JP2008233163A - Image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an image forming apparatus capable of maintaining cleaning performance for a long period of time without causing filming and capable of giving high picture quality with excellent reproducibility of minute dots. <P>SOLUTION: The image forming apparatus has an image carrier, a charging means, an exposure means, a developing means, a transfer means, a fixing means and a cleaning means for cleaning off a transfer residual toner, wherein the cleaning means comprises a blade type elastic member the tip end of which is abutted on the image carrier wherein the abutted portion between the image carrier and the elastic member has a surface pressure of 2 MPa to 8 MPa, the toner contains at least a binder resin, a colorant, a release agent and a layered inorganic mineral in which interlayer ions are at least partially modified with organic ions, and the atomic density (%) of a specified element constituting the layered inorganic mineral is at least 0.5 atomic%, when the toner is measured by XPS. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an image forming apparatus using an electrostatic charge image toner used as a developer when developing an electrostatic charge image formed by electrophotography, electrostatic recording or the like.

  The image forming apparatus includes a charging step for uniformly charging an image forming area on the surface of the image carrier, an exposure step for writing on the image carrier, a developing step for forming an image with toner frictionally charged on the image carrier, The image is fixed on the printing paper after a transfer process in which the image on the image carrier is transferred directly to the printing paper or indirectly via an intermediate transfer body. Further, the untransferred toner remaining without being transferred onto the image carrier is scraped off from the image carrier by the cleaning process, and enters the next image forming process.

  As the developer used, there are a two-component developer composed of a toner and a carrier and a one-component developer composed of only a magnetic or non-magnetic toner. The production of these toners is generally a kneading and pulverization method in which a resin, pigment, charge control agent, and release agent are melt-kneaded, cooled and then pulverized and classified, but the particle size and shape are not uniform, and these are controlled. It is difficult to do. Under such circumstances, recently, there has been an attempt to control the particle size of toner particles intentionally to solve the above-mentioned problems, and polymerized toner methods such as emulsion polymerization method and dissolution suspension method as aqueous granulation. Became popular.

  In recent years, photoconductors have been repeatedly used in order to avoid dust due to environmental considerations. In particular, in order to have high image quality and high durability, the initial performance of the photoconductor used is good, and further, the performance of the photoconductor is repeatedly used over a long period of time for charging, exposure, development, transfer, cleaning, and static elimination. Very few things are needed. In order to obtain a stable image even after repeated use, the photoreceptor is required to have high mechanical strength such as abrasion resistance and prevention of adhesion of toner or paper dust.

  Furthermore, there is an increasing demand for higher image quality, and in particular, there is an increasing demand for toner diameter reduction and particle size uniformity in order to realize high-definition images in color image formation. When an image is formed using a toner having a wide particle size distribution, the problem that the fine powder toner contaminates the developing roller, charging roller, charging blade, photoconductor, carrier, etc., and the toner scatters increases. And it was difficult to achieve high reliability at the same time. On the other hand, when the particle size is uniform and the particle size distribution is sharp, the development behavior of the individual toner particles is uniform, and the reproducibility of minute dots is greatly improved.

Those having high resolution and high sensitivity tend to have low film strength or hardness of the photosensitive material used. In order to maintain high resolution and high sensitivity performance, in addition to the material used for the photoconductor not changing in quality over a long period of time, it should not cause filming due to toner adhering to the photoconductor surface, It is important that the surface deposits do not become worn or scratched by operations such as cleaning.
In order to solve the above-mentioned drawbacks, conditions such as defining the substance of the charge transfer layer, which is the outermost surface layer of the photoreceptor (Patent Document 1), defining the material of the cleaning blade (Patent Document 2), and contact have been studied. .
However, when a toner having a spherical shape and a small particle size is used, the contact pressure of the cleaning blade inevitably increases, causing a reduction in the life of the photosensitive member.

In addition, since the edge portion of the cleaning blade is deformed by the frictional resistance with the photoconductor, a minute space is generated between the photoconductor and the cleaning blade. As the toner having a smaller particle size enters and stays in this space, heat is generated in a minute region, and a release agent or a fluidizing agent contained in the toner becomes a causative substance to form a film on the surface of the photoreceptor. The occurrence of so-called filming, which is considered to be fixed in a shape, can be mentioned. When filming was possible, an abnormal image such as a white spot on the solid portion of the image was generated, resulting in an abnormal image.
JP-A-5-158248 JP-A-3-20768

  The present invention has been made in view of the above problems, and an object of the present invention is to provide an image forming apparatus that is excellent in cleaning property and capable of high durability without causing filming on the surface of the photoreceptor.

The present invention is as follows.
(1) An image carrier, a charging unit that charges the surface of the image carrier, an exposure unit that writes a latent image by exposing the image carrier, and a latent image written on the image carrier. Developing means for developing a toner on the image to form a visible image; Transfer means for transferring the visible image to a recording medium directly or via an intermediate transfer member; and fixing the transferred image transferred to the recording medium. In the image forming apparatus having a fixing unit and a cleaning unit that cleans transfer residual toner on the image carrier that has not been completely transferred, the cleaning unit is a blade-like elastic member that abuts against the image carrier. The contact portion between the image carrier and the elastic member has a surface pressure of 2 MPa to 8 MPa, and the toner is at least one of a binder resin, a colorant, a release agent, and ions between layers. Part An image having a layered inorganic mineral modified with organic ions, and an atomic concentration% of a specific element constituting the layered inorganic mineral when the toner is measured by XPS is 0.5 atomic% or more Forming equipment.
(2) The toner is a toner obtained by granulating by dispersing and / or emulsifying an oil phase and / or monomer phase containing at least a toner composition and / or a toner composition precursor in an aqueous medium. The image forming apparatus as described in (1) above, wherein
(3) The toner is characterized in that, in the distribution of the modified layered inorganic mineral in the toner, the abundance in the 0.5 μm region from the layer on the toner surface is higher than the abundance of the blended toner composition ratio. The image forming apparatus according to (1) or (2).
(4) The image forming apparatus according to any one of (1) to (3), wherein the toner has an average circularity of 0.930 to 0.970.
(5) The toner is a toner obtained by externally adding fine particles having an average primary particle diameter of 50 to 500 nm and a bulk density of 0.3 g / cm ³ or more on the surface of the toner base particles. The image forming apparatus according to any one of (1) to (4).
(6) Any of the above (1) to (5), wherein the modified layered inorganic mineral is a layered inorganic mineral obtained by modifying at least part of metal cations between layers of the layered inorganic mineral with an organic cation. An image forming apparatus according to claim 1.
(7) In the toner, an oil phase, which is a solution and / or a dispersion obtained by dissolving and / or dispersing a toner composition containing at least a binder resin and / or a binder resin precursor, is dispersed and / or dispersed in an aqueous medium. Alternatively, the image forming apparatus according to any one of (1) to (4) above, wherein the toner is obtained by emulsifying and granulating.
(8) In the solution or dispersion, 0.05 to 2% by weight of a layered inorganic mineral obtained by modifying at least part of ions between layers with organic ions is contained in the solid content of the solution or dispersion. (8) The image forming apparatus as described in (7) above.
(9) The image forming apparatus according to any one of (1) to (8), wherein the binder resin contained in the toner contains at least two types of binder resins.
(10) The image forming apparatus according to (9), wherein the first binder resin contained in the binder resin is a resin having a polyester skeleton.
(11) The image forming apparatus according to (10), wherein the first binder resin is a polyester resin.
(12) The image forming apparatus according to any one of (1) to (11), wherein the polyester resin is an unmodified polyester resin.
(13) The image forming apparatus according to any one of (7) to (12), wherein the binder resin precursor is a modified polyester resin.
(14) The toner dissolves at least a binder resin, the binder resin precursor, a compound that extends or crosslinks with the binder resin precursor, a colorant, a release agent, and the modified layered inorganic mineral in an organic solvent. Alternatively, it is obtained by dispersing, dissolving or dispersing the solution or dispersion in an aqueous medium, and removing the solvent from the obtained solution or dispersion. The image forming apparatus according to any one of (10) to (13).
(15) A ratio (Dv / Dn) between the volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner is 1.00 to 1.30, (1) to (14) The image forming apparatus according to any one of the above.
(16) The image forming apparatus as described in any one of (1) to (15) above, wherein 1 to 20% by number of particles of 2 μm or less of the toner are included.
(17) The content of the polyester resin component contained in the binder resin of the toner is 50 to 100% by weight, according to any one of (1) to (16), Image forming apparatus.
(18) The image forming apparatus as described in any one of (1) to (17) above, wherein the toner has a glass transition point of 40 to 70 ° C.
(19) The image forming apparatus as described in any one of (1) to (18) above, wherein the toner is used as a two-component developer.

  According to the present invention, a modified layered inorganic mineral is used in the toner, and the contact between the toner, the image carrier, and the elastic member having an atomic concentration of 0.5 atomic% or more derived from the modified layered inorganic mineral on the outermost surface of the toner. By setting the surface pressure within a specific range, it is possible to ensure film cleaning without causing filming, to obtain high image quality with excellent microdot reproducibility, and high reliability. And an image forming apparatus.

Embodiments of the present invention will be described below.
The toner used in the image forming apparatus of the present invention is a toner that is granulated by dispersing and / or emulsifying an oil phase and / or monomer phase containing at least a toner composition and / or a toner composition precursor in an aqueous medium. The toner composition has a layered inorganic mineral in which at least some of the ions in the interlayer are modified with organic ions, and the atomic concentration% of the specific element constituting the layered inorganic mineral when the toner is measured by XPS. It needs to be 0.5 atomic% or more.
That is, the layered inorganic mineral needs to be present on the toner surface, and when the amount is 0.5 atomic% or more, an image forming apparatus that does not cause filming can be obtained.

Although this is estimated at present, the layered inorganic mineral modified with organic ions is present on the surface of the toner, so that when the friction between the photoconductor and the blade occurs, one of the layered inorganic mineral on the surface becomes the layered mineral. Because of this structure, it acts as a mode of a lubricant, and it is possible to achieve both cleaning / filming by equalizing the pressure of the blade, etc., and the other is a wax component and other components that can cause a toner fixing component. By causing some interaction, it is presumed that early outflow of toner is prevented and filming is prevented.
Therefore, by using this material, it is possible to stabilize the behavior at the nip between the photoconductor and the cleaning blade, so that no filming occurs, the load on the photoconductor is low, and a highly durable image forming apparatus is possible. It becomes.

