JP2017142379A - toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that has high low-temperature fixability, can suppress an external additive from being embedded in a toner base particle, and can maintain high transfer efficiency, the toner being capable of providing stable image quality for a long period and highly efficient in saving energy.SOLUTION: Toner particles included in a toner including the toner particles and fine particles on the surface thereof have surface with a matrix-domain structure. A matrix part in the matrix-domain structure is formed of a resin having a 1/2 method temperature Tm of 125°C or less in melt viscosity measurement by a flow tester temperature raising test at 4.093×10Pa with a die diameter of 1 mm, and a domain part is formed of a polyethylene resin having a density of less than 0.930 g/cma and a weight average molecular weight of 10000 to 5000000. On the surface of the toner particle, an average value of the most proximate distances in the domain parts formed of the polyethylene is 400 nm or less, and an average value of the abundance ratios in the domain parts present on the toner surface is 50% or less.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a toner used for image formation by an image forming apparatus using an electrophotographic system such as a copying machine, a printer, a facsimile machine, or a multifunction machine of these.

2. Description of the Related Art In recent years, an image forming apparatus adopting an electrophotographic system is not only a function as a copying machine for copying a manuscript, but also a multifunction machine that combines functions as an information output device connected to other information devices by digitization. It is widely spread throughout the world. The performance required for the toner used in such a multifunction machine is also increasing, such as high definition, high quality, high image quality, high speed, and high reliability.
In particular, since the environment used by the expansion of the market has expanded, there is a need for a toner having the performance to provide stable image quality that does not depend on the environment.
Further, from the viewpoint of reliability, there is a need to provide a toner suitable for an image forming apparatus that can output an image without degrading image quality even when long-term image output is performed.
On the other hand, in a fixing system in an image forming apparatus, from the viewpoint of energy saving by reducing power consumption, a light pressure fixing system such as a film fixing and a belt fixing with a small heat capacity is becoming mainstream from a conventional hard roller system having a large heat capacity. . In light pressure fixing systems, the heat capacity of fixing members such as thin films and belts has been reduced in order to shorten the time required to reach the fixing set temperature (temperature control temperature) and to improve the quick start. Yes. In order to reduce the heat capacity of the fixing member, the temperature reduction degree of the fixing member increases when high-speed continuous copying is performed as compared with the conventional hard roller system. Therefore, a toner that can be fixed at a lower temperature is required, and as a performance desired for the toner, further improvement in the low-temperature fixability has been demanded.
Further, generally used toner is a functional particle for imparting functions such as fluidity and chargeability and a spacer effect between each member in contact with the toner and the toner. The additive is adhered to the surface of the toner base particles (resin). However, it is known that repeating the image output over a long period of time causes a phenomenon that the toner receives a share in the image forming apparatus and the external additive is liberated from the mother particles or buried in the mother particles. ing. As a result, when the chargeability and fluidity of the toner are lowered and the spacer effect on the photosensitive member is further reduced, all of the toner that forms an electrostatic charge image is transferred from the photosensitive member to the recording medium or the intermediate transfer member. It becomes difficult, that is, the transfer efficiency is lowered. As a result, the image quality may be impaired, for example, the density uniformity in a high density image or the like is significantly reduced.

In order to satisfy the above requirements, a toner that does not deteriorate image quality even after long-term image output, that is, has high durability performance and low-temperature fixability, is required more than ever.
As a method for improving the properties of the toner by combining the components constituting the toner, Patent Document 1 discloses a method for improving the properties of the toner using a combination of the following components.
・ Polyolefin resin with a ring structure as a binder resin.
-Polypropylene wax or polyethylene wax as a release agent.
・ Organic boron compounds with a specific structure as charge control agents.
A polyolefin resin having a cyclic structure is colorless and transparent, has high light transmittance, and has low hygroscopicity.
In Patent Document 1, it is possible to provide a toner excellent in productivity, heat storage, fixing characteristics under low temperature and low humidity, transparency, and environmental stability by combining each of the above components. It is described that it is possible to provide a developing device that suppresses the occurrence. Further, Patent Document 1 describes that a fluidity improver such as silica can be added to the toner.

JP 2004-219507 A

However, even with a toner using a combination of components for obtaining low-temperature fixability and environmental stability as in Patent Document 1, if image output is performed over a long period of time, performance for durability cannot be obtained, and the toner base In some cases, external additives are embedded in the particles, resulting in deterioration of transferability.
The present invention was made to achieve both low-temperature fixability and durability, has high low-temperature fixability, can suppress the burying of external additives in toner base particles, and maintains high transfer efficiency. The object is to provide a possible toner. Another object of the present invention is to provide a highly energy-saving toner that can provide stable image quality over a long period of time.

The toner according to the present invention is
Toner having toner particles and fine particles on the surface of the toner particles,
The toner particle surface has a matrix-domain structure;
The matrix part in the matrix-domain structure contains a resin having a ½ method temperature Tm of 125 ° C. or lower in melt viscosity measurement of 4.093 × 10 ⁵ Pa by a flow tester temperature rising method and a die diameter of 1 mm,
The domain part in the matrix-domain structure comprises a polyethylene resin having a density of less than 0.930 g / cm ³ and a weight average molecular weight of 10,000 to 5,000,000;
On the toner particle surface, the average value of the closest distance of the domain part is 400 nm or less,
The toner is characterized in that the average value of the abundance ratio of the domain portions existing on the surface of the toner particles is 50% or less.

  According to the present invention, it is possible to provide a toner having high low-temperature fixability and capable of suppressing the burying of an external additive, satisfying stable image quality over a long period of time, and high energy saving. .

1 is a schematic view of an example of an electrophotographic image forming apparatus to which the toner of the present invention can be applied. FIG. 3 is a schematic view of an example of an electrophotographic process cartridge to which the toner of the present invention can be applied.

The toner according to the present invention includes toner particles and fine particles, and has a configuration in which fine particles on the surface of the toner particles are fixed. The surface of the toner particles has a matrix-domain structure.
The matrix portion contains a resin having a 1/2 method temperature Tm of 125 ° C. or lower in the measurement of the melt viscosity of 4.093 × 10 ⁵ Pa by a flow tester temperature rising method and a die diameter of 1 mm. The domain part includes a polyethylene resin having a density of less than 0.930 g / cm ³ and a weight average molecular weight of 10,000 to 5,000,000. In the matrix-domain structure, the average value of the closest distances between the adjacent domain parts is 400 nm or less, and the average value of the abundance ratio of the domain parts existing on the toner particle surface is 50% or less.
Further, in the matrix-domain structure, a configuration (sea island-like configuration) in which independent domain portions are dispersedly arranged in a matrix portion continuously spreading on the surface is formed on at least a part of the toner core particle surface. Has been.

In the following, embodiments of the present invention are shown, and the present invention will be described more specifically.
(I) Image Forming Apparatus An example of an image forming apparatus to which the toner of the present invention can be applied will be described below.
FIG. 1 is a schematic configuration diagram of an image forming apparatus as a full-color laser printer using an electrophotographic process. FIG. 2 is a schematic view of a process cartridge that can be detachably attached to the image forming apparatus shown in FIG.
First, an overall schematic configuration of the image forming apparatus will be described. However, the dimensions, materials, shapes, and relative arrangements of the components described in the embodiments described below are intended to limit the scope of the present invention only to those unless otherwise specified. It is not a thing.
In the main body of the image forming apparatus shown in FIG. 1, four mounting portions for the cartridge 11 are prepared. Each mounting portion is provided with a primary transfer device 5 for transferring the toner image to the intermediate transfer body 6. A cartridge 11 filled with toners of yellow, magenta, cyan, and black is mounted from the upstream side in the moving direction of the intermediate transfer member 6. A color image can be formed by sequentially transferring each color image necessary for obtaining a target color image to the intermediate transfer body 6. Each color toner stored in the developing device of each process cartridge 11 is a toner according to the present invention described later.
The toner image on the intermediate transfer body 6 is transferred to a recording medium 8 such as paper in a secondary transfer device 7.
The latent image formation in each process cartridge 11 is performed by exposure with laser light from the laser optical device 3.
FIG. 2 shows an outline of the configuration of the process cartridge 11. The process cartridge 11 includes a photoreceptor 1, a charging roller 2, a developing device 4, and a cleaning blade 9. Each of these components is integrated into the process cartridge main body, and is configured as a cartridge type that can be attached to and detached from the image forming apparatus main body.
The toner image is formed by the process cartridge 11 shown in FIG. 2 by the following operation. The photoconductor 1 as an image carrier is rotated in the direction of an arrow r and charged to a uniform potential Vd by a charging roller 2 as a charging device. Next, exposure is performed with laser light from a laser optical device 3 which is an exposure device shown in FIG. 1, and an electrostatic latent image is formed on the surface thereof. The electrostatic latent image is developed by the developing device 4 and visualized as a toner image. The visualized toner image on the photoreceptor 1 is transferred to the paper 8 as a recording medium through the primary transfer and the secondary transfer described above. Untransferred toner remaining on the photoreceptor 1 without being transferred is scraped off by a cleaning blade 9 which is a cleaning device. The cleaned photoreceptor 1 repeats the above-described operation to form an image. On the other hand, the paper 8 on which the toner image has been transferred is fixed by the fixing device 10 and then discharged outside the apparatus.

The photoreceptor 1 is an organic photoreceptor layer having a multilayer structure in which a positive charge injection prevention layer, a charge generation layer, and a charge transport layer are sequentially laminated on the peripheral surface of an aluminum (Al) cylinder that is a conductive substrate. Is formed. Further, arylate was used as the charge transport layer of the photoreceptor 1, and the thickness of the charge transport layer was adjusted to 23 μm.
The charge transport layer is formed by dissolving a charge transport material together with a binder in a solvent. Examples of organic charge transport materials include acrylic resins, styrene resins, polyesters, polycarbonate resins, polyarylate, polysulfone, polyphenylene oxide, epoxy resins, polyurethane resins, alkyd resins, and unsaturated resins. These charge transport materials can be used alone or in combination of two or more.
The charging roller 2 has a structure in which a semiconductive rubber layer is provided on the peripheral surface of a core metal which is a conductive support, and the resistance of the charging roller is a voltage of 200 V with respect to the conductive drum. When applied, it exhibits a resistance of about 105Ω.
The developing device 4 includes a toner 12 that is a developer, a developing container 13 that is a developer container, a developing roller 14 that is a developer carrying member, a supply roller 15 that supplies the toner 12 to the developing roller 14, and development. A regulation blade 16 is provided as a developer regulation member for the toner amount on the roller 14.
The developing roller 14 has a configuration in which a conductive rubber layer 14b mixed with a conductive agent is provided on a peripheral surface of a cored bar electrode 14a having an outer diameter of φ6 (mm), which is a conductive support. The outer diameter of the developing roller 14 was φ11.5 (mm). Here, as the material of the rubber layer 14b, a general rubber material such as silicone rubber, urethane rubber, EPDM (ethylene / propylene copolymer), hydrin rubber, or rubber in which two or more of these are mixed can be used. It is. In this example, a developing roller was used in which a silicone rubber layer (thickness 2.5 mm) and a urethane rubber layer (layer thickness 10 μm) were formed in this order on the cored bar electrode 14a. Examples of the conductive agent for imparting conductivity to the rubber layer include carbon particles, metal particles, and ion conductive particles. A desired resistance value can be obtained by dispersing the conductive agent in the rubber layer. In this example, carbon particles were used as the conductive agent. Further, in order to adjust the hardness of the entire developing roller, the developing roller 14 having a desired hardness was produced by adjusting the amount of silicone rubber and the amount of silica as a filler.
The supply roller 15 rotates in contact with the developing roller 14, and one end of the regulating blade 16 is in contact with the developing roller 14.

