450 parts of ethyl acetate, and the temperature was raised to 80 ° C. with stirring. The sample was kept at 80 ° C. for 5 hours and then cooled to 30 ° C. in 1 hour. Next, 410 parts of [Masterbatch 1] and 100 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Material solution 2].

  [Raw material solution 2] 1500 parts are transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by IMEX), liquid feeding speed is 1 kg / hr, disk peripheral speed is 6 m / sec, and 0.5 mm zirconia beads are 80% by volume. The pigment and WAX were dispersed under the conditions of filling and 3 passes. Next, 470 parts of a 70% ethyl acetate solution of [Polyester 1], 250 parts of a 55% ethyl acetate solution of [Polyester 2], and 95 parts of ethyl acetate were added, followed by one pass with a bead mill under the above conditions, [Pigment / WAX dispersion liquid] 2] was obtained. The solid content of the obtained [Pigment / WAX Dispersion 2] was measured to be 49.3% by mass, and the amount of ethyl acetate based on the solid content was 103% by mass.

<Emulsification process>
[Pigment / WAX Dispersion 2], 976 parts, was mixed for 1 minute at 5,000 rpm with a TK homomixer (made by Tokushu Kika), and then added at 5,000 rpm with a TK homomixer (made by Tokushu Kika). After mixing for 1 minute, 1200 parts of [Aqueous phase 2] was added and mixed for 2 minutes while adjusting at 8,000 to 15,000 rpm with a TK homomixer to obtain [Emulsion slurry 2].

<Protrusion formation process>
[Emulsified slurry 2] 20 parts of [resin dispersion 1] are added to a container containing 100 parts of a stirrer and a thermometer, mixed and stirred for 10 minutes, the temperature is raised to 60 ° C., and further 60 minutes The mixture was stirred to obtain [Composite Particle Slurry 2].

<Desolvation and washing ⇒ Drying>
Except that [Composite Particle Slurry 1] in Example 1 was changed to [Composite Particle Slurry 2], [Toner Base 4] was prepared in the same manner, except that [Toner Base 4] was used (Example 1). ) To obtain [Toner 4].

(Example 5)
[Toner] in the same manner as in Example 1 except that the addition amount of [Resin Dispersion 1] was changed to 42 parts and the addition amount of ion-exchanged water was changed to 31 parts in the <projection formation> step of Example 1. [Mother 5] was prepared, and [Toner 5] was obtained in the same manner as in Example 1 except that [Mother toner 5] was used.

(Example 6)
[Toner] in the same manner as in Example 1 except that the amount of [resin dispersion 1] was changed to 318 parts and the amount of ion-exchanged water was changed to 231 parts in the <projection formation> step of Example 1. [Mother 6] was produced, and [Toner 6] was obtained in the same manner as in Example 1 except that [Mother toner 6] was used.

(Example 7)
By mixing 100 parts of [Toner Base 1] of Example 1 with the external additive shown in Table 1 using a Henschel mixer and passing through a sieve having an opening of 60 μm, coarse particles and aggregates are removed, and [Toner 7 ] Was obtained.

(Example 8)
By mixing 100 parts of [Toner Base 1] of Example 1 with the external additive shown in Table 1 using a Henschel mixer and passing through a sieve having an opening of 60 μm, coarse particles and aggregates are removed, and [Toner 8 ] Was obtained.

(Comparative Example 1)
[Toner Base 7] was prepared in the same manner as in Example 1 except that [Resin Dispersion 1] of Example 1 was not added, and (Example 1) except that [Toner Base 7] was used. Similarly, [Toner 9] was obtained.

(Comparative Example 2)
[Toner Base 8] was the same as Example 1 except that the amount of [Resin Dispersion 1] was changed to 530 parts and the amount of ion-exchanged water was changed to 385 parts in the <Protrusion Formation> step of Example 1. [Toner 10] was obtained in the same manner as in Example 1 except that [Toner Base 8] was used.

(Comparative Example 3)
By mixing 100 parts of [toner base 1] of Example 1 with the external additive of Table 1 using a Henschel mixer and passing through a sieve having an opening of 60 μm, coarse particles and aggregates are removed, and [toner 11 ] Was obtained.

(Comparative Example 4)
By mixing 100 parts of [toner base 1] of Example 1 with the external additive of Table 1 using a Henschel mixer and passing through a sieve having an opening of 60 μm, coarse particles and aggregates are removed, and [Toner 12 ] Was obtained.