Further, in the present invention, it has a layered inorganic mineral in which at least a part of interlayer ions of the layered inorganic mineral is modified with organic ions, and the surface pressure of the contact portion between the image carrier and the elastic member is 2 MPa to 6 MPa. As a result, the cleaning performance can be greatly improved, and the wear of the cleaning blade can be greatly suppressed.
The cleaning step is a step of removing toner remaining on the image carrier, and can be performed using a cleaning unit. A blade cleaner can be used as the cleaning means. In addition, when using a toner having a reduced particle size or a spherical shape, it is necessary to increase the pressing force of the cleaning blade against the image carrier to prevent the toner from entering.

Until now, “linear pressure” has been generally used as a characteristic value representing the force for preventing toner from entering the cleaning blade. The “linear pressure” is a value [gf / cm] obtained by dividing the total load applied to the cleaning blade by the length of the edge portion of the cleaning blade pressed against the image carrier.
Specifically, the tip of the cleaning blade is pressed against the image carrier so that the tip of the blade is in a stick state, and a sheet-shaped sensor with a thickness of 0.1 [mm] is sandwiched at the pressed position, and the sensor This is a value obtained by dividing the output value (load [g] applied to the pressing position) by the length [cm] of the pressing position in the image carrier axis direction.
The sheet-like sensor has a large number of electrodes arranged in two directions (row direction and column direction) perpendicular to each other, and the surface thereof is covered with a film resin. In these electrodes, a pressure-sensitive resistance material and a charge generation material are installed in a lattice shape, and when an external pressure is applied to the lattice-shaped intersection, the resistance value changes according to the load. This change in resistance value appears as a change in the current value flowing in the row direction and the column direction. Therefore, the layer load is obtained from the current value.

However, when this "linear pressure" is increased, the cleaning performance of the small and spherical toner that is difficult to clean is improved, while the wear of the image carrier progresses, the drive torque of the image carrier increases, Deterioration such as increased wear of the cleaning blade occurs.
Further, the characteristic value of “linear pressure” cannot sufficiently evaluate the ability to prevent the toner from entering. The reason is that in the cleaning blade pressing position, a nip is formed between the image carrier and the image carrier in contact with the surface instead of a line. "Is the value obtained by dividing the total load applied to the cleaning blade by the length of the cleaning blade pressing position in the axial direction of the image carrier, and does not consider the contact area of the cleaning blade with the image carrier at all. .

Therefore, as another characteristic value for preventing the toner from entering, it is conceivable to use “surface pressure” obtained by dividing the total load applied to the cleaning blade by the contact area of the cleaning blade with the image carrier. Even when the same load is applied to the cleaning blade, this "surface pressure" changes the contact area of the cleaning blade with the image carrier depending on the hardness, thickness, free length, shape, etc. of the rubber blade. It varies depending on the material, shape, support method, etc. On the other hand, when the surface pressure is less than 2 MPa, the load applied to the photosensitive member from the tip of the cleaning blade is too small, and the toner slips through and causes poor cleaning. On the other hand, when the pressure exceeds 6 MPa, the load on the photoconductor is too large and the photoconductor wear is promoted.
When the atomic concentration derived from the modified layered inorganic mineral on the toner surface is 0.5 atomic% or less, the advantage of the modified layered inorganic mineral on the surface cannot be obtained, and filming occurs due to heat generation in the cleaning portion.
For these reasons, when the load applied to the cleaning portion is dropped, a cleaning failure occurs as described above.

The toner of the present invention can be used as a so-called pulverization method, but is preferably used as a toner prepared in an aqueous system. In a so-called pulverized toner that undergoes a kneading and pulverizing step, the additive is uniformly dispersed to some extent in the kneading step and is present in the toner. For this reason, although the material which becomes a grinding | pulverization interface may come to the surface, it is difficult to control surface uneven distribution. For this reason, in order to obtain a layered inorganic mineral on the surface with the above-mentioned toner that requires uneven distribution of the surface, it is necessary to increase the addition amount, but as a side effect, a problem occurs in terms of fixability / spent property, and sufficient quality is obtained. I can't get it. The surface unevenness can be verified as follows by using XPS (X-ray Photoelectron Spectroscopy).
XPS is a photoelectron X-ray that can usually detect an atomic concentration of about several tens of nanometers from the particle surface.

On the other hand, in the aqueous system, the toner is granulated as an oil phase in the aqueous system, and is modified with organic ions between the layers at a level suitable for being unevenly distributed in the vicinity of the surface inside the toner particles. Can be made possible. That is, the modified layered inorganic mineral has a characteristic that it moves to the surface side in the oil droplets and tends to be unevenly distributed on the toner surface. When the amount of modification with organic ions between layers is small, the hydrophobicity of the layered inorganic mineral is insufficient, making it difficult to separate the layered inorganic mineral between layers, making it difficult to disperse in the toner, and the atomic concentration on the surface The quantity is not observed as well.
When the amount of modification of the layered inorganic mineral with organic ions is increased, the ionic species are changed, or surface treatment is performed to increase the hydrophobicity, the inorganic mineral is uniformly dispersed in the toner or unevenly distributed in the center of the toner. Have a tendency to
The present invention can be achieved by appropriately selecting the water phase, the oil phase, and the layered inorganic mineral so that the uneven distribution state is defined.

The organic solvent can be appropriately selected according to the purpose, but since the removal is easy, the boiling point is preferably less than 150 ° C. Specifically, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, And methyl isobutyl ketone. Of these, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride and the like are preferable, and ethyl acetate is particularly preferable. These may be used alone or in combination of two or more.
The amount of the organic solvent used can be appropriately selected according to the purpose, but is preferably 40 to 300 parts by weight, more preferably 60 to 140 parts by weight, and more preferably 80 to 140 parts by weight with respect to 100 parts by weight of the toner material. More preferably, 120 parts by weight.

  Toner materials other than the layered inorganic mineral obtained by modifying at least part of the metal cations of the binder resin, colorant, and modified layered inorganic mineral with an organic cation can be appropriately selected according to the purpose. As a binder resin, any one of a monomer, a polymer, a compound having an active hydrogen group and a polymer having reactivity to the active hydrogen group is contained, and if necessary, a release agent and other components are further added. You may contain.

The modified layered inorganic mineral will be described.
A layered inorganic mineral is an inorganic mineral made up of layers with a thickness of several nanometers. To modify it means to introduce organic ions into the ions existing between the layers. Specifically, it is described in JP-T-2003-515795, JP-T-2006-500605, and JP-T-2006-503313. This is called intercalation in a broad sense.
As the layered inorganic mineral, smectite group (montmorillonite, saponite, etc.), kaolin group (kaolinite, etc.), magadiite, and kanemite are known. The modified layered inorganic mineral is highly hydrophilic due to its modified layered structure. Therefore, when used in toners that are dispersed in an aqueous medium and granulated without modifying the layered inorganic mineral, the layered inorganic mineral migrates into the aqueous medium and the toner cannot be deformed. By doing so, the hydrophilicity becomes high, and it is easily deformed during granulation, dispersed and refined, and the charge adjusting function is sufficiently exhibited. Such modified inorganic minerals are particularly abundant in the surface portion of the toner particles, and perform a charge control function and contribute to low-temperature fixing. At this time, the content of the modified layered inorganic mineral in the toner material is preferably 0.05 to 2% by weight.

The modified layered inorganic mineral used in the present invention is preferably one having a smectite basic crystal structure modified with an organic cation. Further, when the layered inorganic mineral is a hydrotalcite or the like, the ion balance becomes a balance in which anions can be introduced by replacing a part of the divalent metal with a trivalent metal. A layered inorganic compound modified with an organic anion by introducing an organic anion into the layered inorganic mineral in this state can also be used.
Examples of the organic ion modifier of the layered inorganic mineral obtained by modifying at least part of the ions of the layered inorganic mineral with organic ions include quaternary alkyl ammonium salts, phosphonium salts and imidazolium salts. A quaternary alkyl ammonium salt is desirable. Examples of the quaternary alkylammonium include trimethylstearylammonium, dimethylstearylbenzylammonium, dimethyloctadecylammonium, oleylbis (2-hydroxyethyl) methylammonium and the like.

Examples of the organic ion modifier include branched, unbranched or cyclic alkyl (C1-C44), alkenyl (C1-C22), alkoxy (C8-C32), hydroxyalkyl (C2-C22), ethylene oxide, propylene oxide, and the like. Sulfates, sulfonates, carboxylates or phosphates are raised. A carboxylic acid having an ethylene oxide skeleton is desirable.
By modifying at least part of the layered inorganic mineral with organic ions, it has moderate hydrophobicity, the oil phase containing the toner composition and / or toner composition precursor has non-Nutnian viscosity, and the toner is deformed Can be At this time, the content of the layered inorganic mineral obtained by modifying a part of the toner material with organic ions is preferably 0.05 to 2% by weight. The layered inorganic mineral partially modified with organic ions can be appropriately selected, and examples thereof include montmorillonite, bentonite, hectorite, attapulgite, sepiolite, and mixtures thereof. Among these, organically modified montmorillonite or bentonite is preferable because the viscosity can be easily adjusted without affecting the toner characteristics and the addition amount can be reduced.

Commercially available layered inorganic minerals partially modified with organic cations include Bentone 3, Bentone 38, Bentone 38V (above, manufactured by Leox), Thixogel VP (manufactured by United catalyst), Kraton 34, Kraton 40, Kraton XL Quartium 18 bentonite such as (made by Southern Clay), and stearalkonium bentonite such as Bentone 27 (made by Leox), Thixogel LG (made by United catalyst), Clayton AF, Clayton APA (made by Southern Clay) Quaternium 18 / benzalkonium bentonite such as Clayton HT and Clayton PS (manufactured by Southern Clay). Particularly preferred are Clayton AF and Clayton APA. Further, as the layered inorganic mineral partially modified with an organic anion, one obtained by modifying DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.) with an organic anion represented by the following general formula (1) is particularly preferable. As what is represented by the following general formula (1), Hytenol 330T (made by Daiichi Kogyo Seiyaku Co., Ltd.) is mentioned, for example.
Formula (1) R ₁ (OR ₂ ) nOSO ₃ M
[Wherein, R ₁ represents an alkyl group having 13 carbon atoms, and R ₂ represents an alkylene group having 2 to 6 carbon atoms. n represents an integer of 2 to 10, and M represents a monovalent metal element]
By using the modified layered inorganic mineral, since it has moderate hydrophobicity, it tends to be present at the interface of the droplets, so that the surface is unevenly distributed and the occurrence of filming can be suppressed.