A urethane foam layer 15b is provided on the peripheral surface of a cored bar electrode 15a having an outer diameter φ5.5 (mm), which is a conductive support provided in the supply roller 15. The outer diameter of the entire supply roller 15 including the urethane foam layer 15b is φ13 (mm). The intrusion amount of the supply roller 15 and the developing roller 14 is 1.2 mm. The supply roller 15 rotates in a direction in which the speeds of the supply roller 15 and the developing roller 14 are opposite to each other. The powder pressure of the toner 12 existing around this acts on the urethane foam layer 15b, and the supply roller 15 rotates, whereby the toner 12 is taken into the urethane foam layer. The supply roller 15 including the toner 12 supplies the toner 12 to the developing roller 14 at a contact portion with the developing roller 14 and further rubs the toner 12 to give the toner 12 a preliminary triboelectric charge. On the other hand, the supply roller 15 that supplies toner to the developing roller 14 also has a role of removing toner remaining on the developing roller 14 without being used for development in the developing unit.
The toner 12 supplied from the supply roller 15 to the developing roller 14 reaches the contact position of the regulating blade 16 with the developing roller 14 and is adjusted to a desired charge amount and toner layer thickness. The regulating blade 16 is a stainless steel (SUS) blade having a thickness of 80 μm, and is disposed in a direction against the rotation of the developing roller 14. The regulating blade 16 regulates the amount of the toner 12 on the developing roller 14 to obtain a uniform toner layer thickness and obtain a desired charge amount by frictional charging by rubbing. Further, a voltage having a potential difference of −200 V with respect to the developing roller 14 was applied to the regulating blade 16. This potential difference is for stabilizing the toner layer on the developing roller 14.
The toner layer formed on the developing roller 14 by the regulating blade 16 is conveyed to the developing unit where the developing roller 14 contacts the photoreceptor 1, and reverse development is performed in the developing unit.

In the developing unit, the intrusion amount of the developing roller 14 into the photosensitive member 1 is set to 40 μm by a roller (not shown) provided at the longitudinal end of the developing roller 14. The surface of the developing roller is deformed by being pressed against the photosensitive member 1, thereby forming a developing nip and developing in a stable contact state. The developing roller 14 rotates in the same direction at a circumferential speed ratio of 117% with respect to the photosensitive member 1 in the photosensitive member 1 and its developing nip. The reason for providing such a peripheral speed difference has a role of stabilizing the amount of toner to be developed.
Next, specific voltages in the present embodiment will be described. A dark potential (Vd) is formed by applying −1050 V to the charging roller 2 and further uniformly charging the surface of the photoreceptor 1 to −500 V. The printing part was adjusted to −100 V (bright potential · Vl) by a laser as an exposure means. At this time, by applying a voltage (Vdc) of −300 V to the developing roller 14, the negative polarity toner is transferred to a bright potential to perform reversal development.
Also, | Vd−Vdc | was called Vback, and Vback was set to 200V.
Further, the amount of toner to be filled in the developing device was set to an amount that can print 3000 images with an image ratio of 5%. A specific example of a horizontal line with an image ratio of 5% means an image in which 19 dot line non-printing is repeated after printing 1 dot line.
In the image forming process, the photoreceptor 1 is rotationally driven in the direction of arrow r in FIG. 1 at a speed of 120 mm / sec. In addition, the image forming apparatus has a low speed mode with a process speed of 60 mm / sec in order to secure a heat quantity for fixing when a thick recording paper (thick paper) is passed. In this embodiment, the operation is performed only in two types of process modes. However, a plurality of process modes may be provided depending on the recording paper, and control corresponding to each process mode can be executed. May be.

By the way, in the toner 12 in the developing device 4, when the fine particles as the external additive adhering to the surface of the toner particles are buried in the toner base particles, the adhesion force of the toner 12 to the photoreceptor 1 increases, and the intermediate transfer member 6. The transfer efficiency on the photosensitive member 1 decreases, and the remaining amount of transfer on the photoreceptor 1 increases. As a result, image defects such as a decrease in density uniformity in a high density image may occur.
Therefore, as a result of repeated studies by the present inventors, it is possible to increase the burial resistance of external additives on the surface of the toner particles by using toner particles having a matrix-domain structure according to the present invention on the surface. As a result, it has been found that the durability of the toner can be remarkably improved.
This mechanism will be described in detail below.
As a result of repeated studies by the present inventors, whether or not the external additive attached to the toner particles is buried in the toner particles due to the shear (shearing force) in the developing device depends on the resin constituting the surface of the toner. It was found that the plastic deformation resistance of the steel strongly influenced.
The particle size of the external additive on the surface of the toner particles is usually several nm to 500 nm, but when image output is performed, a share is applied in various places inside the developing device. For example, a share is applied to the toner at the rubbing portions such as between the developing roller 14 and the supply roller 15, between the developing roller 14 and the regulating blade 16, and between the developing roller 14 and the photoreceptor 1. At that time, the external additive on the surface of the toner particles is pressed against each member to deform the surface of the toner particles formed mainly of the resin. Since the share is removed after passing through the rubbing part, the external additive on the toner particle surface is also unloaded, but the amount of plastic deformation is determined according to the elastic deformation rate of the resin contained on the toner particle surface, and the plasticity External additives are embedded by the amount of deformation.
The domain portion in the matrix-domain structure on the surface of the toner particles according to the present invention contains low-density polyethylene having high elastic deformation characteristics, that is, polyethylene having a density of less than 0.930 g / cm ³ , and the image forming operation can be performed for a long time. The external additive present in this part can maintain a state where it is hardly buried. Furthermore, by setting the distance between the domain portions to be equal to or less than a certain distance, the external additive that is not buried even when the printing operation is performed for a long time works effectively as a spacer, and the transfer efficiency can be maintained over a long period of time.
On the other hand, low density polyethylene generally tends to have a relatively high melting temperature as compared with resins used in toners. If the entire toner particle surface is covered only with low-density polyethylene, a shell that is hard to break is formed on the toner particle surface even at a temperature at which the inside of the toner particle melts at the fixing portion. Therefore, it is necessary to set the fixing temperature high. is there. Therefore, low density polyethylene on the toner particle surface is arranged in a domain shape in a matrix portion containing a resin having a low melting temperature, and the ratio thereof is set to a certain amount or less, so that the resin in the matrix portion is melted in advance. Wax and resin inside the toner can be melted from that portion. As a result, it is not necessary to increase the fixing temperature greatly.

An example of a method for producing an electrophotographic toner according to an embodiment of the present invention will be described below.
(II) Toner Production Method As an example of the toner production method according to the present invention, a matrix-domain structure is formed on the surface of several μm-sized core particles containing a binder resin, pigment, wax, charge control agent, and the like. Examples thereof include a method in which resin fine particles to be adhered are attached by an acid agglomeration method, and are further crushed thermally and the surface is smoothed.
The toner manufacturing method according to the present embodiment includes the following steps.
(1) A step of producing toner core particles.
(2) A step of producing an aqueous dispersion of resin fine particles constituting the matrix portion and an aqueous dispersion of resin fine particles constituting the domain portion, respectively.
(3) A step of attaching resin fine particles to the surface of the toner core particles.
(4) A step of smoothing the surface of the toner core particles to which the resin fine particles are adhered.

Hereinafter, each step will be described.
(1) Preparation of toner core particles As the binder resin that can be used for forming the toner particle core particles (toner core particles), known binders can be used. Vinyl resins such as styrene-acrylic resins and polyesters can be used. Resin or hybrid resin in which they are bonded can be used.
In the method of directly obtaining toner core particles by a polymerization method, a monomer for forming them is used. Specific examples of monomers include styrene monomers such as styrene, o- (m-, p-) methylstyrene, o- (m-, p-) ethylstyrene; methyl acrylate, ethyl acrylate, acrylic Acrylates such as propyl acid, butyl acrylate, octyl acrylate, dodecyl acrylate, stearyl acrylate, behenyl acrylate, 2-ethylhexyl acrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, acrylonitrile, acrylamide Mer: methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, octyl methacrylate, dodecyl methacrylate, stearyl methacrylate, behenyl methacrylate, 2-ethylhexyl methacrylate, dimethylamino methacrylate Le, diethylaminoethyl methacrylate, methacrylonitrile, methacrylate based monomers, such as methacrylic acid amide; butadiene, isoprene, olefinic monomers such as cyclohexene is preferably used.
These can be used alone or in combination of two or more. When two or more kinds of resins are used in combination as a binder resin, generally, two or more kinds of monomers are used so that the theoretical glass transition temperature (Tg) of the mixed resin is 40 to 75 ° C. It can mix and use suitably. The theoretical glass transition temperature is J. Brandrup, E.I. H. Immergut, "Polymer Handbook", (USA), 3rd edition, John Wiley & Sons, 1989, p. 209-277.
By setting the theoretical glass transition temperature within the above range, the transparency of the toner image of each color in the case of full-color image formation should be improved while ensuring the storage stability and durability stability of the toner. Can do.
Furthermore, in order to increase the mechanical strength of the toner core particles and to control the molecular weight of the binder resin, a crosslinking agent can be used during the synthesis of the binder resin.

As the crosslinking agent, difunctional linking agents such as divinylbenzene, 2,2-bis (4-acryloxyethoxyphenyl) propane, 2,2-bis (4-methacryloxyphenyl) propane, diallyl phthalate, ethylene glycol di Acrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene Glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200, # 400, # 600 diacrylate, dipropylene glycol diacrylate, polypropylene glycol diacrylate Acrylate include those obtained by changing the polyester type diacrylate, and the above diacrylate dimethacrylate.
Polyfunctional crosslinkers include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate and its methacrylate, triallyl cyanurate, triallyl isocyanurate and triallyl Trimellitate is mentioned.
These crosslinking agents can be used alone or in combination of two or more as required.
The crosslinking agent is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the monomer in terms of toner fixability and offset resistance. Can be used.