The toner obtained as described above was evaluated by the following method.
<Cleanability>
Using a color electrophotographic apparatus (IPSiO SP C220), after outputting 2000 image charts with a 1% image area, a white solid image was output, and the presence or absence of cleaning failure was evaluated in four stages.
◎ ・ ・ ・ No cleaning failure, very good level ○ ・ ・ ・ Cleaning level, but no problem in practical use △ ・ ・ ・ Cleaning level, practically problematic level × ・ ・ ・ Cleaning failure Conspicuous level

<Photoconductor shaving>
Using a color electrophotographic apparatus (IPSiO SP C220), 2000 image charts having a 1% image area were output, and then the surface of the photosensitive member was evaluated by four stages of visual observation.
◎ ・ ・ ・ No streak, very good level ○ ・ ・ ・ Striped, but practically no problem △ ・ ・ ・ Striped, practically problematic level × ... Levels where streaks are conspicuous

<Fixability>
Toner was put in the modified IPSiO SP C220, and 19 sheets of 50 mm square unfixed solid images were printed on Ricoh's My Recycle Paper 100T eye paper with an adhesion amount set to 11 g / m ² . .
Next, using the modified fixing unit, the system speed was set to 180 mm / sec, and the prepared unfixed solid image was passed through to fix the image. The fixing temperature was tested from 120 ° C to 200 ° C in 10 ° C increments. The fixed image was folded inward, spread again, and then lightly rubbed with an eraser. The lowest temperature at which the crease did not disappear was defined as the minimum fixing temperature.
〔Evaluation criteria〕
A: Fixing lower limit temperature is less than 130 ° C. ○: Fixing lower limit temperature is 130 ° C. or more and less than 140 ° C. Δ: Fixing lower limit temperature is 140 ° C. or more and less than 150 ° C. ×: Fixing lower limit temperature is 150 ° C. or more.

Dv / Dn in Table 1 means the volume average particle diameter and number average particle diameter of the toner.
External additives H20TM (manufactured by Clariant Japan Co., Ltd.), RY50 (manufactured by Nippon Aerosil Co., Ltd.), and RX50 (manufactured by Nippon Aerosil Co., Ltd.) are silica, each having a BET specific surface area, The surface treatment and the primary particle diameter are as shown in Table 2 below.

DESCRIPTION OF SYMBOLS 1 Latent image carrier 2 Charging apparatus 3 Exposure apparatus 4 Developing means 5 Cleaning part 6 Intermediate transfer body 7 Support roller 8 Transfer roller 9 Heating roller 10 Aluminum core 11 Elastic body layer 12 PFA surface layer 13 Heater 14 Pressure roller 15 Aluminum core Gold 16 Elastic layer 17 PFA surface layer 18 Unfixed image 19 Fixing means 40 Developing roller 41 Thin layer forming member 42 Supply roller L Exposure P Recording paper T Electrostatic charge image developing toner

JP 2008-090256 A

Claims (10)

A toner for developing a dry electrostatic image containing at least a binder resin and a colorant,
The toner has a protrusion on the surface,
The average length of the long side of the protrusion is 0.1 μm or more and 0.5 μm or less,
The standard deviation of the length of the long side of the protrusion is 0.2 or less,
The coverage of the toner surface by the protrusions is 10% to 90%,
The toner contains a silicone oil-treated external additive,
The total amount of silicone oil in the toner is 0.2 to 0.5% by mass with respect to the toner,
The toner for developing an electrostatic charge image, wherein an additive amount of the external additive is 0.5 to 4 parts by mass with respect to 100 parts by mass of the toner. The toner for developing an electrostatic charge image according to claim 1, wherein the external additive has a BET specific surface area of 10 to 50 m ² / g.   The electrostatic charge image developing toner according to claim 1, wherein the external additive is silica.   The electrostatic image developing toner according to claim 1, wherein the external additive has an average primary particle size of 30 to 150 nm. The toner for an electrostatic charge image developer according to any one of claims 1 to 4, wherein an amount of the silicone oil as the external additive is ² to 10 mg / m ² per surface area of the external additive. 6. The electrostatic image developing toner according to claim 1, wherein the protrusion is made of a resin, and the resin is made of a resin containing styrene. The toner for developing an electrostatic charge image according to any one of claims 1 to 6, wherein the ratio of the weight of the resin constituting the protruding portion to the total weight of the toner is 1% or more and 20% or less. . 8. The toner according to claim 1, wherein the toner is obtained by manufacturing a core particle of the toner and then performing a process of fusing the protrusion to the surface of the core particle. The electrostatic image developing toner according to claim 1. A latent image carrier for carrying a latent image;
Charging means for uniformly charging the surface of the latent image carrier;
Exposure means for exposing the surface of the charged latent image carrier on the basis of image data and writing an electrostatic latent image;
Toner removal means for removing residual toner with a cleaning blade after transfer,
A toner that visualizes the latent image;
Developing means for supplying and developing toner on the electrostatic latent image formed on the surface of the latent image carrier;
Transfer means for transferring the visible image on the surface of the latent image carrier to the transfer target;
Fixing means for fixing a visible image on the transfer target;
An image forming apparatus comprising:
An image forming apparatus, wherein the toner is the toner according to claim 1. The latent image carrier, the developing means for developing at least the latent image on the latent image carrier with a developer, and the toner removing means for removing the residual toner on the latent image carrier after the transfer with a cleaning blade are integrated. In the process cartridge configured to be detachable from the image forming apparatus,
A process cartridge using the toner according to claim 1 as the toner.