The colorant can be appropriately selected from known dyes and pigments according to the purpose. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow ( GR, A, RN, R), Pigment Yellow L, Benzidine Yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Iso Indolinone Yellow, Bengala, Pengdan, Pepper Red, Cadmium Red, Cadmium Mercury Red, Antimony Zhu, Permanent Red 4R, Para Red, Faise Red, p-Chloro-o-nitroaniline red, Resol Fast Scarlet G, Brilli Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pogment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon , Oil red, quinacridone red, pyrazolone red, polyazo red, chrome vermilion, benzidine oren , Perinone orange, oil orange, cobalt blue, cerulean blue, alkaline blue rake, peacock blue rake, Victoria blue rake, metal-free phthalocyanine blue, phthalocyanine blue, fast sky blue, indanthrene blue (RS, BC), indigo, Ultramarine blue, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridian, emerald green, pigment green B, naphthol green B, green Gold, Acid Green Lake, Malachite Green Lake, Phthalocyanine Green, Anthraquinone Green, Titanium Oxide, Examples thereof include zinc white, litbon, and mixtures thereof. As the colorant that can be used particularly preferably, pigment red such as PR122, PR269, PR184, PR57: 1, PR238, PR146, PR185, etc .; Pigment yellow such as PY93, PY128, PY155, PY180, PY74; PB15: 3 Pigment blue, etc. These may be used alone or in combination of two or more.

The colorant may be used by being dispersed in a solvent together with the binder resin or the like, or may be used as a dispersion of a colorant obtained by dispersing the colorant in the solvent. In addition, when dispersing the colorant, in order to apply an appropriate shearing force, a part of a binder resin or the like may be added to adjust the viscosity.
The dispersed particle diameter of the colorant is preferably 1 μm or less. When a toner produced using a colorant having a dispersed particle diameter exceeding 1 μm is used, the image quality may be easily deteriorated, and in particular, the OHP light transmittance may be easily deteriorated.
The dispersed particle size of the colorant can be measured using a particle size distribution measuring apparatus Microtrac ultrafine particle size distribution analyzer UPA-EX150 (manufactured by Nikkiso Co., Ltd.) using a laser Doppler method.

  The content of the colorant in the toner can be appropriately selected according to the purpose, but is usually 1 to 15% by weight, and preferably 3 to 10% by weight. When the content of the colorant is less than 1% by weight, the coloring power of the toner decreases. When the content of the coloring agent exceeds 15% by weight, poor pigment dispersion occurs in the toner. May be reduced.

  In the present invention, the aqueous medium preferably contains a polymer dispersant. The polymer dispersant is preferably a water-soluble polymer. The water-soluble polymer can be appropriately selected from known ones, and examples thereof include sodium carboxymethyl cellulose, hydroxyethyl cellulose, and polyvinyl alcohol. These may be used alone or in combination of two or more.

When the toner material is emulsified or dispersed in the aqueous medium using the liquid containing the toner material, the liquid containing the toner material is preferably dispersed in the aqueous medium while stirring.
A known disperser or the like can be appropriately used for the dispersion. Specific examples of the disperser include a low speed shear disperser, a high speed shear disperser, a friction disperser, a high pressure jet disperser, and an ultrasonic disperser. Especially, since the particle diameter of a dispersion (oil droplet) can be controlled to 2-20 micrometers, a high-speed shearing disperser is preferable.
When a high-speed shearing disperser is used, conditions such as the number of rotations, dispersion time, dispersion temperature and the like can be appropriately selected according to the purpose. The rotation speed is preferably 1000 to 30000 rpm, more preferably 5000 to 20000 rpm. In the case of a batch system, the dispersion time is preferably 0.1 to 5 minutes, and the dispersion temperature is preferably 0 to 150 ° C. and more preferably 40 to 98 ° C. under pressure. In general, the dispersion temperature is high.

The method for forming the toner base particles can be appropriately selected from known methods. Specifically, a method for forming toner base particles using a suspension polymerization method, an emulsion polymerization aggregation method, a dissolution suspension method, or the like, a method for forming toner base particles while producing an adhesive substrate, etc. Among these, a method of forming toner base particles while producing an adhesive substrate is preferable. Here, the adhesive base material is a base material having adhesiveness to a recording medium such as paper.
A method of forming toner base particles while producing an adhesive substrate is a method in which a toner material contains a compound having an active hydrogen group and a polymer having reactivity to the active hydrogen group, and is active in an aqueous medium. This is a method of forming toner base particles while producing an adhesive substrate by reacting a compound having a hydrogen group with a polymer having reactivity with an active hydrogen group. In addition, the adhesive base material may further contain a known binder resin.
The toner thus obtained preferably contains a colorant, and may further contain other components such as a release agent and a charge control agent that are appropriately selected as necessary.

The weight average molecular weight of the adhesive substrate is preferably 3000 or more, more preferably 5000 to 1000000, and particularly preferably 7000 to 500000. When the weight average molecular weight is less than 3000, the hot offset resistance may be lowered.
The glass transition temperature of the adhesive substrate is preferably 30 to 70 ° C, more preferably 40 to 65 ° C. When the glass transition temperature is less than 30 ° C., the heat-resistant storage stability of the toner may deteriorate, and when it exceeds 70 ° C., the low-temperature fixability may not be sufficient. Note that a toner containing a polyester resin subjected to a crosslinking reaction or an elongation reaction as an adhesive substrate has good storage stability even when the glass transition temperature is low.

  The glass transition temperature can be measured as follows using a TG-DSC system TAS-100 (manufactured by Rigaku Corporation). First, about 10 mg of toner is put in an aluminum sample container, and the sample container is placed on a holder unit and set in an electric furnace. After heating from room temperature to 150 ° C. at a heating rate of 10 ° C./min, the sample is left at 150 ° C. for 10 minutes, and the sample is cooled to room temperature and left for 10 minutes. Then, the DSC curve is measured with a differential scanning calorimeter (DSC) after heating to 150 ° C. at a heating rate of 10 ° C./min in a nitrogen atmosphere. From the obtained DSC curve, the glass transition temperature can be calculated from the contact point between the tangent line and the base line of the endothermic curve near the glass transition temperature using the analysis system in the TG-DSC system.

The adhesive substrate is appropriately selected according to the purpose, but a polyester resin or the like is preferably used.
The polyester resin is appropriately selected depending on the purpose, but a urea-modified polyester resin or the like is preferably used.
The urea-modified polyester resin is obtained by reacting an amine as a compound having an active hydrogen group and a polyester prepolymer having an isocyanate group as a polymer having reactivity with the active hydrogen group in an aqueous medium. In addition, when synthesizing the urea-modified polyester resin, a urethane bond may be formed by adding an alcohol in addition to the amine. The molar ratio of the urethane bond to the urea bond thus formed (to distinguish it from the urethane bond of the polyester prepolymer having an isocyanate group) is preferably 0 to 9, and preferably 1/4 to 4. Is more preferable.
3 to 7/3 is particularly preferable. If this ratio is greater than 9, the hot offset resistance may decrease.

  Specific examples of the adhesive substrate include a polyester prepolymer obtained by reacting a 2-condensate of bisphenol A ethylene oxide and a polycondensate of isophthalic acid with isophorone diisocyanate, and urethanized with isophorone diamine, and bisphenol A ethylene oxide 2 Mixtures of polyadducts of molar adducts and isophthalic acid; bisphenol A ethylene oxide 2 molar adducts and polycondensates of isophthalic acid reacted with isophorone diisocyanate and uread with isophorone diamine, and bisphenol A mixture of ethylene oxide 2 mol adduct and terephthalic acid polycondensate; bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid A mixture of a polyester prepolymer obtained by reacting a condensate with isophorone diisocyanate and uread with isophorone diamine, and a polycondensate of bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid; Polyester prepolymer prepared by reacting bisphenol A ethylene oxide 2-mole adduct / bisphenol A propylene oxide 2-mole adduct and terephthalic acid polycondensate with isophorone diisocyanate, and oleaminated with isophoronediamine, 2 mol of bisphenol A propylene oxide Mixture of adduct and polycondensate of terephthalic acid; bisphenol A ethylene oxide 2-mole adduct and polycondensate of terephthalic acid with isophorone diisocyanate A mixture of a polyester prepolymer obtained by urea formation with hexamethylenediamine and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid; polycondensation of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid A mixture of a polyester prepolymer obtained by reacting a product with isophorone diisocyanate with urea and hexamethylenediamine, and a polycondensate of bisphenol A ethylene oxide 2-mole adduct / bisphenol A propylene oxide 2-mole adduct and terephthalic acid; A polyester prepolymer obtained by reacting a bicondensate of bisphenol A ethylene oxide 2 mol and a polycondensate of terephthalic acid with isophorone diisocyanate, and urethanized with ethylenediamine, and bisphenol A polyester prepolymer prepared by reacting bisphenol A ethylene oxide 2-mole adduct and isophthalic acid polycondensate with diphenylmethane diisocyanate in urea with hexamethylenediamine Of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid polycondensate; bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid / dodecenyl succinic anhydride A polyester prepolymer obtained by reacting a polycondensate with diphenylmethane diisocyanate and uread with hexamethylenediamine, and a bisphenol A ethylene oxide 2-mole adduct / bisphenol A mixture of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid polycondensate; bisphenol A ethylene oxide 2 mol adduct and isophthalic acid polycondensate reacted with toluene diisocyanate in urea with hexamethylenediamine And a mixture of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid polycondensate.

The compound having an active hydrogen group acts as an elongation agent, a crosslinking agent or the like when a polymer having reactivity to the active hydrogen group undergoes an elongation reaction, a crosslinking reaction, or the like in an aqueous medium. Specific examples of the active hydrogen group include a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), amino group, carboxyl group, mercapto group and the like. In addition, an active hydrogen group may be individual, and 2 or more types of mixtures may be sufficient as it.
The compound having an active hydrogen group can be appropriately selected according to the purpose. However, when the polymer having reactivity to the active hydrogen group is a polyester prepolymer having an isocyanate group, an elongation reaction with the polyester prepolymer. Amines are preferred because they can have a high molecular weight by a crosslinking reaction or the like.