The toner of the present invention may be either magnetic toner or non-magnetic toner.
When used as a magnetic toner, the following magnetic materials are preferably used when forming the toner core particles. That is, iron oxide such as magnetite, maghemite, ferrite, iron oxide containing other metal oxides, metal such as Fe, Co, Ni, or these metals and Al, Co, Cu, Pb, Mg, Examples thereof include alloys with metals such as Ni, Sn, Zn, Sb, Be, Bi, Cd, Ca, Mn, Se, Ti, W, and V, and mixtures thereof.
Specific examples of the magnetic material include, for example, triiron tetroxide (Fe ₃ O ₄ ), γ-iron sesquioxide (γ-Fe ₂ O ₃ ), iron oxide zinc (ZnFe ₂ O ₄ ), and iron yttrium oxide (Y ₃ Fe ₅ O _12), iron oxide cadmium (CdFe ₂ O _4), iron oxide gadolinium _{(Gd 3 Fe 5 O 12)} , oxidized iron-copper (CuFe ₂ O _4), oxidation Tetsunamari _(PbFe 12 _{O 19),} oxide Iron nickel (NiFe ₂ O ₄ ), iron neodymium oxide (NdFe ₂ O ₃ ), iron barium oxide (BaFe ₁₂ O ₁₉ ), iron magnesium oxide (MgFe ₂ O ₄ ), iron oxide manganese (MnFe ₂ O ₄ ), oxidation Examples thereof include iron lanthanum (LaFeO ₃ ), iron powder (Fe), cobalt powder (Co), and nickel powder (Ni).
The magnetic materials described above can be used alone or in combination of two or more.
A magnetic material particularly suitable for the purposes of the present invention is a fine powder of iron trioxide or γ-iron trioxide.
These magnetic materials have an average particle diameter of 0.1 to 2 μm (preferably 0.1 to 0.3 μm), magnetic properties when 795.8 kA / m is applied, and a coercive force of 1.6 to 12 kA / m, saturation. From the viewpoint of toner developability, the magnetization is preferably 5 to 200 Am ² / kg (preferably 50 to 100 Am ² / kg), and the residual magnetization is 2 to 20 Am ² / kg.
The amount of these magnetic materials added can be 10 to 200 parts by weight, preferably 20 to 150 parts by weight, based on 100 parts by weight of the binder resin.

On the other hand, as a colorant added to the toner core particles when used as a nonmagnetic toner, known colorants such as various conventionally known dyes and pigments can be used.
For example, as a colorant for magenta, for example, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 49, 50, 51, 52, 53, 54, 55, 57, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 163, 202, 206, 207, 209; I. Pigment Violet 19; C.I. I. Vat Red 1, 2, 10, 13, 15, 23, 29, 35 and the like.
Examples of cyan colorants include C.I. I. Pigment Blue 2, 3, 15: 1, 15: 3, 16, 17, 25, 26; I. Vat Blue 6; C.I. I. Acid Blue 45; or a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on the phthalocyanine skeleton.
Examples of the colorant for yellow include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 65, 73, 74, 83, 93, 155, 180; I. Solvent Yellow 9, 17, 24, 31, 35, 58, 93, 100, 102, 103, 105, 112, 162, 163; C.I. I. Vat Yellow 1, 3, 20, etc. are mentioned.
As the black colorant, for example, carbon black, aniline black, acetylene black, and those that are toned in black using the yellow / magenta / cyan colorant shown above can be used.
The amount of these colorants to be used varies depending on the kind of the colorant, but it is 0.1 to 60 parts by mass, preferably 0.5 to 50 parts by mass with respect to 100 parts by mass of the binder resin. it can.

The toner core particles can contain a wax component that can act as a release agent, if necessary. Specific examples of the wax component include petroleum waxes such as paraffin wax, microcrystalline wax, petrolatum, and derivatives thereof, montan wax and derivatives thereof, hydrocarbon waxes and derivatives thereof according to the Fischer-Tropsch method, and polyolefin waxes represented by polyethylene. And derivatives thereof, natural waxes such as carnauba wax and candelilla wax, and derivatives thereof. Derivatives include oxides, block copolymers with vinyl monomers, and graft modified products.
Also included are alcohols such as higher aliphatic alcohols, fatty acids such as stearic acid and palmitic acid, or acid amides and esters of these compounds, hydrogenated castor oil and derivatives thereof, plant waxes, animal waxes and the like.
These wax components can be used alone or in combination of two or more.
The addition amount of the wax component is preferably 2.5 to 15.0 parts by mass, more preferably 3.0 to 10.0 parts by mass with respect to 100 parts by mass of the binder resin.
By setting the addition amount of the wax component within the above range, desired charging characteristics can be obtained while maintaining oil-less fixability.

Further, for the purpose of adjusting the charging characteristics, the charge control agent may be used for the preparation of the toner core particles in such an amount that the target charging characteristics can be adjusted according to the developing system used. Examples of charge control agents that can be used include the following.
Negatively chargeable charge control agents include sulfonic acid groups, sulfonate groups, or sulfonic acid ester group-containing polymer compounds; salicylic acid derivatives and metal complexes thereof; monoazo metal compounds; acetylacetone metal compounds; aromatic oxycarboxylic acids Or aromatic mono- or polycarboxylic acids, or metal salts, anhydrides or esters thereof; phenol derivatives such as bisphenol; urea derivatives; boron compounds; calixarene. At least one of these negatively chargeable charge control agents can be used.
Examples of positively chargeable charge control agents include nigrosine-modified products with nigrosine and fatty acid metal salts, guanidine compounds, imidazole compounds, tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate. Quaternary ammonium salts such as, and onium salts such as phosphonium salts thereof and their lake pigments, triphenylmethane dyes and these lake pigments (as rake agents include phosphotungstic acid, phosphomolybdic acid, Phosphotungstic molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.), metal salts of higher fatty acids, dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide Diorganotin oxides such as, dibutyl tin borate, dioctyl tin borate, and the like diorgano tin borate such as dicyclohexyl tin borate. At least one of these positively chargeable charge control agents can be used.

In the present invention, the number average particle diameter (D1) of the toner is preferably in the range of 3.0 to 15.0 μm from the viewpoint of charging stability and obtaining a high-quality image. More preferably, it is in the range of 12.0 μm.
The number average particle diameter (D1) of the toner is mainly determined by the particle diameter of the toner core particles, but the adjustment method differs depending on the manufacturing method of the toner core particles.
For example, in the case of the suspension polymerization method, D1 of the toner core particles can be adjusted by controlling the concentration of the dispersant used in preparing the aqueous dispersion medium, the reaction stirring speed, or the reaction stirring time.

The toner core particles can be produced by various methods. Examples of the method for producing toner core particles include the following methods.
A kneading and pulverizing method in which a binder resin, a pigment, and a release agent are mixed, and toner particles are obtained through a kneading, pulverizing, and classification process.
A suspension polymerization method in which a polymerizable monomer, a pigment, and a release agent are mixed, dispersed or dissolved, granulated in an aqueous medium, and toner particles are obtained by a polymerization reaction.
A solution suspension method in which a binder resin, a pigment, and a release agent are dissolved or dispersed in an organic solvent, granulated in an aqueous medium, and then desolvated to obtain toner particles.
An emulsion aggregation method in which fine particles of a binder resin, a pigment, and a release agent are finely dispersed in an aqueous medium and aggregated into a toner particle size to obtain toner particles.
It is preferable to use a production method of granulating in an aqueous medium, such as a suspension polymerization method, a dissolution suspension method, or an emulsion aggregation method, which can obtain a toner having a high average circularity relatively easily.
Hereinafter, an embodiment of the production of toner core particles using the suspension polymerization method and the emulsion aggregation method will be described.

(Suspension polymerization method)
In order to produce toner core particles by the suspension polymerization method, the polymerizable monomer composition for preparing the binder resin, the colorant, the wax component, and the polymerization initiator are mixed to prepare a polymerizable monomer composition. Prepare. The polymerizable monomer composition is dispersed in an aqueous medium, and the particles of the polymerizable monomer composition are granulated in the aqueous medium. Next, the toner core particles are obtained by polymerizing the polymerizable monomer in the particles of the polymerizable monomer composition in an aqueous medium.
Examples of the polymerization initiator used in the suspension polymerization method include known polymerization initiators. Specific examples of the polymerization initiator include azo polymerization initiators, organic peroxide polymerization initiators, inorganic peroxide polymerization initiators, and photopolymerization initiators.
Specific examples of compounds that can be used as the azo polymerization initiator include 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2 ′. -Azo compounds such as azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis (isobutyrate). it can.
Specific examples of compounds that can be used as an organic peroxide polymerization initiator include benzoyl peroxide, di-tert-butyl peroxide, tert-butyl peroxyisopropyl monocarbonate, tert-hexyl peroxybenzoate, and tert-butyl. Mention may be made of organic peroxides such as peroxybenzoate.
Specific examples of the compound that can be used as the inorganic peroxide polymerization initiator include potassium persulfate and ammonium persulfate.
Examples of the photopolymerization initiator include acetophenone series, benzoin ether series, and ketal series.
Furthermore, redox initiators such as hydrogen peroxide-ferrous iron, BPO-dimethylaniline, cerium (IV) salt-alcohol can be used.
A polymerization initiator can be used individually or in combination of 2 or more types. The polymerization disclosure agent can be selected according to the polymerization method, and the polymerization initiator selected with reference to the 10-hour half-life temperature in the polymerization method to be used can be used alone or in admixture of two or more.
The addition amount of the polymerization initiator is preferably in the range of 0.1 to 20 parts by mass, more preferably in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

As the aqueous medium, an aqueous medium that can be used for toner core particle formation can be selected from aqueous media that are used for known polymerization suspension methods. As the aqueous medium, an aqueous medium comprising at least water and a dispersion stabilizer is preferable. The dispersion stabilizer may be added to water together with the polymerizable monomer composition or may be previously contained on the water side. As the dispersion stabilizer, known inorganic and organic dispersion stabilizers can be used.
Examples of inorganic dispersion stabilizers include calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, and calcium sulfate. , Barium sulfate, bentonite, silica, alumina and the like. Examples of the organic dispersion stabilizer include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, starch and the like.
Further, a nonionic, anionic or cationic surfactant can be used as the dispersion stabilizer.