  The amines can be appropriately selected depending on the purpose, and specific examples include diamines, trivalent or higher amines, amino alcohols, amino mercaptans, amino acids, and those obtained by blocking these amino groups. Diamines and mixtures of diamines and small amounts of trivalent or higher amines are preferred. These may be used alone or in combination of two or more. Examples of diamines include aromatic diamines, alicyclic diamines, and aliphatic diamines. Specific examples of the aromatic diamine include phenylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylmethane, and the like. Specific examples of the alicyclic diamine include 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, diaminocyclohexane, isophorone diamine and the like. Specific examples of the aliphatic diamine include ethylene diamine, tetramethylene diamine, hexamethylene diamine and the like. Specific examples of the trivalent or higher amine include diethylenetriamine and triethylenetetramine. Specific examples of amino alcohols include ethanolamine and hydroxyethylaniline. Specific examples of amino mercaptans include aminoethyl mercaptan and aminopropyl mercaptan. Specific examples of amino acids include aminopropionic acid and aminocaproic acid. Specific examples of those in which the amino group is blocked include ketimine compounds and oxazolidone compounds obtained by blocking the amino group with ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone.

  In addition, a reaction terminator can be used in order to stop the elongation reaction, the crosslinking reaction, and the like of the compound having an active hydrogen group and a polymer having reactivity with the active hydrogen group. When a reaction terminator is used, the molecular weight and the like of the adhesive substrate can be controlled within a desired range. Specific examples of the reaction terminator include monoamines such as diethylamine, dibutylamine, butylamine and laurylamine, and ketimine compounds in which these amino groups are blocked.

  The ratio of the equivalent of the isocyanate group of the polyester prepolymer to the equivalent of the amino group of the amine is preferably 1/3 to 3, more preferably 1/2 to 2, and particularly preferably 2/3 to 1.5. . If this ratio is less than 1/3, the low-temperature fixability may be lowered. If it exceeds 3, the molecular weight of the urea-modified polyester resin may be lowered, and the hot offset resistance may be lowered.

The polymer having reactivity to active hydrogen groups (hereinafter sometimes referred to as “prepolymer”) can be appropriately selected from known resins and the like, such as polyol resin, polyacrylic resin, polyester resin, and epoxy resin. And derivatives thereof. Among them, it is preferable to use a polyester resin in terms of high fluidity and transparency at the time of melting. These may be used alone or in combination of two or more.
The functional group capable of reacting with the active hydrogen group of the prepolymer includes an isocyanate group, an epoxy group, a carboxyl group, the following chemical structural formula -COCl
In particular, an isocyanate group is preferable. The prepolymer may have one of such functional groups or two or more kinds. As a prepolymer, the molecular weight of the polymer component can be easily adjusted, and oil-less low-temperature fixing characteristics in dry toners, in particular, good releasability and fixability even in the absence of a release oil application mechanism to a fixing heating medium. Since it can ensure, it is preferable to use the polyester resin which has an isocyanate group etc. which can produce | generate a urea bond.
The polyester prepolymer containing an isocyanate group can be appropriately selected according to the purpose. Specific examples include a reaction product of a polyisocyanate with a polyester resin having an active hydrogen group obtained by polycondensation of a polyol and a polycarboxylic acid.

The polyol can be appropriately selected according to the purpose, and a diol, a trihydric or higher alcohol, a mixture of a diol and a trihydric or higher alcohol, etc. can be used, but the diol or the diol and a small amount of a trihydric or higher alcohol. Is preferred. These may be used alone or in combination of two or more.
Specific examples of the diol include alkylene glycols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol; diethylene glycol, triethylene glycol, dipropylene Diols having an oxyalkylene group such as glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol; alicyclic diols such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A; alicyclic diols including ethylene oxide and propylene oxide , With addition of alkylene oxide such as butylene oxide; bisphenols such as bisphenol A, bisphenol F and bisphenol S; bisphenols with ethyleneoxy , Propylene oxide, alkylene oxide adducts of bisphenols such as those obtained by adding alkylene oxides such as butylene oxide. In addition, it is preferable that carbon number of alkylene glycol is 2-12. Among these, alkylene glycols having 2 to 12 carbon atoms or alkylene oxide adducts of bisphenols are preferred, alkylene oxide adducts of bisphenols or alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbons. The mixture of is particularly preferred.

Examples of trihydric or higher alcohols include trihydric or higher aliphatic alcohols, trihydric or higher polyphenols, and alkylene oxide adducts of trihydric or higher polyphenols. Specific examples of the trihydric or higher aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol and the like. Specific examples of the trihydric or higher polyphenols include trisphenol PA, phenol novolak, cresol novolak and the like. Specific examples of adducts of trivalent or higher polyphenols with alkylene oxides include those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide to trihydric or higher polyphenols.
When a diol and a trihydric or higher alcohol are mixed and used, the weight ratio of the trihydric or higher alcohol to the diol is preferably 0.01 to 10%, more preferably 0.01 to 1%.

  The polycarboxylic acid can be appropriately selected according to the purpose, and dicarboxylic acid, trivalent or higher carboxylic acid, a mixture of dicarboxylic acid and trivalent or higher carboxylic acid, and the like can be used. And a small amount of a trivalent or higher polycarboxylic acid mixture is preferred. These may be used alone or in combination of two or more.

  Specific examples of the dicarboxylic acid include divalent alkanoic acid, divalent alkenoic acid, and aromatic dicarboxylic acid. Specific examples of the divalent alkanoic acid include succinic acid, adipic acid, sebacic acid and the like. The number of carbon atoms of the divalent alkenoic acid is preferably 4 to 20, and specific examples include maleic acid and fumaric acid. The aromatic dicarboxylic acid preferably has 8 to 20 carbon atoms, and specific examples thereof include phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid. Among these, a divalent alkenoic acid having 4 to 20 carbon atoms or an aromatic dicarboxylic acid having 8 to 20 carbon atoms is preferable.

  As the trivalent or higher carboxylic acid, trivalent or higher aromatic carboxylic acid or the like can be used. The carbon number of the trivalent or higher aromatic carboxylic acid is preferably 9 to 20, and specific examples thereof include trimellitic acid and pyromellitic acid. As the polycarboxylic acid, an acid anhydride or lower alkyl ester of any of dicarboxylic acid, trivalent or higher carboxylic acid, and a mixture of dicarboxylic acid and trivalent or higher carboxylic acid can be used. Specific examples of the lower alkyl ester include methyl ester, ethyl ester, isopropyl ester and the like. In the case of using a mixture of dicarboxylic acid and trivalent or higher carboxylic acid, the weight ratio of trivalent or higher carboxylic acid to dicarboxylic acid is preferably 0.01 to 10%, more preferably 0.01 to 1%. preferable.

As for the mixing ratio at the time of polycondensation of the polyol and the polycarboxylic acid, the equivalent ratio of the hydroxyl group of the polyol to the carboxyl group of the polycarboxylic acid is usually preferably 1 to 2, more preferably 1 to 1.5, 1.02-1.3 is particularly preferred.
The content of the structural unit derived from the polyol in the polyester prepolymer having an isocyanate group is preferably 0.5 to 40% by weight, more preferably 1 to 30% by weight, and particularly preferably 2 to 20% by weight. When this content is less than 0.5% by weight, the hot offset resistance is lowered, and it may be difficult to achieve both the heat-resistant storage stability and the low-temperature fixability of the toner, and exceeds 40% by weight. In this case, the low-temperature fixability may be lowered. Polyisocyanate can be appropriately selected according to the purpose, but aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, araliphatic diisocyanate, isocyanurates, and these are blocked with phenol derivatives, oximes, caprolactam, etc. And the like.

  Specific examples of the aliphatic diisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methyl 2,6-diisocyanatocaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, tetra And methyl hexane diisocyanate. Specific examples of the alicyclic diisocyanate include isophorone diisocyanate and cyclohexylmethane diisocyanate. Specific examples of the aromatic diisocyanate include tolylene diisocyanate, diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4′-diisocyanatodiphenyl, 4,4′-diisocyanato-3,3′-dimethyldiphenyl. 4,4′-diisocyanato-3-methyldiphenylmethane, 4,4′-diisocyanato-diphenyl ether, and the like. Specific examples of the araliphatic diisocyanate include α, α, α ′, α′-tetramethylxylylene diisocyanate. Specific examples of the isocyanurates include tris (isocyanatoalkyl) isocyanurate, tris (isocyanatocycloalkyl) isocyanurate, and the like. These may be used alone or in combination of two or more.

When the polyisocyanate and the polyester resin having a hydroxyl group are reacted, the equivalent ratio of the isocyanate group of the polyisocyanate to the hydroxyl group of the polyester resin is usually preferably 1 to 5, more preferably 1.2 to 4, more preferably 1 .5-3 are particularly preferred. When the equivalent ratio exceeds 5, the low-temperature fixability may decrease, and when it is less than 1, the offset resistance may decrease.
The content of the structural unit derived from polyisocyanate in the polyester prepolymer containing an isocyanate group is preferably 0.5 to 40% by weight, more preferably 1 to 30% by weight, further 2 to 20% by weight. preferable. When this content is less than 0.5% by weight, the hot offset resistance may be lowered, and when it exceeds 40% by weight, the low-temperature fixability may be lowered.
The average number of isocyanate groups that the polyester prepolymer has per molecule is preferably 1 or more, more preferably 1.2 to 5, and still more preferably 1.5 to 4. When the average number is less than 1, the molecular weight of the urea-modified polyester resin is lowered, and the hot offset resistance may be lowered.

  1000-30000 is preferable and, as for the weight average molecular weight of the polymer which has the reactivity with respect to an active hydrogen group, 1500-15000 are more preferable. When the weight average molecular weight is less than 1000, the heat resistant storage stability may be lowered, and when it exceeds 30000, the low temperature fixability may be lowered. In addition, a weight average molecular weight is obtained by measuring tetrahydrofuran soluble part using a gel permeation chromatography (GPC).

The GPC measurement can be performed as follows, for example. First, the column is stabilized in a 40 ° C. heat chamber. At this temperature, tetrahydrofuran is used as a column solvent at a flow rate of 1 ml per minute, and 50 to 200 μl of a tetrahydrofuran solution adjusted to a sample concentration of 0.05 to 0.6% by weight is injected and measured. In measuring the molecular weight, the molecular weight is calculated from the relationship between the logarithmic value of the calibration curve prepared from several kinds of standard samples and the number of counts. As a standard sample for preparing a calibration curve, the molecular weight is 6 × 10 ² , 2.1 × 10 ² , 4 × 10 ² , 1.75 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ and 4.48 × 10 ⁶ monodisperse polystyrene (manufactured by Pressure Chemical or Toyo Soda Industry Co., Ltd.) can be used. At this time, it is preferable to use about 10 kinds of standard samples. A refractive index detector can be used as the detector.

  In the present invention, the binder resin can be appropriately selected according to the purpose, and a polyester resin or the like can be used, but an unmodified polyester resin that is not modified is preferable. Thereby, low temperature fixability and glossiness can be improved. Examples of the unmodified polyester resin include a polycondensate of a polyol and a polycarboxylic acid. The non-modified polyester resin is preferably partially compatible with the urea-modified polyester resin, that is, has a similar structure compatible with each other in terms of low-temperature fixability and hot offset resistance. . The weight average molecular weight of the unmodified polyester resin is preferably 1000 to 30000, and more preferably 1500 to 15000. When the weight average molecular weight is less than 1000, the heat resistant storage stability may be lowered. For this reason, it is preferable that content of the component whose weight average molecular weight is less than 1000 is 8-28 weight%. On the other hand, if the weight average molecular weight exceeds 30000, the low-temperature fixability may be lowered.

The glass transition temperature of the unmodified polyester resin is usually 30 to 70 ° C, more preferably 35 to 60 ° C, and still more preferably 35 to 55 ° C. When the glass transition temperature is less than 30 ° C., the heat-resistant storage stability of the toner may be lowered, and when it exceeds 70 ° C., the low-temperature fixability may be lowered.
The hydroxyl value of the unmodified polyester resin is preferably 5 mgKOH / g or more, more preferably 10 to 120 mgKOH / g, and still more preferably 20 to 80 mgKOH / g. When the hydroxyl value is less than 5 mgKOH / g, it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability.
The acid value of the unmodified polyester resin is preferably 1.0 to 50.0 mgKOH / g, and more preferably 1.0 to 30.0 mgKOH / g. Thereby, the toner is easily negatively charged.

  When the toner contains an unmodified polyester resin, the weight ratio of the polyester prepolymer having an isocyanate group to the unmodified polyester resin is preferably 5/95 to 25/75, more preferably 10/90 to 25/75. preferable. When the weight ratio is less than 5/95, the hot offset resistance may be lowered, and when it exceeds 25/75, the low-temperature fixability and the glossiness of the image may be lowered.

  In the present invention, the toner may further contain a release agent, a charge control agent, resin particles, inorganic particles, a fluidity improver, a cleaning property improver, a magnetic material, a metal soap, and the like.

<Release agent>
The release agent can be appropriately selected from known ones according to the purpose, and waxes having a carbonyl group, polyolefin waxes, long-chain hydrocarbons, and the like can be used. Waxes having a carbonyl group are preferred. These may be used alone or in combination of two or more.
Specific examples of the wax having a carbonyl group include carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerol tribehenate, 1,18- Esters having a plurality of alkanoic acid residues such as octadecandiol diol stearate; Esters having a plurality of alkanol residues such as tristearyl trimellitic acid and distearyl maleate; and a plurality of alkanoic acid residues such as dibehenyl amide An amide having a plurality of monoamine residues such as trimellitic acid tristearyl amide; a distearyl ketoalkylketone and the like, and an ester having a plurality of alkanoic acid residues is particularly preferable. Specific examples of the polyolefin wax include polyethylene wax and polypropylene wax. Specific examples of the long chain hydrocarbon include paraffin wax and sazol wax.

The melting point of the release agent is preferably 40 to 160 ° C, more preferably 50 to 120 ° C, and particularly preferably 60 to 90 ° C. When the melting point is less than 40 ° C., the wax may adversely affect the heat resistant storage stability, and when it exceeds 160 ° C., cold offset may occur during fixing at a low temperature.
The melt viscosity of the release agent is preferably 5 to 1000 cps and more preferably 10 to 100 cps at a temperature 20 ° C. higher than the melting point of the wax. If the melt viscosity is less than 5 cps, the releasability may be lowered, and if it exceeds 1000 cps, the effect of improving the hot offset resistance and the low-temperature fixability may not be obtained. The content of the release agent in the toner is preferably 0 to 40% by weight, and more preferably 3 to 30% by weight. When the content exceeds 40% by weight, the fluidity of the toner may be lowered.

<Charge control agent>
Known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified 4 Secondary ammonium salts or compounds, tungsten simple substances or compounds, fluorine activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Bontron 03 of a nigrosine dye, Bontron P-51 of a quaternary ammonium salt, Bontron S-34 of a metal-containing azo dye, E-82 of an oxynaphthoic acid metal complex, E-84 of a salicylic acid metal complex , Phenolic condensate E-89 (above, Orient Chemical Industries, Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, Hodogaya Chemical Co., Ltd.), quaternary ammonium salt copy Charge PSY VP2038, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit) Manufactured), copper phthalocyanine, perylene, quinacridone, azo series Fee, a sulfonic acid group, a carboxyl group, and polymer compounds having a functional group such as quaternary ammonium salts. Of these, substances that control the negative polarity of the toner are particularly preferably used.

  The amount of charge control agent used is determined by the type of binder resin, the presence or absence of additives used as necessary, and the toner production method including the dispersion method, and is not uniquely limited. Preferably, it is used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin. The range of 0.2 to 5 parts by weight is preferable. When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, the effect of the charge control agent is reduced, the electrostatic attraction with the developing roller is increased, the developer fluidity is lowered, and the image density is lowered. Invite.

<Resin particles>
The resin particle is not particularly limited as long as it is a resin that can form an aqueous dispersion in an aqueous medium, and can be appropriately selected from known resins according to the purpose, and may be a thermoplastic resin. A thermosetting resin may be used. Specific examples include vinyl resins, polyurethane resins, epoxy resins, polyester resins, polyamide resins, polyimide resins, silicon resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, polycarbonate resins, and the like. Among these, one or more resins selected from the group consisting of vinyl resins, polyurethane resins, epoxy resins, and polyester resins are preferable because an aqueous dispersion of fine spherical resin particles is easily obtained. These may be used alone or in combination of two or more.

The vinyl resin is a resin obtained by homopolymerizing or copolymerizing a vinyl monomer. Specifically, a styrene- (meth) acrylic acid ester copolymer, a styrene-butadiene copolymer, (meth) Acrylic acid-acrylic acid ester polymer, styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- (meth) acrylic acid copolymer, and the like.
Further, as the resin particles, a copolymer obtained by polymerizing a monomer having a plurality of unsaturated groups can also be used. The monomer having a plurality of unsaturated groups can be appropriately selected according to the purpose. Specifically, sodium salt Eleminol RS-30 (manufactured by Sanyo Chemical Industries), divinylbenzene, a methacrylic acid ethylene oxide adduct sulfate ester. 1,6-hexanediol diacrylate, etc.

  The resin particles can be obtained by polymerization using a known method, but are preferably used as an aqueous dispersion of resin particles. As a method for preparing an aqueous dispersion of resin particles, in the case of a vinyl resin, an aqueous dispersion of resin particles is obtained by polymerizing a vinyl monomer using a suspension polymerization method, an emulsion polymerization method, a seed polymerization method, or a dispersion polymerization method. In the case of polyaddition or condensation resins such as polyester resins, polyurethane resins, and epoxy resins, a precursor such as a monomer or oligomer or a solution thereof is dispersed in an aqueous medium in the presence of an appropriate dispersant. After that, heating or adding a curing agent to cure, a method for producing an aqueous dispersion of resin particles, a precursor such as a monomer or oligomer, or an appropriate emulsifier is dissolved in the solution, and then water is added. Method of phase inversion emulsification: Resin is pulverized and classified using a mechanical pulverizer or jet pulverizer to obtain resin particles, which are then dispersed in water in the presence of an appropriate dispersant. After obtaining resin particles by spraying a resin solution in the form of a mist, the resin particles are dispersed in water in the presence of an appropriate dispersant, a poor solvent is added to the resin solution, or the solvent is heated. By cooling the dissolved resin solution, the resin particles are precipitated, and after removing the solvent to obtain resin particles, a method of dispersing the resin particles in water in the presence of an appropriate dispersant, a resin solution, Disperse in an aqueous medium in the presence of an appropriate dispersant, then remove the solvent by heating, reduced pressure, etc., dissolve an appropriate emulsifier in the resin solution, and then add water to emulsify the phase. Methods and the like.

<Inorganic particles>
The inorganic particles can be appropriately selected from known ones according to the purpose, and specifically, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide. , Tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride Etc. These may be used alone or in combination of two or more.

<External additive>
The toner used in the present invention was obtained by externally adding fine particles (hereinafter simply referred to as fine particles) having an average primary particle size of 50 to 500 nm and a bulk density of 0.3 g / cm ³ or more to the surface of the toner base particles. A toner is preferable.
By using fine particles having an average primary particle size of 50 to 500 nm and a bulk density of 0.3 g / cm ³ or more as an external additive, a small particle size toner that can be used as an auxiliary material for cleaning and that achieves particularly high image quality. When used, improvement in developability and transferability is improved.
In addition, although silica etc. are often used for a normal fluid improvement agent, for example, the average primary particle diameter of this silica is 10-30 nm normally, and a bulk density is 0.1-0.2 g / cm < ³ >.

  In the present invention, the presence of fine particles having appropriate characteristics on the surface of the toner serves as an auxiliary material for cleaning. Further, the fine particles have a very small contact area with the toner particles, the photoconductor, and the charge imparting member and are evenly contacted with each other. Further, the toner is moderately detached from the surface of the toner and accumulated at the tip of the cleaning blade, and the so-called dam effect has an effect of preventing the phenomenon of toner passing through the blade. Since these characteristics have an effect of reducing the share received by the toner particles, the filming effect of the toner due to the low rheological component contained in the toner is exhibited for high-speed fixing (low energy fixing). In addition, when fine particles having an average primary particle size in the range of 50 to 500 μm are used, the excellent cleaning performance can be fully utilized, and since the particle size is extremely small, the powder fluidity of the toner is improved. There is no reduction. Further, although the details are not clear, even if the surface-treated fine particles are externally added to the toner or the carrier is contaminated, the degree of developer deterioration is small.

The average primary particle size (hereinafter referred to as the average particle size) of the fine particles is 50 to 500 nm, and particularly preferably 100 to 400 nm. If the thickness is less than 50 nm, the fine particles may be buried in the concave and convex portions on the toner surface to lower the role of the rollers. On the other hand, when the particle size is larger than 500 μm, when the fine particles are located between the blade and the surface of the photosensitive member, the order is the same level as the contact area of the toner itself, and the toner particles to be cleaned pass, that is, defective cleaning occurs. It becomes easy.
When the bulk density is less than 0.3 g / cm ³ , although there is a contribution to improving fluidity, the scattering and adhesion of the toner and fine particles are increased, so that the toner and roller effect and the cleaning part accumulate. As a result, the so-called dam effect that prevents toner cleaning failure is reduced.