Specific examples of the surfactant include sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, calcium oleate and the like.
The dispersion stabilizers can be used alone or in combination of two or more.
Among the above dispersion stabilizers, in the present invention, it is preferable to use a poorly water-soluble inorganic dispersion stabilizer that is soluble in acid, such as calcium phosphate.
When preparing an aqueous dispersion medium using a hardly water-soluble inorganic dispersion stabilizer, the dispersion stabilizer is in a range of 0.2 to 2.0 parts by mass with respect to 100 parts by mass of the polymerizable monomer. It is preferable to use it at such a ratio in terms of obtaining better droplet stability in the aqueous medium of the polymerizable monomer composition.
It is preferable to prepare an aqueous medium using water in the range of 300 to 3000 parts by mass with respect to 100 parts by mass of the polymerizable monomer composition.
When preparing an aqueous medium in which a poorly water-soluble inorganic dispersion stabilizer is dispersed, a commercially available poorly water-soluble dispersion stabilizer can be used as it is.
In order to obtain dispersion stabilizer particles having a fine and uniform particle size in an aqueous medium, a preparation method in which particles of a hardly water-soluble inorganic dispersion stabilizer are produced under high-speed stirring in water is preferable. For example, when calcium phosphate is used as a dispersion stabilizer, a preferable dispersion stabilizer can be obtained by mixing sodium phosphate aqueous solution and calcium chloride aqueous solution under high speed stirring to form calcium phosphate fine particles in the aqueous solution. it can.

(Emulsion aggregation method)
When the emulsion aggregation method is used, toner core particles can be produced through the following steps, for example.
A step of preparing an aqueous dispersion of components for forming toner core particles such as the binder resin, the colorant, and the wax mentioned above (dispersing step)
A step of mixing an aqueous dispersion of toner core particle forming components and aggregating these components to form aggregate particles (aggregation step).
A step of heating the aggregate particles and fusing the constituent components of the aggregate particles to form the corner core particles (fusion step).
-Toner core particle washing process and drying process.
In the dispersion step of each toner core particle forming component, a dispersant such as a surfactant can be used. Specifically, an aqueous dispersion of the toner core particle forming component can be obtained by dispersing the toner core particle forming component together with a surfactant in an aqueous medium. As the aqueous medium, those usable in the production of toner core particles can be selected from those used in known emulsion aggregation methods. The aqueous medium can be prepared using at least water and a dispersant. The dispersant may be added to water together with the component for forming the toner core particles or may be preliminarily contained on the water side.
The aqueous dispersion of the toner core particle forming component can be produced by a known method. For the preparation of the aqueous dispersion, for example, a media type dispersing machine such as a rotary shearing homogenizer, a ball mill, a sand mill, or an attritor, a high-pressure opposed collision type dispersing machine, or the like is preferably used.
Examples of the surfactant include water-soluble polymers, inorganic compounds, and ionic or nonionic surfactants. In particular, in order to obtain high dispersibility, ionicity is preferable, and an anionic surfactant is particularly preferably used.
From the viewpoint of detergency and surface activity, the molecular weight of the surfactant is preferably in the range of 100 to 10,000, and more preferably in the range of 200 to 5,000.
Specific examples of the surfactant include water-soluble polymers such as polyvinyl alcohol, methylcellulose, carboxymethylcellulose, and sodium polyacrylate; sodium dodecylbenzenesulfonate, sodium octadecylsulfate, sodium oleate, sodium laurate, stearic acid Anionic surfactants such as potassium; cationic surfactants such as laurylamine acetate and lauryltrimethylammonium chloride; zwitterionic surfactants such as lauryldimethylamine oxide; polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether , Surfactants such as nonionic surfactants such as polyoxyethylene alkylamine; tricalcium phosphate, aluminum hydroxide, calcium sulfate, calcium carbonate Um, and inorganic compounds such as barium carbonate.
In addition, these may be used individually by 1 type and may be used in combination of 2 or more type as needed.

The method for forming the aggregate particles is not particularly limited, but a pH adjuster, an aggregating agent, a stabilizer and the like are added and mixed in the aqueous dispersion mixture of the components for forming the toner core particles, A method of suitably adding temperature, mechanical power (stirring) and the like can be suitably exemplified.
Although it does not specifically limit as a pH adjuster, Acids, such as alkalis, such as ammonia and sodium hydroxide, nitric acid, and a citric acid, are mentioned. These may be used alone or in combination of two or more.
The flocculant is not particularly limited, and examples thereof include inorganic metal salts such as sodium chloride, magnesium carbonate, magnesium chloride, magnesium nitrate, magnesium sulfate, calcium chloride, and aluminum sulfate, as well as divalent or higher metal complexes. Can be mentioned. These may be used alone or in combination of two or more.
As the stabilizer, surfactants are mainly exemplified. The surfactant as the stabilizer is not particularly limited. For example, water-soluble polymers such as polyvinyl alcohol, methylcellulose, carboxymethylcellulose, and sodium polyacrylate; sodium dodecylbenzenesulfonate, sodium octadecylsulfate, olein Anionic surfactants such as sodium laurate, sodium laurate, potassium stearate; cationic surfactants such as laurylamine acetate and lauryltrimethylammonium chloride; zwitterionic surfactants such as lauryldimethylamine oxide; polyoxyethylene Nonionic surfactants such as alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkylamines, etc .; tricalcium phosphate, aluminum hydroxide Chloride, calcium sulfate, calcium carbonate, and inorganic compounds such as barium carbonate. In addition, these may be used individually by 1 type and may be used in combination of 2 or more type as needed.

The average particle size of the aggregated particles formed here is not particularly limited, but it is usually preferable to control the average particle size to be approximately the same as the average particle size of the toner core particles to be obtained. The particle size of the aggregate particles can be easily controlled by, for example, appropriately setting / changing the temperature at the time of addition / mixing of the flocculant and the like and the conditions of stirring and mixing. Further, in order to prevent adhesion between the aggregate particles and fusion between the toner core particles in the subsequent fusing step, a pH adjuster, a surfactant, and the like can be added as appropriate during the aggregation step.
In the fusing step, the toner core particles are formed by heating the aggregate particles and fusing the components constituting the aggregate particles. The heating temperature in the fusing step may be not less than the glass transition temperature (Tg) of the binder resin contained in the aggregate particles and lower than the decomposition temperature of the binder resin. For example, under the same stirring as in the aggregation step, by stopping the progress of aggregation by adding a surfactant or adjusting pH, and heating to a temperature equal to or higher than the glass transition temperature of the binder resin contained in the aggregate particles. The components constituting the aggregate particles are fused and united. The heating time may be such that the fusion is sufficiently performed. Specifically, the heating may be performed for about 10 minutes to 10 hours.

(2) Preparation of aqueous dispersion of resin fine particles constituting matrix portion and aqueous dispersion of resin fine particles constituting domain portion Hereinafter, a matrix-domain structure is formed on the surface of toner core particles, which is a feature of the toner of the present invention. The material for the preparation and the preparation method thereof will be described.
The matrix part includes a resin that satisfies the condition that the 1/2 method temperature Tm is 125 ° C. or lower in the melt viscosity measurement of 4.093 × 10 ⁵ Pa by a flow tester temperature rising method and a die diameter of 1 mm, and the matrix part is applied. It is preferably made of a resin having characteristics. As the resin for forming the matrix portion, a resin that satisfies the above-described conditions and can be used for the surface treatment of the toner core particles can be selected and used. As the resin for forming the matrix portion, a vinyl resin such as styrene-acrylic resin, a polyester resin, or a hybrid resin obtained by combining them can be used. From the viewpoint of environmental charge stability, it is more preferable to use an olefin polymer having a highly hydrophobic cyclic structure.
By using an olefin polymer having a cyclic structure, the low temperature fixability is high, and not only the burying of the external additive is suppressed, but also the environmental chargeability can be further stabilized. As a result, it is possible to provide a highly energy-saving toner that satisfies stable image quality over a long period of time without depending on the environment.
The olefin polymer having a cyclic structure can be obtained by, for example, metathesis polymerization using a metallocene catalyst or a Ziegler catalyst. That is, this polymerization method is a polymerization method using a catalyst for double bond opening and ring-opening polymerization reaction.
This cyclic olefin polymer is known per se, and synthesis examples thereof are disclosed in, for example, JP-A-5-339327, JP-A-5-9223, JP-A-6-271628, European Patent Application Publication (A No. 203799, 407870, 283164, and 156464, and the like.

As the cyclic olefin polymer, a copolymer of the following monomers is preferable because it is colorless and transparent and has a high light transmittance.
At least one kind of lower alkene (α-olefin, acyclic olefin in a broad sense) having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms.
-At least 1 type of the cyclic | annular and / or polycyclic compound (For example, a cyclic | annular (cyclo) olefin and a polycyclic olefin) which has at least 1 double bond of carbon numbers 3-17, Preferably it is 5-12.

Examples of the lower alkene include ethylene, propylene, and butylene, and examples of the cyclic olefin include norbornene, tetracyclododecene (TCD), dicyclopentadiene (DCPD), and cyclohexene. Among these, ethylene is particularly preferable as the lower alkene.
As the cyclic olefin, norbornene is preferably selected.
On the other hand, according to the patent document disclosing the above-mentioned cyclic olefin polymer, the cyclic olefin polymer is preferably at least one type of cyclic olefin monomer, optionally -78 to 150 ° C with one type of acyclic olefin monomer. Can be obtained by polymerization under conditions of 20 to 80 ° C. and pressure of 0.01 to 64 bar. This reaction is performed in the presence of a co-catalyst such as aluminoxane and a catalyst made of at least one metallocene made of zirconium or hafnium, for example. Other useful cyclic olefin polymers are described in European Patent Application (A) 317262, and hydrogenated polymers and copolymers of styrene and dicyclopentadiene can also be used.
The cyclic olefin polymer used in the present invention is particularly 100 to 100,000, more preferably 500 to 50,000, and 200 to 300,000, preferably 3000 to 200,000. And what has the glass transition point in -20 degreeC-180 degreeC, Preferably 40-80 degreeC is preferable.

The domain part of the matrix-domain structure which is a feature of the present invention includes a polyethylene resin having a density of less than 0.930 g / cm ³ and a weight average molecular weight of 10,000 to 5,000,000. It is preferable to become. As this polyester resin, a known polyester resin that satisfies the above-described characteristics and can be used for the surface treatment of toner core particles can be selected and used. Further, a polyester polymer obtained by a known polymerization method that satisfies the above characteristics and can be used for the surface treatment of toner core particles can be selected and used.
Since polyethylene is highly hydrophobic like an olefin polymer having a cyclic structure, it is excellent in environmental charge stability.
Specific examples of polyethylene that satisfies the above characteristics include high-pressure low-density polyethylene obtained by a high-pressure method and medium-low pressure polyethylene that uses a catalyst to copolymerize α-olefins and ethylene at medium and low pressure. It can be appropriately selected and used accordingly.
As a method for producing the high-pressure polyethylene, various production methods are known, and can be appropriately selected from these known production methods.
For example, in a high-pressure polyethylene production method using radical polymerization, radical chain reaction occurs, and the radical movement causes a molecular structure with various length branches. Since crystallization is inhibited, a low-density and flexible polyethylene can be obtained.
Various production methods are also known for medium-low pressure polyethylene, and can be appropriately selected from these known production methods. Examples of the method for producing the medium / low pressure method polyethylene include a method using a polymerization reaction using a metallocene catalyst as described in JP-A-11-60617. In this polymerization reaction, a linear structure is usually obtained, and in ethylene homopolymerization, there is almost no branching, and high-density polyethylene is produced. On the other hand, by copolymerizing ethylene with α-olefins such as propylene, 1-butene and 1-hexene, a short branch is introduced to lower the crystallinity, and a linear low density polyethylene can be obtained. .
As a polymerization method using a catalyst in which such a metal atom serves as an active site, the following various processes have been developed and used, and known processes can be appropriately selected and used.
A solution polymerization process in which polyethylene is polymerized in a dissolved state in a solvent.
・ Slurry polymerization process using a supported catalyst on silica or magnesium compound and the resulting polyethylene as a slurry in the solvent.
A gas phase polymerization process that polymerizes in a floating state in ethylene or other gases.
It is also possible to adjust the molecular weight distribution and the like by changing the conditions in two or more continuous reaction vessels for polymerization.

Next, details of a step of preparing a first aqueous dispersion as an aqueous dispersion of resin fine particles constituting the matrix portion and a second aqueous dispersion as an aqueous dispersion of resin fine particles constituting the domain portion will be described in detail. To state.
The resin constituting the matrix portion is dissolved in a solvent that can dissolve the resin and is insoluble in water, thereby creating an oil phase. This oil phase is mixed with an aqueous phase in which an anionic surfactant is dissolved in ion-exchanged water, and an oil-in-water emulsion (O / W type) emulsion having an oil phase size of several μm is applied by applying a shearing force with a stirrer. Is made. The obtained emulsion is further subjected to a process of applying a high shearing force and, in some cases, applying a high shearing force under heating, whereby an oil-in-water droplet (O / W type) having an oil phase size of about several tens of nm to 1 μm. ) Emulsions can be made. A wet atomization apparatus (for example, Nanomizer manufactured by Yoshida Kikai Kogyo Co., Ltd., Starburst manufactured by Sugino Machine Co., Ltd.) or the like can be used for the refinement treatment of the oil droplets.
Thereafter, by performing distillation under reduced pressure to remove the solvent, it is possible to obtain a first aqueous dispersion in which resin particles constituting a matrix portion having a particle size of about several tens of nm to 1 μm are dispersed.

The production process of the second aqueous dispersion of resin fine particles constituting the domain part can also be performed in the same manner as the first aqueous dispersion. First, a polyethylene resin having a density of less than 0.930 g / cm ³ and a weight average molecular weight of 10,000 to 5,000,000 constituting the domain part is dissolved in a solvent that can dissolve the polyethylene resin and is insoluble in water. Create a phase. This oil phase is mixed with an aqueous phase in which an anionic surfactant is dissolved in ion-exchanged water, and an oil-in-water emulsion (O / W type) emulsion having an oil phase size of several μm is applied by applying a shearing force with a stirrer. Is made. The obtained emulsion is further subjected to a process of applying a high shearing force and, in some cases, applying a high shearing force under heating, whereby an oil-in-water droplet (O / W type) having an oil phase size of about several tens of nm to 1 μm. ) Emulsions can be made. A wet atomization apparatus (for example, Nanomizer manufactured by Yoshida Kikai Kogyo Co., Ltd., Starburst manufactured by Sugino Machine Co., Ltd.) or the like can also be used for the refinement of the oil droplets.
Thereafter, by performing distillation under reduced pressure to remove the solvent, it is possible to obtain a second aqueous dispersion in which the resin particles constituting the domain part having a particle size of several tens of nm to 1 μm are dispersed.
In addition, the process of producing the aqueous dispersion of resin fine particles constituting the matrix part and the domain part is not limited to the above-described method, and other methods such as emulsion polymerization may be used.

(3) Step of attaching resin fine particles for forming matrix-domain structure to toner core particle surface The first aqueous dispersion liquid and the second aqueous dispersion liquid prepared in the above step (2) are used as a target matrix-domain structure. To obtain a mixture of the aqueous dispersion.
This mixed solution is mixed in a toner core particle size aqueous dispersion in which the toner core particles prepared in the step (1) are dispersed with an anionic surfactant, and a slight amount of dilute hydrochloric acid as an aggregating agent is added to the mixed solution while stirring. Add one by one. By adding this dilute hydrochloric acid, it is possible to obtain an aqueous dispersion of toner core particles in which resin fine particles constituting the matrix portion and the domain portion are dispersed and adhered substantially uniformly.
In addition to the above-described wet method, a dry method using a high-speed fluid mixer such as a Henschel mixer may be used as a method for coating the surface of the toner core particles with the resin fine particles for constituting the matrix portion and the resin fine particles for constituting the domain portion. It is also possible to use it.
When the emulsion aggregation method is used for the preparation of the toner core particles, the above-described adhesion step of the resin fine particles for constituting the matrix portion and the resin fine particles for constituting the domain portion may be performed before the step of fusing the aggregate particles. it can. In other words, the resin particles for forming the matrix part and the resin particles for constituting the domain part are attached to the aggregate particles composed of the toner core particle forming component, and then the fusion process is performed, so that these resin fine particles are attached to the surface. Toner core particles can be obtained. In this case, the fusion and smoothing can be performed by the same heat treatment by setting the conditions for the heat treatment in the fusion step as the conditions for the smoothing treatment of the surface of the toner core particles in step (4) described later.

(4) The step of smoothing the surface of the toner core particles to which the resin fine particles have adhered The toner core particles to which the resin fine particles constituting the matrix portion and the domain portion obtained in the step (3) are substantially uniformly attached to the surface are dried and Either or both of the wet methods can be used to smooth the resin fine particles on the surface to obtain substantially spherical toner particles.
As an example of the wet process, there may be mentioned a method having a process of heating the aqueous dispersion of toner core particles that has undergone the process (3) under conditions for smoothing. In this heating step, by melting the resin fine particles constituting the matrix part and the domain part on the surface of the toner core particle, it is possible to obtain toner particles whose surface is smoothed according to the shape of the toner core particle.
When heating is performed until a predetermined average circularity is achieved, the toner particles are cooled to room temperature under appropriate conditions.
The toner particles according to the present invention can be obtained by washing, filtering, drying, etc. the toner particles obtained after this step.
In addition, as an example of the dry process, the toner core particles contained in the aqueous dispersion liquid that has undergone the process (3) are washed, filtered, dried, subjected to mechanical surface treatment in a dry state, and the surface is smoothened. A method for obtaining particles can be mentioned. For this mechanical surface treatment, an apparatus such as a stirrer such as a Henschel mixer or a surface reformer such as a hybridizer can be used. By applying a shearing force to the toner core particles under the conditions and time for smoothing by such an apparatus, the resin fine particles on the toner core particles are mechanically crushed, and the surface is smoothed so that the toner particles according to the present invention can be obtained. Can be obtained.
In the toner of the present invention, an external additive can be added to the obtained toner from the viewpoint of charge amount adjustment and durability characteristics. The type and amount of the external additive cannot be generally defined, but fine powders such as silica, titanium oxide, alumina, or double oxides thereof, or those obtained by surface treatment thereof can be used.
In order to maintain the transfer efficiency after durability, it is more preferable to add a relatively large external additive having a particle size of about 80 nm to several hundreds of nm to function as spacer particles.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
The following methods were used for the measurement of physical properties in each Example and each Comparative Example.
(A) Measurement Method of Melt Viscosity 1/2 Method Temperature Tm of Resin by Flow Tester Temperature Raising Method Constant-load capillary extrusion rheometer CFD is used for measurement of melt viscosity 1/2 method temperature Tm of resin by the flow tester temperature rising method. A temperature rise test using a −500 flow tester apparatus (manufactured by Shimadzu Corporation) was used.
Specific measurement conditions are as follows.
Die diameter: 1.0mm
Die length: 1.0mm
Weight weight: 500g
Temperature increase rate: 4 ° C./min Preheating time: 420 seconds Sample preparation: 2 g of resin made into pellets with a diameter of 1 cm was used. Calculation of 1/2 method temperature Tm was performed as follows.
In the temperature rising test using a flow tester, the measurement is performed by drawing a plot of temperature and piston stroke, that is, a flow curve. The lowest point Smin of the piston stroke after the softening temperature Ts when the state of the sample in the flow curve shifts from the solid region to the transition region, and the outflow end point are defined as Smax. At this time, the temperature at the piston stroke position STm represented by the following equation is the melting temperature Tm in the 1/2 method.
STm = Smin + (Smax−Smin) / 2 = (Smax + Smin) / 2
(B) Measurement of weight average molecular weight The molecular weight of polyethylene was measured using gel permeation chromatography (hereinafter referred to as GPC). As a solvent, it measured using orthochlorobenzene which is a soluble solvent of polyethylene, and calculated | required the weight average molecular weight Mw of the polyethylene in each Example.
(C) Particle size measurement As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) equipped with a 100 μm aperture tube is used. For setting the measurement conditions and analyzing the measurement data, the attached software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter) was used to measure the number average particle diameter D1.