In fine particles of the present invention, as the inorganic _{compound, SiO 2, TiO 2, AlO} 3, MgO, CuO, ZnO, SnO 2, CeO 2, Fe 2 O 3, BaO, CaO, K 2 O, Na 2 O, ZrO _{2, CaO · SiO 2, K} 2 O (TiO 2) n, Al 2 O 3 · 2SiO 2, CaCO 3, MgCO 3, BaSO 4, MgSO 4, can be exemplified SrTiO ₃ or the like, preferably, SiO ₂ , TiO ₂ and Al ₂ O ₃ . In particular, these inorganic compounds may be hydrophobized with various coupling agents, hexamethyldisilazane, dimethyldichlorosilane, octyltrimethoxysilane, and the like.

The organic compound fine particles may be thermoplastic resins or thermosetting resins, such as vinyl resins, polyurethane resins, epoxy resins, polyester resins, polyamide resins, polyimide resins, silicon resins, phenol resins, melamine resins, Examples include urea resins, aniline resins, ionomer resins, and polycarbonate resins. As the resin fine particles, two or more of the above resins may be used in combination. Of these, vinyl resins, polyurethane resins, epoxy resins, polyester resins, and combinations thereof are preferred because an aqueous dispersion of fine spherical resin particles is easily obtained.
Specific examples of vinyl resins include polymers obtained by homopolymerization or copolymerization of vinyl monomers, such as styrene- (meth) acrylic acid ester copolymers, styrene-butadiene copolymers, (meth) acrylic acid. -Acrylic ester copolymer, styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- (meth) acrylic acid copolymer, and the like.

The bulk density of the fine particles was measured by the following method.
Using a 100 ml graduated cylinder, fine particles were gradually added to make 100 ml.
At that time, no vibration was applied. The bulk density was measured by the difference in weight before and after placing the fine particles of the graduated cylinder.
Bulk density (g / cm ³ ) = fine particle amount (g / 100 ml) ÷ 100
The fine particles of the present invention can be externally added and adhered to the toner surface by mechanically mixing and adhering the toner base particles and fine particles using various known mixing devices, or in the liquid phase. There is a method in which the base particles and the fine particles are uniformly dispersed with a surfactant or the like, and are dried after the adhesion treatment.

<Toner production method>
As an example of a toner production method, a method for forming toner base particles while producing an adhesive substrate will be described below. In such a method, preparation of an aqueous medium phase, preparation of a liquid containing a toner material, emulsification or dispersion of the toner material, formation of an adhesive substrate, removal of the solvent, a polymer having reactivity to active hydrogen groups And the synthesis of a compound having an active hydrogen group.
The aqueous medium can be prepared by dispersing the resin particles in the aqueous medium. The addition amount of the resin particles in the aqueous medium is preferably 0.5 to 10% by weight.

The liquid containing the toner material is prepared in a solvent by using a compound having an active hydrogen group, a polymer having reactivity to the active hydrogen group, a rheology additive, a colorant, a release agent, a charge control agent, and an unmodified polyester. It can be carried out by dissolving or dispersing a toner material such as a resin.
In the toner material, components other than the polymer having reactivity with the active hydrogen group may be added and mixed in the aqueous medium when the resin particles are dispersed in the aqueous medium, or the toner material contains the toner material. When the liquid is added to the aqueous medium, it may be added to the aqueous medium.

  The emulsification or dispersion of the toner material can be performed by dispersing a liquid containing the toner material in an aqueous medium. Then, when the toner material is emulsified or dispersed, an adhesive base is formed by subjecting a compound having an active hydrogen group and a polymer having reactivity to the active hydrogen group to an extension reaction and / or a crosslinking reaction.

Adhesive substrates such as urea-modified polyester resins contain, for example, a liquid containing a polymer having reactivity with active hydrogen groups such as polyester prepolymers having isocyanate groups, and active hydrogen groups such as amines. It may be produced by emulsifying or dispersing together with a compound in an aqueous medium and subjecting both to an extension reaction and / or a crosslinking reaction in the aqueous medium. It may be produced by emulsifying or dispersing in an added aqueous medium and by subjecting both to an extension reaction and / or a crosslinking reaction in the aqueous medium, and after emulsifying or dispersing the liquid containing the toner material in the aqueous medium. Then, a compound having an active hydrogen group is added, and an extension reaction and / or a cross-linking reaction are performed on both from the particle interface in an aqueous medium. It may be. When both are subjected to an extension reaction and / or a crosslinking reaction from the particle interface, a urea-modified polyester resin is preferentially formed on the surface of the toner to be produced, and a concentration gradient of the urea-modified polyester resin can be provided in the toner.
The reaction conditions for producing the adhesive substrate can be appropriately selected according to the combination of the polymer having reactivity with active hydrogen groups and the compound having active hydrogen groups. The reaction time is preferably 10 minutes to 40 hours, more preferably 2 hours to 24 hours. The reaction temperature is preferably 0 to 150 ° C, more preferably 40 to 98 ° C.

In a water-based medium, a method for stably forming a dispersion containing a polymer capable of reacting with an active hydrogen group such as a polyester prepolymer having an isocyanate group includes a reaction with an active hydrogen group in the aqueous medium phase. Examples thereof include a method in which a liquid prepared by dissolving or dispersing a toner material such as a polymer, a colorant, a release agent, a charge control agent, and an unmodified polyester resin in a solvent is added and dispersed by shearing force.
Dispersion can be performed using a known disperser, and examples of the disperser include a low-speed shear disperser, a high-speed shear disperser, a friction disperser, a high-pressure jet disperser, and an ultrasonic disperser. Although mentioned, since the particle diameter of a dispersion can be controlled to 2-20 micrometers, a high-speed shearing disperser is preferable.
When a high-speed shearing disperser is used, conditions such as the number of rotations, dispersion time, dispersion temperature and the like can be appropriately selected according to the purpose. The rotation speed is preferably 1000 to 30000 rpm, more preferably 5000 to 20000 rpm. In the case of a batch system, the dispersion time is preferably 0.1 to 5 minutes, and the dispersion temperature is preferably 0 to 150 ° C., more preferably 40 to 98 ° C. under pressure. The dispersion temperature is generally easier to disperse when the temperature is higher.

The amount of the aqueous medium used when emulsifying or dispersing the toner material is preferably 50 to 2000 parts by weight, and more preferably 100 to 1000 parts by weight with respect to 100 parts by weight of the toner material. If the amount used is less than 50 parts by weight, the dispersion state of the toner material may be deteriorated, and toner mother particles having a predetermined particle diameter may not be obtained. If the amount used exceeds 2000 parts by weight, the production cost is high. May be.
In the step of emulsifying or dispersing the liquid containing the toner material, it is preferable to use a dispersant from the viewpoint of stabilizing the dispersion such as oil droplets so as to obtain a desired shape and sharpening the particle size distribution.

The dispersant can be appropriately selected according to the purpose, and examples thereof include surfactants, sparingly water-soluble inorganic compound dispersants, and polymeric protective colloids, and surfactants are preferred. These may be used alone or in combination of two or more.
As the surfactant, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, and the like can be used.
Examples of the anionic surfactant include alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters and the like, and those having a fluoroalkyl group are preferably used. As an anionic surfactant having a fluoroalkyl group, a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, disodium perfluorooctanesulfonylglutamate, 3- [ω-fluoroalkyl (C6-C11) oxy ] Sodium 1-alkyl (C3-C4) sulfonate, sodium 3- [ω-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonate, fluoroalkyl (C11-C20) carboxylic acid or Its metal salt, perfluoroalkylcarboxylic acid (C7 to C13) or its metal salt, perfluoroalkyl (C4 to C12) sulfonic acid or its metal salt, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- (2 -Hydroxyethyl) perfluorooctance Examples include sulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, and the like. Commercially available surfactants having a fluoroalkyl group include Surflon S-111, S-112, S-113 (manufactured by Asahi Glass Co., Ltd.), Fluorard FC-93, FC-95, FC-98, FC-129. (Above, manufactured by Sumitomo 3M), Unidyne DS-101, DS-102 (above, manufactured by Daikin Industries, Ltd.), MegaFuck F-110, F-120, F-113, F-191, F-812, F- 833 (above, manufactured by Dainippon Ink Co., Ltd.), Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (above, manufactured by Tochem Products), Footage 100, 150 (above, manufactured by Neos).

  As cationic surfactants, amine salt type surfactants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline; alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts And quaternary ammonium salt type surfactants such as alkylisoquinolinium salts and benzethonium chloride. Among them, aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, aliphatic quaternary ammonium salts such as perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts, benzalkonium salts, benzethonium chloride, Examples include pyridinium salts and imidazolinium salts. Commercially available cationic surfactants include Surflon S-121 (manufactured by Asahi Glass Co., Ltd.); Florard FC-135 (manufactured by Sumitomo 3M); Unidyne DS-202 (manufactured by Daikin Industries), MegaFuck F-150, F -824 (manufactured by Dainippon Ink Co., Ltd.); Xtop EF-132 (manufactured by Tochem Products);

Examples of nonionic surfactants include fatty acid amide derivatives and polyhydric alcohol derivatives.
Specific examples of the amphoteric surfactant include alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine, N-alkyl-N, N-dimethylammonium betaine and the like.
Specific examples of the hardly water-soluble inorganic compound dispersant include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.
Polymeric protective colloids include monomers having carboxyl groups, alkyl (meth) acrylates having hydroxyl groups, vinyl ethers, vinyl carboxylates, amide monomers, acid chloride monomers, monomers having nitrogen atoms or heterocyclic rings thereof, and the like. Examples thereof include homopolymers or copolymers obtained by polymerization, polyoxyethylene resins, and celluloses. In addition, the homopolymer or copolymer obtained by polymerizing the above monomers includes those having a structural unit derived from vinyl alcohol.

  Specific examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride and the like. Specific examples of the (meth) acrylic monomer containing a hydroxyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, and γ-acrylate. -Hydroxypropyl, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, etc. Is mentioned.