Example 1
(1) Step of producing toner core particles As toner core particles, resin fine particles C1 were produced by suspension polymerization. Detailed steps are shown below.
(1-1) Polymerizable monomer composition preparation step The following components were mixed and then dispersed by a ball mill for 3 hours.
-Styrene 82.0 mass parts-2-ethylhexyl acrylate 18.0 mass parts-Divinylbenzene 0.1 mass part-C.I. I. Pigment Blue 15: 3 5.5 parts by mass / polyester resin 5.0 parts by mass (polycondensation product of propylene oxide-modified bisphenol A and isophthalic acid (glass transition point 65 ° C., weight average molecular weight (Mw) 10,000, number average molecular weight (Mn) 6000))
The obtained dispersion was transferred to a reactor equipped with a propeller stirring blade and heated to 60 ° C. while stirring at a rotation speed of 300 rpm. 12.0 parts by mass of ester wax (peak temperature of maximum endothermic peak in DSC measurement: 70 ° C., number average molecular weight (Mn) 704), 2,2′-azobis (2,4-dimethylvalero) was added to the heated dispersion. (Nitrile) 3.0 parts by mass was added and dissolved to obtain a polymerizable monomer composition.
(1-2) Dispersion stabilizer preparation process K. 710 parts by mass of ion-exchanged water and 450 parts by mass of a 0.1 mol / L sodium phosphate aqueous solution were added to and mixed in a 2 l four-necked flask equipped with a homomixer (manufactured by Primix). The mixture thus obtained was heated to 60 ° C. while stirring at a rotational speed of 12000 rpm. To this, 68.0 parts of 1.0 mol / L-calcium chloride aqueous solution was added, and an aqueous dispersion medium containing calcium phosphate as a minute hardly water-soluble dispersion stabilizer was prepared.
(1-3) Granulation / polymerization step The polymerizable monomer composition obtained in the step (1-1) is charged into the aqueous dispersion medium containing calcium phosphate obtained in the step (1-2). The mixture was granulated for 15 minutes while maintaining the rotation speed of 12000 rpm. Thereafter, the stirrer was replaced from the high-speed stirrer to the propeller stirring blade, the polymerization was continued for 5 hours at an internal temperature of 60 ° C., the internal temperature was raised to 80 ° C., and the polymerization was further continued for 3 hours. After completion of the polymerization reaction, the residual monomer was distilled off at 80 ° C. under reduced pressure, and then the mixture was cooled to 30 ° C. to obtain a polymer fine particle dispersion.
(1-4) Washing Step The polymer fine particle dispersion obtained in the above step (1-3) was transferred to a washing vessel, and diluted hydrochloric acid was added while stirring to adjust the pH to 1.5. The dispersion was stirred for 2 hours and then solid-liquid separated with a filter to obtain polymer fine particles. This was put into 1200 parts by mass of ion-exchanged water and stirred to obtain a dispersion again, followed by solid-liquid separation with a filter. This operation was performed three times to obtain resin fine particles C1 having a particle diameter of about 5 μm as toner core particles.

(2) Preparation of aqueous dispersion of resin fine particles constituting matrix portion and aqueous dispersion of resin fine particles constituting domain portion (2-1) Step of preparing aqueous dispersion of resin fine particles constituting matrix portion Matrix portion The material for forming resin fine particles constituting and the composition thereof were as follows.
Cycloolefin copolymer (COC) resin (TOPAS (TM) manufactured by Polyplastics: Flow tester 1/2 method temperature Tm 108.84 ° C.): 100 parts by mass Chloroform: 300 parts by mass Anionic surfactant (Daiichi Kogyo) Non-sar LN1 manufactured by Pharmaceutical Co., Ltd .: 8 parts by mass, ion-exchanged water: 933 parts by mass COC resin as a resin constituting the matrix part and chloroform are mixed and dissolved in a heating environment at 60 ° C. to prepare an oil phase. A water phase is prepared by mixing and dissolving an anionic surfactant and ion-exchanged water. The oil phase and the aqueous phase are mixed so as to have the above composition, and stirred for about 10 minutes under the condition of 8000 to 9000 rpm with a robotics manufactured by PRIMIX Co., Ltd., and an oil-in-water droplet having an oil phase size of about 1 μm (O / W type) An emulsion was made.
Further, the obtained emulsion was treated about three times with a starburst manufactured by Sugino Machine Co. at room temperature to produce an oil-in-water (O / W type) emulsion having an oil phase size of about 130 nm.
This emulsion was distilled under reduced pressure to remove chloroform, and the solid content concentration was adjusted by adding ion-exchanged water, and an aqueous dispersion E1 (solid content) in which COC resin particles having a number average particle diameter of about 120 nm were dispersed. A concentration of 10% by mass) was prepared.
(2-2) Step of Producing Aqueous Dispersion of Resin Fine Particles Constructing Domain Part The material for forming the resin fine particles constituting the domain part and the composition thereof were as follows.
Polyethylene resin (Exelen FX351 manufactured by Sumitomo Chemical Co., Ltd., density 0.898 g / cm ³ , weight average molecular weight (Mw): 80000, flow tester 1/2 method temperature Tm 139.98 ° C.): 100 parts by mass xylene: 300 parts by mass・ Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd. Nonsar LN1: 8 parts by mass ・ Ion exchange water: 925 parts by mass) Polyethylene resin as a resin constituting the domain part and xylene are mixed and dissolved in a heating environment at 80 ° C. The oil phase is prepared by mixing and dissolving the anionic surfactant and ion-exchanged water to prepare the aqueous phase.The oil phase and the aqueous phase are mixed so as to have the above composition, and the robotics manufactured by Primics Co., Ltd. Was stirred for about 10 minutes under the condition of 8000 to 9000 rpm to prepare an oil-in-water (O / W type) emulsion having an oil phase size of several μm.
Further, the obtained emulsion was heated to 80 ° C. and treated about three times with a starburst manufactured by Sugino Machine, to produce an oil-in-water (O / W type) emulsion having an oil phase size of about 130 nm. This emulsion was distilled under reduced pressure to remove xylene, and further, ion-exchanged water was added to adjust the solid content concentration, and an aqueous dispersion F1 (solid content) in which polyethylene resin particles having a number average particle diameter of about 120 nm were dispersed. A concentration of 10% by mass) was prepared.

(3) Step of adhering resin fine particles to toner core particle surfaces The materials used in the resin fine particle adhering step and the blending ratio thereof were as follows.
a) Toner core particle C1: 10 parts by mass b) 0.1% by mass aqueous solution of anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK): 48 parts by mass c) 0.2% by mass aqueous solution of anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Non-Sal LN1): 0.5 parts by mass d) Ion exchange water: 133 parts by mass e) Resin fine particle aqueous dispersion E1: 9.5 parts by mass f) Resin fine particle aqueous dispersion F1: 0 .5 parts by mass g) 0.1% by mass aqueous solution of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK): 115.2 parts by mass The toner core particle C1 (a) component prepared in the step (1) ), An anionic surfactant 0.1 mass% aqueous solution (b) component), an anionic surfactant 0.2 mass% aqueous solution (c) component) and ion-exchanged water (d) component) Toner core particle dispersion by mixing with To prepare.
Further, the resin fine particle aqueous dispersion E1 (e) component constituting the matrix part prepared in the step (2), the resin fine particle aqueous dispersion F1 (f) component constituting the domain part), and the anionic surfactant 0.1% by weight aqueous solution (g) component) is mixed in the above blending ratio to prepare a shell fine particle dispersion.
The toner core particle dispersion liquid and the shell fine particle dispersion liquid prepared as described above are mixed so as to have the above blending ratio, and the obtained liquid mixture is heated with stirring to 43 ° C. in a heating water bath. When the liquid temperature reaches 43 ° C., 2 mol / l hydrochloric acid is added dropwise to the mixture at a rate of 14 ml / min while stirring is continued. At any time, a small amount of the mixed solution was extracted, and hydrochloric acid was added until the filtrate passed through a 2 μm microfilter became transparent to prepare an aqueous dispersion T1 of toner core particles to which resin fine particles adhered substantially uniformly. The transparent filtrate from the microfilter shows a state where almost no resin fine particles are present in a dispersed state in the mixed solution and almost all the resin fine particles are attached to the core particles.
(4) The step of smoothing the surface of the toner core particles to which the resin fine particles are adhered. The aqueous dispersion T1 obtained in the step (3) is repeatedly washed with water and filtered to remove the surfactant and then the dryer. Was dried to produce toner core particles T2 having resin particles substantially uniformly attached to the surface.
Thereafter, the particle T2 is treated with a hybridizer type 1 manufactured by Nara Machinery Co., Ltd. for 6 minutes at 2500 rpm to fix and smooth the resin fine particles adhering to the surface of the toner core particle T2, thereby forming a matrix-domain structure on the surface. Toner particles having the following characteristics were prepared.
With respect to the toner particles obtained in the above examples, 100 parts by mass of toner particles are 1.8 parts by mass of hydrophobized silica fine powder having a specific surface area measured by the BET method of 200 m ² / g and a particle diameter of about 30 nm. And 2.0 parts by mass of hydrophobized silica fine powder having a particle size of about 100 nm and a specific surface area measured by the BET method of 40 m ² / g were dry-mixed with a Henschel mixer (Mitsui Mining Co., Ltd.). The external addition process was performed.

(Example 2)
The present embodiment basically conforms to the first embodiment, but differs in the following points.
In step (3) of Example 1, the amounts of the resin fine particle aqueous dispersion E1 constituting the matrix portion and the resin fine particle aqueous dispersion F1 constituting the domain portion were changed as follows.
e) Resin fine particle aqueous dispersion E1: 9.0 parts by mass f) Resin fine particle aqueous dispersion F1: 1.0 part by mass (Example 3)
The present embodiment basically conforms to the first embodiment, but differs in the following points.
In step (3) of Example 1, the amounts of the resin fine particle aqueous dispersion E1 constituting the matrix portion and the resin fine particle aqueous dispersion F1 constituting the domain portion were changed as follows.
e) Resin fine particle aqueous dispersion E1: 7.5 parts by mass f) Resin fine particle aqueous dispersion F1: 2.5 parts by mass (Example 4)
The present embodiment basically conforms to the first embodiment, but differs in the following points.
In the steps (2-1) and (2-2) of Example 1,
An anionic surfactant (Non-Sal LN1 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 10 parts by mass, an aqueous dispersion E2 in which COC resin particles having a number average particle diameter of about 60 nm are dispersed (solid content concentration: 10% by mass) Then, an aqueous dispersion F2 (solid content concentration 10% by mass) in which polyethylene resin particles having a number average particle diameter of about 60 nm were dispersed was prepared.
Further, in the step (3) of Example 1, the resin fine particle aqueous dispersion E1 constituting the matrix portion is changed to E2, and the resin fine particle aqueous dispersion F1 constituting the domain portion is changed to F2, and the respective amounts are as follows It was changed as follows.
e) Resin fine particle aqueous dispersion E2: 9.7 parts by mass f) Resin fine particle aqueous dispersion F2: 0.3 parts by mass (Example 5)
The present embodiment basically conforms to the fourth embodiment, but differs in the following points.
In step (3) in Example 4, the amounts of the resin fine particle aqueous dispersion E2 constituting the matrix portion and the resin fine particle aqueous dispersion F2 constituting the domain portion were changed as follows.
e) Resin fine particle aqueous dispersion E2: 8.7 parts by mass f) Resin fine particle aqueous dispersion F2: 1.3 parts by mass