  Specific examples of vinyl ether include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether and the like. Specific examples of vinyl carboxylate include vinyl acetate, vinyl propionate, vinyl butyrate and the like. Specific examples of the amide monomer include acrylamide, methacrylamide, diacetone acrylamide, N-methylol acrylamide, N-methylol methacrylamide and the like. Specific examples of the acid chloride monomer include acrylic acid chloride and methacrylic acid chloride. Specific examples of the monomer having a nitrogen atom or a heterocyclic ring thereof include vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, and ethyleneimine. Specific examples of the polyoxyethylene-based resin include polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, Examples include polyoxyethylene lauryl phenyl ether, polyoxyethylene phenyl stearate, and polyoxyethylene pelargonate phenyl. Specific examples of celluloses include methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and the like.

When emulsifying or dispersing the toner material, a dispersant can be used as necessary. Specific examples of the dispersant include acids such as calcium phosphate salts and those that are soluble in alkali. When calcium phosphate is used as the dispersant, the calcium phosphate salt can be removed by dissolving the calcium salt with hydrochloric acid or the like and washing it with water or decomposing with an enzyme.
A catalyst can be used for the elongation reaction and / or the crosslinking reaction in producing the adhesive substrate. Specific examples of the catalyst include dibutyltin laurate and dioctyltin laurate.

As a method for removing the organic solvent from the dispersion liquid such as an emulsified slurry, the temperature of the entire reaction system is gradually raised to evaporate the organic solvent in the oil droplets, and the dispersion liquid is sprayed in a dry atmosphere to obtain the oil. Examples include a method of removing the organic solvent in the droplets.
When the organic solvent is removed, toner base particles are formed. The toner base particles can be washed, dried, etc., and further classified. Classification may be performed by removing fine particle portions by a cyclone, decanter, centrifugation, or the like in the liquid, or classification may be performed after drying.

The obtained toner base particles may be mixed with particles such as a colorant, a release agent, and a charge control agent. At this time, by applying a mechanical impact force, it is possible to prevent particles such as a release agent from detaching from the surface of the toner base particles.
As a method of applying mechanical impact force, a method of applying impact force to a mixture using a blade rotating at a high speed, throwing the mixture into a high-speed air current, and accelerating the particles or particles to an appropriate collision plate The method of making it collide etc. is mentioned. As an apparatus used in this method, an Ong mill (manufactured by Hosokawa Micron Corporation), an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) and a pulverization air pressure are lowered, a hybridization system (manufactured by Nara Machinery Co., Ltd.) Kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar and the like.

The toner of the present invention may be manufactured using the toner manufacturing method of the present invention.
Since the toner of the present invention has a smooth surface, it has excellent properties such as transferability and chargeability, and can form a high-quality image. Further, when the toner of the present invention contains an adhesive substrate obtained by reacting a compound having an active hydrogen group with a polymer having reactivity to the active hydrogen group in an aqueous medium, the transferability and fixability are improved. Further excellent properties such as Therefore, the toner of the present invention can be used in various fields and can be suitably used for image formation by electrophotography.

  The volume average particle diameter (Dv) of the toner of the present invention is preferably 3 to 8 μm, and more preferably 4 to 7 μm. When the volume average particle diameter is less than 3 μm, in the two-component developer, the toner may be fused to the surface of the carrier during a long period of stirring in the developing device, and the charging ability of the carrier may be reduced. In the case of a one-component developer, toner filming on the developing roller and toner fusion to a member such as a blade for thinning the toner may occur. When the volume average particle diameter exceeds 8 μm, it becomes difficult to obtain a high-resolution and high-quality image, and when the toner in the developer is balanced, the fluctuation of the toner particle diameter may increase. .

The ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) of the toner of the present invention is preferably 1.00 to 1.30, and preferably 1.00 to 1.25. Is more preferable, and 1.05-1.25 is still more preferable. As a result, in the two-component developer, even if the toner balance for a long period of time is performed, the toner particle diameter in the developer is little changed, and good and stable developability can be obtained even in the case of long-term stirring in the developing device. . In the case of a one-component developer, even if the balance of the toner is performed, the fluctuation of the toner particle diameter is reduced, and the toner filming on the developing roller and the toner on a member such as a blade for thinning the toner Therefore, even when the developing apparatus is used (stirred) for a long period of time, good and stable developability can be obtained, so that a high-quality image can be obtained. When this ratio exceeds 1.30, it is difficult to obtain a high-resolution and high-quality image, and when the balance of the toner in the developer is performed, the variation in the toner particle diameter may increase. is there.
The toner particles are preferably 1 to 20% by number of particles of 2 μm or less. Outside this range, the amount of fine powder component increases, resulting in a broad charge amount distribution, and the toner particle exposure state and toner composition dispersion state differ between the fine powder component and the component having an average particle size. Image quality cannot be maintained.

  The ratio of the volume average particle diameter to the volume average particle diameter and the number average particle diameter can be measured as follows using a particle size measuring device Multisizer III (manufactured by Beckman Coulter, Inc.). First, 0.1 to 5 ml of a surfactant such as alkyl benzene sulfonate is added as a dispersant to 100 to 150 ml of an aqueous electrolyte solution such as an about 1 wt% sodium chloride aqueous solution. Next, about 2 to 20 mg of a measurement sample is added. The aqueous electrolyte solution in which the sample is suspended is subjected to a dispersion treatment for about 1 to 3 minutes using an ultrasonic disperser, and then the volume and number of toners are measured using a 100 μm aperture to determine the volume distribution and number distribution. calculate. From the obtained distribution, the volume average particle diameter and the number average particle diameter of the toner can be obtained.

The average circularity of the toner of the present invention is preferably 0.930 to 0.970, and more preferably 0.945 to 0.965. The circularity is a value obtained by dividing the circumference of a circle having an area equal to the projected area of the sample by the circumference of the sample. The content of particles having a circularity of less than 0.94 in the toner is preferably 15% or less. If the average circularity is less than 0.94, satisfactory transferability and a high-quality image free from dust may not be obtained. If it exceeds 0.97, an image forming apparatus employing blade cleaning or the like may not be used. In addition, poor cleaning of the photoconductor and the transfer belt may occur, resulting in contamination on the image. For example, when forming an image with a high image area ratio, such as a photographic image, toner that has formed an untransferred image due to poor paper feed or the like accumulates on the photoconductor, causing image smudges or touching the photoconductor The charging roller or the like to be charged may be contaminated and the original charging ability may not be exhibited.
The average circularity can be measured by an optical detection band method in which a suspension containing toner is passed through an imaging unit detection band on a flat plate, a particle image is optically detected by a CCD camera, and analyzed. It can be measured using a flow type particle image analyzer FPIA-2100 (manufactured by Sysmex Corporation).

The toner has a shape factor SF1 of 115 or more and 130 or less. SF1 is defined by the following equation.
SF1 = π (L / 2) 2 / A × 100
Here, L is an average value of the maximum length of the toner, and A is an average value of the projected area of the toner. The true sphere SF1 is 100, and as SF1 becomes larger than 100, the shape changes from spherical to indefinite. In addition, L and A sample 100 images of the carrier which expanded 300 times using FE-SEM S-800 (made by Hitachi, Ltd.), for example, via an interface, for example, image It is obtained by introducing into an analyzer Luzex AP (manufactured by Nireco) and analyzing.

The specific surface area of the toner of the present invention is preferably ^{0.5~3.0m 2 / g, 0.5~2.5m 2 /} g is more preferable. When the specific surface area is less than 0.5 m ² / g, the effect of the external additive added to the toner cannot be obtained, and the fluidity and chargeability of the toner may deteriorate, exceeding 3.0 m ² / g. In this case, the transferability may be deteriorated. The specific surface area can be measured using the BET method. Specifically, nitrogen gas can be adsorbed on the surface of the sample using a specific surface area measuring device Tristar 3000 (manufactured by Shimadzu Corporation), and measurement can be performed using the BET multipoint method.

  The penetration of the toner of the present invention is preferably 15 mm or more, and more preferably 20 to 30 mm. When the penetration is less than 15 mm, the heat resistant storage stability may be deteriorated. The penetration can be measured by a penetration test (JIS K2235-1991). Specifically, the toner is filled in a 50 ml glass container and left in a thermostat at 50 ° C. for 20 hours, and then the toner is cooled to room temperature and a penetration test is performed. In addition, it has shown that heat resistance preservability is excellent, so that the value of penetration is large.

The toner of the present invention preferably has a low fixing minimum temperature and a high offset non-occurrence temperature from the viewpoint of achieving both low-temperature fixability and offset resistance. For this purpose, it is preferable that the fixing lower limit temperature is less than 140 ° C. and the offset non-occurrence temperature is 200 ° C. or more. Here, the lower limit fixing temperature is the lower limit of the fixing temperature at which the residual ratio of the image density becomes 70% or more after a copy test is performed using an image forming apparatus and the obtained image is rubbed with a pad. The offset non-occurrence temperature can be obtained by measuring a temperature at which no offset occurs using an image forming apparatus adjusted to be developed with a predetermined amount of toner.
The thermal characteristics of the toner are also called flow tester characteristics, and are evaluated as a softening temperature, an outflow start temperature, a 1/2 method softening point, and the like. These thermal characteristics can be measured by an appropriately selected method, and can be measured using an elevated flow tester CFT500 type (manufactured by Shimadzu Corporation).

The softening temperature of the toner of the present invention is preferably 30 ° C. or higher, and more preferably 50 to 90 ° C. When the softening temperature is less than 30 ° C., the heat resistant storage stability may be deteriorated. The outflow start temperature of the toner of the present invention is preferably 60 ° C. or higher, and more preferably 80 to 120 ° C. When the outflow start temperature is less than 60 ° C., at least one of heat resistant storage stability and offset resistance may be deteriorated.
The 1/2 method softening point of the toner of the present invention is preferably 90 ° C. or higher, more preferably 100 to 170 ° C. When the 1/2 method softening point is less than 90 ° C., the offset resistance may be deteriorated.
The glass transition temperature of the toner of the present invention is preferably 40 to 70 ° C, more preferably 45 to 65 ° C. When the glass transition temperature is less than 40 ° C., the heat-resistant storage stability of the toner may deteriorate, and when it exceeds 70 ° C., the low-temperature fixability may not be sufficient. The glass transition temperature can be measured using a differential scanning calorimeter DSC-60 (manufactured by Shimadzu Corporation) or the like.