(Example 6)
The present embodiment basically conforms to the first embodiment, but differs in the following points.
In the steps (2-1) and (2-2) of Example 1,
Anionic surfactant (Non-Sal LN1 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 6.5 parts by mass, an aqueous dispersion E3 in which COC resin particles having a number average particle size of about 195 nm are dispersed (solid content concentration: 10% by mass) And an aqueous dispersion F3 (solid content concentration 10% by mass) in which polyethylene resin particles having a number average particle diameter of about 195 nm are dispersed.
Further, in the step (3) of Example 1, the resin fine particle aqueous dispersion E1 constituting the matrix portion was changed to E3, and the resin fine particle aqueous dispersion F1 constituting the domain portion was changed to F3. It was changed as follows.
e) Resin fine particle aqueous dispersion E3: 8.7 parts by mass f) Resin fine particle aqueous dispersion F3: 1.3 parts by mass (Example 7)
This example is basically the same as Example 6, but differs in the following points.
In step (3) in Example 6, the amounts of the resin fine particle aqueous dispersion E3 constituting the matrix portion and the resin fine particle aqueous dispersion F3 constituting the domain portion were changed as follows.
e) Resin fine particle aqueous dispersion E3: 8.2 parts by mass f) Resin fine particle aqueous dispersion F3: 1.8 parts by mass (Example 8)
This example is basically the same as Example 6, but differs in the following points.
In step (3) in Example 6, the amounts of the resin fine particle aqueous dispersion E3 constituting the matrix portion and the resin fine particle aqueous dispersion F3 constituting the domain portion were changed as follows.
e) Resin fine particle aqueous dispersion E3: 7.5 parts by mass f) Resin fine particle aqueous dispersion F3: 2.5 parts by mass (Example 9)
This example is basically the same as Example 6, but differs in the following points.
In step (3) in Example 6, the amounts of the resin fine particle aqueous dispersion E3 constituting the matrix portion and the resin fine particle aqueous dispersion F3 constituting the domain portion were changed as follows.
e) Resin fine particle aqueous dispersion E3: 5.5 parts by mass f) Resin fine particle aqueous dispersion F3: 4.5 parts by mass (Example 10)
The present embodiment basically conforms to the first embodiment, but differs in the following points.
In the steps (2-1) and (2-2) of Example 1,
-Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd. non-sar LN1) It was 5.0 mass parts. Using this condition, an aqueous dispersion E4 (solid content concentration of 10% by mass) in which COC resin particles having a number average particle size of about 290 nm were dispersed and polyethylene resin particles having a number average particle size of about 290 nm were dispersed. An aqueous dispersion F4 (solid content concentration 10% by mass) was prepared.
Further, in the step (3) of Example 1, the resin fine particle aqueous dispersion E1 constituting the matrix portion is changed to E4, and the resin fine particle aqueous dispersion F1 constituting the domain portion is changed to F4. It was changed as follows.
e) Resin fine particle aqueous dispersion E4: 7.5 parts by mass f) Resin fine particle aqueous dispersion F4: 2.5 parts by mass

(Example 11)
This example is basically the same as Example 10, but differs in the following points.
In step (3) in Example 10, the amounts of the resin fine particle aqueous dispersion E4 constituting the matrix portion and the resin fine particle aqueous dispersion F4 constituting the domain portion were changed as follows.
e) Resin fine particle aqueous dispersion E4: 6.0 parts by mass f) Resin fine particle aqueous dispersion F4: 4.0 parts by mass (Example 12)
This example is basically the same as Example 10, but differs in the following points.
In step (3) in Example 10, the amounts of the resin fine particle aqueous dispersion E4 constituting the matrix portion and the resin fine particle aqueous dispersion F4 constituting the domain portion were changed as follows.
e) Resin fine particle aqueous dispersion E4: 5.0 parts by mass f) Resin fine particle aqueous dispersion F4: 5.0 parts by mass (Example 13)
The present embodiment basically conforms to the first embodiment, but differs in the following points.
In the steps (2-1) and (2-2) of Example 1,
Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd. non-sar LN1): 3.5 parts by mass. Using this condition, an aqueous dispersion E5 (solid content concentration 10% by mass) in which COC resin particles having a number average particle diameter of about 380 nm are dispersed and an aqueous system in which polyethylene resin particles having a number average particle diameter of about 380 nm are dispersed. Dispersion F5 (solid content concentration 10% by mass) was prepared.
Further, in the step (3) of Example 1, the resin fine particle aqueous dispersion E1 constituting the matrix portion is changed to E5, and the resin fine particle aqueous dispersion F1 constituting the domain portion is changed to F5. It was changed as follows.
e) Resin fine particle aqueous dispersion E5: 6.5 parts by mass f) Resin fine particle aqueous dispersion F5: 3.5 parts by mass (Example 14)
The present embodiment basically conforms to the thirteenth embodiment, but differs in the following points.
In step (3) in Example 10, the amounts of the resin fine particle aqueous dispersion E5 constituting the matrix portion and the resin fine particle aqueous dispersion F5 constituting the domain portion were changed as follows.
e) Resin fine particle aqueous dispersion E5: 6.0 parts by mass f) Resin fine particle aqueous dispersion F5: 4.0 parts by mass

(Example 15)
The present embodiment basically conforms to the first embodiment, but differs in the following points.
In the steps (2-1) and (2-2) of Example 1,
Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd. non-sar LN1): 2.0 parts by mass. Using this condition, an aqueous dispersion E6 (solid content concentration of 10% by mass) in which COC resin particles having a number average particle size of about 580 nm were dispersed and polyethylene resin particles having a number average particle size of about 580 nm were dispersed. An aqueous dispersion F6 (solid content concentration 10% by mass) was prepared.
Further, in the step (3) of Example 1, the resin fine particle aqueous dispersion E1 constituting the matrix portion was changed to E6, and the resin fine particle aqueous dispersion F1 constituting the domain portion was changed to F6. It was changed as follows.
e) Resin fine particle aqueous dispersion E6: 5.0 parts by mass f) Resin fine particle aqueous dispersion F6: 5.0 parts by mass (Example 16)
The present embodiment basically conforms to the first embodiment, but differs in the following points.
In step (2-1) of Example 1,
In a reactor (flask with high shear stirring device), 150 parts by mass of ion-exchanged water, 1.5 parts by mass of a nonionic surfactant (Sanyo Kasei Co., Ltd .: Nonipol 400) and an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd.) (Product: Neogen RK) 3.5 parts by mass was added.
On the other hand, the following components were mixed to prepare a solution.
Styrene: 71 parts by mass n butyl acrylate: 29 parts by mass Divinylbenzene: 0.95 parts by mass Octanethiol: 0. 35 parts by mass / carbon tetrabromide: 0.7 parts by mass The resulting solution was added to the reactor and slowly mixed with each of the above-mentioned components while adding ammonium persulfate 3.2%. 10 parts by mass of ion-exchanged water in which part by mass was dissolved was dropped over 10 minutes. After 10 minutes, the contents were heated in an oil bath while stirring the contents until the temperature reached 65 ° C., and after 1 hour, the temperature was further raised to 70 ° C. and emulsion polymerization was continued under a nitrogen atmosphere for 4 hours. An aqueous system in which styrene acrylic resin particles having a number average particle size of about 120 nm are dispersed by cooling to a room temperature at a rate of 2 ° C. per minute after a predetermined time and further adjusting the solid content concentration with ion-exchanged water Dispersion E7 (solid content concentration 10% by mass) was prepared.
A part of the aqueous dispersion E7 was dried, and the flow tester 1/2 method temperature of the styrene acrylic resin was measured. The Tm was 118.9 ° C.
Further, in the step (3) of Example 1, the resin fine particle aqueous dispersion E1 constituting the matrix part is changed to E7, and the resin fine particle aqueous dispersion E7 constituting the matrix part and the resin fine particle aqueous dispersion constituting the domain part are used. The liquid F1 was changed as follows.
e) Resin fine particle aqueous dispersion E7: 7.5 parts by mass f) Resin fine particle aqueous dispersion F1: 2.5 parts by mass

(Example 17)
The present embodiment basically conforms to the first embodiment, but differs in the following points.
In the step (2-2) of Example 1, the resin was a polyethylene resin (Sumitomo Chemical FX-452 manufactured by Sumitomo Chemical Co., Ltd .: density 0.880 g / cm ³ , weight average molecular weight (Mw) 60000, flow tester 1/2 method Temperature Tm124.20 ° C.): 100 parts by mass. Using this condition, an aqueous dispersion F7 (solid content concentration of 10% by mass) in which polyethylene resin particles having a number average particle diameter of about 120 nm were dispersed was prepared.
Further, in the step (3) of Example 1, the resin fine particle aqueous dispersion F1 constituting the domain part is changed to F7, the resin fine particle aqueous dispersion E1 constituting the matrix part, and the resin fine particle aqueous system constituting the domain part. The amount of dispersion F7 was changed as follows.
e) Resin fine particle aqueous dispersion E1: 7.5 parts by mass f) Resin fine particle aqueous dispersion F7: 2.5 parts by mass

(Comparative Example 1)
This comparative example basically conforms to the first embodiment, but differs in the following points.
In step (3) of Example 1, the amounts of the resin fine particle aqueous dispersion E1 constituting the matrix portion and the resin fine particle aqueous dispersion F1 constituting the domain portion were changed as follows.
e) Resin fine particle aqueous dispersion E1: 9.7 parts by mass f) Resin fine particle aqueous dispersion F1: 0.3 parts by mass (Comparative Example 2)
This comparative example basically conforms to Example 6, but differs in the following points.
In step (3) in Example 6, the amounts of the resin fine particle aqueous dispersion E3 constituting the matrix portion and the resin fine particle aqueous dispersion F3 constituting the domain portion were changed as follows.
e) Resin fine particle aqueous dispersion E3: 9.0 parts by mass f) Resin fine particle aqueous dispersion F3: 1.0 part by mass (Comparative Example 3)
This comparative example basically conforms to Example 10, but differs in the following points.
In step (3) in Example 10, the amounts of the resin fine particle aqueous dispersion E4 constituting the matrix portion and the resin fine particle aqueous dispersion F4 constituting the domain portion were changed as follows.
e) Resin fine particle aqueous dispersion E4: 8.0 parts by mass f) Resin fine particle aqueous dispersion F4: 2.0 parts by mass (Comparative Example 4)
This comparative example basically conforms to Example 10, but differs in the following points.
In step (3) in Example 10, the amounts of the resin fine particle aqueous dispersion E4 constituting the matrix portion and the resin fine particle aqueous dispersion F4 constituting the domain portion were changed as follows.
e) Resin fine particle aqueous dispersion E4: 4.3 parts by mass f) Resin fine particle aqueous dispersion F4: 5.7 parts by mass (Comparative Example 5)
This comparative example basically conforms to Example 13, but the following points are different.
In step (3) in Example 13, the amounts of the resin fine particle aqueous dispersion E5 constituting the matrix portion and the resin fine particle aqueous dispersion F5 constituting the domain portion were changed as follows.
e) Resin fine particle aqueous dispersion E5: 7.5 parts by mass f) Resin fine particle aqueous dispersion F5: 2.5 parts by mass

(Comparative Example 6)
This comparative example basically conforms to Example 13, but the following points are different.
In step (3) in Example 13, the amounts of the resin fine particle aqueous dispersion E5 constituting the matrix portion and the resin fine particle aqueous dispersion F5 constituting the domain portion were changed as follows.
e) Resin fine particle aqueous dispersion E5: 4.3 parts by mass f) Resin fine particle aqueous dispersion F5: 5.7 parts by mass (Comparative Example 7)
This comparative example is basically the same as Example 15, but differs in the following points.
In step (3) in Example 15, the amounts of the resin fine particle aqueous dispersion E6 constituting the matrix part and the resin fine particle aqueous dispersion F6 constituting the domain part were changed as follows.
e) Resin fine particle aqueous dispersion E6: 5.5 parts by mass f) Resin fine particle aqueous dispersion F6: 4.5 parts by mass

(Comparative Example 8)
This comparative example is basically the same as Example 15, but differs in the following points.
In step (3) in Example 15, the amounts of the resin fine particle aqueous dispersion E6 constituting the matrix part and the resin fine particle aqueous dispersion F6 constituting the domain part were changed as follows.
e) Resin fine particle aqueous dispersion E6: 4.3 parts by mass f) Resin fine particle aqueous dispersion F6: 5.7 parts by mass (Comparative Example 9)
The present embodiment basically conforms to the first embodiment, but differs in the following points.
In the step (3) of Example 1, the resin fine particle dispersion was only the resin fine particle aqueous dispersion E1 constituting the matrix portion.
e) Resin fine particle aqueous dispersion E1: 10.0 parts by mass f) Resin fine particle aqueous dispersion F1: 0 parts by mass (Comparative Example 10)
This comparative example basically conforms to the first embodiment, but differs in the following points.
In the step (2-1) of Example 1, the resin is a COC resin (TOPAS (TB) manufactured by Polyplastics Co., Ltd .: Flow tester 1/2 method temperature Tm147.2 ° C.): 100 parts by mass, and the number average particle diameter is An aqueous dispersion E8 (solid content concentration of 10% by mass) in which about 120 nm of COC resin particles was dispersed was prepared.
Further, in the step (3) of Example 1, the resin fine particle aqueous dispersion E1 constituting the matrix part is changed to E8, and the resin fine particle aqueous dispersion E8 constituting the matrix part and the resin fine particle aqueous dispersion constituting the domain part are used. The amount of the liquid F1 was changed as follows.
e) Resin fine particle aqueous dispersion E8: 7.5 parts by mass f) Resin fine particle aqueous dispersion F1: 2.5 parts by mass (Comparative Example 11)
This comparative example basically conforms to the first embodiment, but differs in the following points.
In the step (2-2) of Example 1, the resin was a polyethylene resin (Prime Polymer Co., Ltd. 3510F: density 0.933 g / cm ³ , weight average molecular weight (Mw) 120,000): 100 parts by mass. Using this condition, an aqueous dispersion F8 (solid content concentration of 10% by mass) in which polyethylene resin particles having a number average particle diameter of about 120 nm were dispersed was prepared.
Further, in the step (3) of Example 1, the resin fine particle aqueous dispersion F1 constituting the domain part is changed to F8, and the resin fine particle aqueous dispersion E1 constituting the matrix part and the resin fine particle aqueous dispersion constituting the domain part are provided. The amount of liquid F8 was changed as follows.
e) Resin fine particle aqueous dispersion E1 7.5 parts by mass f) Resin fine particle aqueous dispersion F8 2.5 parts by mass

(Measuring method of domain part abundance ratio and closest distance average value)
In the toners described in Examples and Comparative Examples, the abundance ratio of the domain part on the toner surface and the average value of the closest distance of the domain part were measured by the following methods.
First, in order to distinguish the matrix portion and the domain portion on the toner surface, the toner without any external addition was dyed with ruthenium, and then a secondary electron image on the toner surface was observed with a scanning electron microscope.
The captured image was binarized into a matrix portion and a domain portion by image analysis software (LUZEX, photoshop, etc.). Thereafter, the existence ratio of the domain part at the toner surface 2 μm × 2 μm and the closest distance of the domain part at the toner surface 2 μm × 2 μm were measured with an automatic image processing analyzer Luzex AP (trade name) manufactured by Nireco.
For the surface of about 20 different toner particles, the abundance ratio of the domain part and the closest distance of the domain part on the toner surface of 2 μm × 2 μm are measured by this method, and the average value thereof is taken. And the average value of the closest distance of the domain part was calculated.
(Evaluation item)
(Evaluation of transfer efficiency)
The transfer efficiency is a transferability index indicating how much of the toner developed on the photoreceptor is transferred onto the intermediate transfer belt. The transfer efficiency was evaluated by filling the toner of the present invention in a drum cartridge of a full-color electrophotographic apparatus (manufactured by Canon: LBP-5050) and continuously forming a solid cyan image on a recording medium. Toner on the intermediate transfer belt when the sum of the density of the toner transferred on the intermediate transfer belt after the formation of 3000 images and the density of the toner remaining on the photoreceptor after transfer is 100% The density ratio was defined as transfer efficiency. The higher this ratio, the better the transfer efficiency after endurance. In the present invention, the evaluation of transfer efficiency was judged according to the following criteria.
A: Very good (transfer efficiency is 98% or more)
B: Good (transfer efficiency is 95% or more and less than 98%)
C: Inferior (transfer efficiency is less than 95%)
If the transfer efficiency was 95% or more, it was judged that the transfer efficiency was good.
(Minimum fixing temperature evaluation)
The image forming apparatus is adjusted in advance so that the amount of toner on the recording paper before fixing at the time of solid image printing is 0.6 mg / cm 2. After the adjustment, a solid image was printed under conditions of 21 points every 5 ° C. from 100 ° C. to 200 ° C., and the obtained images were subjected to an offset image test and a fixability test.
In determining the fixing temperature, there is a hot offset limit temperature on the high temperature side, and when this temperature is exceeded, a hot offset phenomenon occurs. On the contrary, the lower temperature side has a fixing limit temperature, and below this temperature, fixing failure occurs.
The fixability limit temperature was set as the minimum fixing temperature, and the low temperature fixability index was ranked as follows.
A: The minimum fixing temperature is less than 135 ° C. B: The minimum fixing temperature is 135 ° C. or more and less than 150 ° C. C: The minimum fixing temperature is 150 ° C. or more. It was judged.
<About evaluation results>
The evaluation results are shown in Table 1.

Examples 1 to 17 well show the effects of the configuration of the present invention.
That is, the matrix part having the matrix-domain structure of the toner particles in Examples 1 to 17 has a 1/2 method temperature Tm in the melt viscosity measurement of 4.093 × 10 ⁵ Pa by a flow tester temperature rising method and a die diameter of 1 mm. It consists of resin which is 125 degrees C or less. Furthermore, the domain part in these matrix-domain structures is comprised with the polyethylene resin whose density is less than 0.930 g / cm < ³ > and whose weight average molecular weight is 10,000-5 million. The average value of the closest distance of the domain portion composed of polyethylene on the surface of the toner particles of these examples is 400 nm or less, and the average value of the abundance ratio of the domain portion existing on the toner surface is 50% or less. Yes.
With these toner configurations, the external additive present in the domain portion functions effectively as a spacer, and the wax and resin inside the toner can be melted at a desired fixing temperature. As a result, both low-temperature fixability can be achieved.
On the other hand, in Comparative Examples 1, 2, 3, 5, and 7, although the external additive was not buried in the polyethylene part that is the domain part, the average value of the closest distance of the domain part was large, so the external additive that was not buried. The agent cannot function as a spacer. As a result, the contact area between the matrix portion in which the external additive is buried and the photosensitive member is increased, so that the desired transfer efficiency cannot be maintained.
Further, since Comparative Example 9 has no polyethylene part as a domain part, all the external additives on the toner surface are buried, and the desired transfer efficiency cannot be maintained.
In Comparative Examples 4, 6, and 8, although the matrix portion having a low melting temperature melts prior to the domain portion, the ratio of the domain portion having a high melting temperature to the entire fine particles covering the toner surface is large. As a result, the minimum fixing temperature became higher than the desired temperature.
In Comparative Example 10, since the melting temperature of the resin constituting the matrix portion was high, the minimum fixing temperature was higher than the desired temperature.
In Comparative Example 11, since the resin constituting the domain portion was a medium density polyethylene resin, the melting temperature was high, and the minimum fixing temperature was higher than the desired temperature.
In the present invention, the average value of the existing ratio of the domain portion existing on the toner surface is 50% or less. However, when the domain portion is extremely small, the portion where the external additive is not buried is almost eliminated. Since the effect is reduced, the average value of the abundance ratio of the domain part is preferably 0.5% or more, and more preferably 3% or more.

3: Laser optical device 5: Primary transfer device 6: Intermediate transfer member 7: Secondary transfer device 8: Paper 10: Fixing device 11: Cartridge

Claims (5)

Toner having toner particles and fine particles on the surface of the toner particles,
The toner particle surface has a matrix-domain structure;
The matrix part in the matrix-domain structure contains a resin having a ½ method temperature Tm of 125 ° C. or lower in melt viscosity measurement of 4.093 × 10 ⁵ Pa by a flow tester temperature rising method and a die diameter of 1 mm,
The domain part in the matrix-domain structure comprises a polyethylene resin having a density of less than 0.930 g / cm ³ and a weight average molecular weight of 10,000 to 5,000,000;
On the toner particle surface, the average value of the closest distance of the domain part is 400 nm or less,
A toner characterized in that the average value of the abundance ratio of domain portions present on the surface of the toner particles is 50% or less.   The toner according to claim 1, wherein the resin constituting the matrix portion includes an olefin polymer having a cyclic structure.   The olefin polymer having the cyclic structure is a cyclic and / or polycyclic olefin having at least one kind of lower alkene having 2 to 12 carbon atoms and at least one double bond having 3 to 17 carbon atoms. The toner according to claim 2, wherein the toner is a copolymer of at least one of the above.   The olefin polymer having the cyclic structure has a number average molecular weight of 100 to 100,000, a weight average molecular weight of 200 to 300,000, and a glass transition point of -20 ° C to 180 ° C. toner.   The toner according to claim 1, comprising an external additive.

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