The density of an image formed using the toner of the present invention is preferably 1.40 or more, more preferably 1.45 or more, and further preferably 1.50 or more. If the image density is less than 1.40, the image density may be low and high image quality may not be obtained. The image density was determined by using a tandem color electrophotographic apparatus “Imagio Neo 450” (manufactured by Ricoh), setting the surface temperature of the fixing roller to 160 ± 2 ° C. A solid image of 1.00 ± 0.1 mg / cm 2 was formed, and the image density at any five positions in the obtained solid image was measured using a spectrometer 938 spectrodensitometer (manufactured by X-Light). The color of the toner of the present invention can be appropriately selected according to the purpose, and can be selected from the group consisting of black toner, cyan toner, magenta toner, and yellow toner. The toner of each color can be obtained by appropriately selecting a colorant.

The developer of the present invention contains the toner of the present invention, and may further contain other components appropriately selected such as a carrier. For this reason, it is excellent in transferability, chargeability, etc., and a high quality image can be formed stably. The developer may be a one-component developer or a two-component developer. However, when used in a high-speed printer or the like that supports an increase in information processing speed in recent years, the lifetime is shortened. A two-component developer is preferred because it improves.
When the developer of the present invention is used as a one-component developer, even if the balance of the toner is performed, the fluctuation of the toner particle diameter is small, the filming of the toner on the developing roller, the blade for thinning the toner, etc. Therefore, good and stable developability and images can be obtained even with long-term stirring in the developing device. When the developer of the present invention is used as a two-component developer, there is little fluctuation in the particle diameter of the toner even if the toner balance is maintained over a long period of time, and good and stable developability even with long-term agitation in the developing device. An image is obtained.

The carrier can be appropriately selected according to the purpose, but a carrier having a core material and a resin layer covering the core material is preferable.
The material of the core material can be appropriately selected from known materials, and examples thereof include 50 to 90 emu / g manganese-strontium-based material, manganese-magnesium-based material, and the like. In order to ensure the image density, it is preferable to use a highly magnetized material such as iron powder of 100 emu / g or more and magnetite of 75 to 120 emu / g. In addition, it is preferable to use a low-magnetization material such as 30-80 emu / g of copper-zinc system because it can reduce the impact of the developer in a spiked state on the photoconductor and is advantageous for high image quality. . These may be used alone or in combination of two or more.

  The volume average particle diameter of the core material is preferably 10 to 150 μm, and more preferably 40 to 100 μm. If the volume average particle size is less than 10 μm, fine particles are increased in the carrier, and magnetization per particle may be reduced to cause carrier scattering. If it exceeds 150 μm, the specific surface area is decreased, and In the case of a full color with many solid portions, the reproduction of the solid portions may be deteriorated.

  The material of the resin layer can be appropriately selected from known resins according to the purpose, but amino resin, polyvinyl resin, polystyrene resin, polyhalogenated olefin, polyester resin, polycarbonate resin, polyethylene , Polyvinyl fluoride, polyvinylidene fluoride, polytrifluoroethylene, polyhexafluoropropylene, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride Examples include fluoroterpolymers such as copolymers of monomers having no fluoro group, silicone resins, and the like. These may be used alone or in combination of two or more.

  Specific examples of the amino resin include urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Specific examples of the polyvinyl resin include acrylic resin, polymethyl methacrylate, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, and polyvinyl butyral. Specific examples of the polystyrene resin include polystyrene and styrene-acrylic copolymer. Specific examples of the polyhalogenated olefin include polyvinyl chloride. Specific examples of the polyester resin include polyethylene terephthalate and polybutylene terephthalate.

  The resin layer may contain conductive powder or the like as necessary. Specific examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. The average particle diameter of the conductive powder is preferably 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control the electric resistance. The resin layer can be formed by preparing a coating solution by dissolving a silicone resin or the like in a solvent, and then applying and drying the coating solution on the surface of the core using a known coating method, followed by baking. it can. As a coating method, a dip coating method, a spray method, a brush coating method, or the like can be used. The solvent can be appropriately selected depending on the purpose, and examples thereof include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, and butyl cellosolve. The baking may be an external heating method or an internal heating method, a method using a fixed electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, a method using a microwave, or the like. Is mentioned.

The content of the resin layer in the carrier is preferably 0.01 to 5.0% by weight. When this content is less than 0.01% by weight, a uniform resin layer may not be formed on the surface of the core material. May occur, and the uniformity of the carrier may be reduced.
The content of the carrier in the two-component developer is preferably 90 to 98% by weight, and more preferably 93 to 97% by weight.
The developer of the present invention can be used for image formation by various known electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method.

Examples of the present invention will be described below, but the present invention is not limited to the following examples. In the examples, “part” means “part by weight”.

(Creation of toner 1)
229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propion oxide 3-mole adduct, 208 parts of terephthalic acid, 46 parts of adipic acid and dibutyltin oxide 2 parts were added and reacted at 230 ° C. under normal pressure for 8 hours. Next, after reacting under reduced pressure of 10 to 15 mmHg for 5 hours, 44 parts of trimellitic anhydride was added to the reaction vessel, and reacted at 180 ° C. for 2 hours under normal pressure. [Unmodified polyester resin 1] Was synthesized.
The obtained [unmodified polyester resin 1] had a number average molecular weight of 2500, a weight average molecular weight of 6700, a glass transition temperature of 43 ° C., and an acid value of 25 mgKOH / g.

  1200 parts of water, 540 parts of carbon black Printex 35 (manufactured by Dexa; DBP oil absorption = 42 ml / 100 mg, pH = 9.5) and 1200 parts of [unmodified polyester resin 1] were used using a Henschel mixer (manufactured by Mitsui Mining). And mixed. The resulting mixture was kneaded at 150 ° C. for 30 minutes using two rolls, then rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron) to prepare [Masterbatch 1].

In a reaction vessel equipped with a stirrer and a thermometer, 378 parts of [Non-modified Polyester Resin 1], 110 parts of carnauba wax, and 947 parts of ethyl acetate were charged, and the temperature was raised to 80 ° C. with stirring. After maintaining the time, it was cooled to 30 ° C. over 1 hour. Next, 500 parts of a master batch and 500 parts of ethyl acetate were charged into the reaction vessel and mixed for 1 hour to obtain a raw material solution.
1324 parts of the obtained raw material solution was transferred to a reaction vessel, and filled with 80% by volume of 0.5 mm zirconia beads using a bead mill Ultra Visco Mill (manufactured by Imex Co., Ltd.). 3 passes under the condition of 6 m / sec. I. Pigment Red and carnauba wax were dispersed to obtain a wax dispersion.

Next, 1324 parts of a 65 wt% ethyl acetate solution of unmodified polyester resin was added to the wax dispersion. 1.0 part of Kraton APA (manufactured by Southern Clay Products) is added to 200 parts of a dispersion obtained by one pass using Ultraviscomil under the same conditions as described above. K. Using a homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.), the mixture was stirred at 7000 rpm for 60 minutes to obtain a dispersion of toner material.
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, 22 parts of trimellitic anhydride And 2 parts of dibutyltin oxide were added and reacted at 230 ° C. for 8 hours under normal pressure. Next, it was made to react under reduced pressure of 10-15mHg for 5 hours, and the intermediate polyester resin was synthesize | combined.
The obtained intermediate polyester resin had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, a glass transition temperature of 55 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 51 mgKOH / g.

Next, 410 parts of the intermediate polyester resin, 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are charged into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Was synthesized. The free isocyanate content of the obtained prepolymer was 1.53% by weight.
In a reaction vessel equipped with a stir bar and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to synthesize a ketimine compound. The amine value of the obtained ketimine compound was 418 mgKOH / g.
In a reaction vessel, 749 parts of a dispersion of toner material, 115 parts of a prepolymer and 2.9 parts of a ketimine compound are charged and mixed at 5,000 rpm for 1 minute using a TK homomixer (manufactured by Tokushu Kika). A mixture was obtained.

In a reaction vessel equipped with a stirring bar and a thermometer, 683 parts of water, 11 parts of reactive emulsifier (sodium salt of sulfuric acid ester of methacrylic acid ethylene oxide adduct), Eleminol RS-30 (manufactured by Sanyo Chemical Industries), styrene 83 Parts, 83 parts of methacrylic acid, 110 parts of butyl acrylate and 1 part of ammonium persulfate were stirred at 400 rpm for 15 minutes to obtain an emulsion. The emulsion was heated, heated to 75 ° C. and reacted for 5 hours. Next, 30 parts of a 1% by weight aqueous ammonium persulfate solution was added and aged at 75 ° C. for 5 hours to prepare a resin particle dispersion.
The volume average particle size of the resin particles contained in the obtained resin particle dispersion was measured using a particle size distribution measuring apparatus Microtrac Ultra Fine Particle Size Distribution Analyzer UPA-EX150 (manufactured by Nikkiso Co., Ltd.) using a laser Doppler method. However, it was 105 nm. A part of the resin particle dispersion was dried to isolate the resin, and the glass transition temperature of the resin was measured. As a result, it was 59 ° C. and the weight average molecular weight was 150,000.

990 parts of water, 83 parts of resin particle dispersion, 37 parts of a 48.5% by weight aqueous solution of dodecyl diphenyl ether disulfonate, Eleminol MON-7 (manufactured by Sanyo Kasei Kogyo Co., Ltd.), 1% by weight aqueous solution of sodium carboxymethylcellulose polymer dispersant 135 parts of BS-H-3 (Daiichi Kogyo Seiyaku Co., Ltd.) and 90 parts of ethyl acetate were mixed and stirred to obtain an aqueous medium.
To 1200 parts of the aqueous medium, 867 parts of the oil phase mixed liquid was added and mixed for 20 minutes at 13000 rpm using a TK homomixer to prepare a dispersion (emulsified slurry).

Next, the emulsified slurry was charged into a reaction vessel in which a stirrer and a thermometer were set, and after removing the solvent at 30 ° C. for 8 hours, aging was performed at 45 ° C. for 4 hours to obtain a dispersed slurry.
The obtained dispersion slurry was measured using Multisizer III (manufactured by Beckman Coulter, Inc.). The volume average particle size was 5.1 μm and the number average particle size was 4.9 μm.
After 100 parts by weight of the dispersion slurry was filtered under reduced pressure, 100 parts of ion-exchanged water was added to the filter cake, mixed at 12000 rpm for 10 minutes using a TK homomixer, and then filtered. The obtained filter cake was added with 10% by weight phosphoric acid to adjust the pH to 3.7, mixed at 12000 rpm for 10 minutes using a TK homomixer, and then filtered.

Furthermore, 300 parts of ion-exchanged water was added to the obtained filter cake, mixed for 10 minutes at 12000 rpm using a TK homomixer, and then filtered twice to obtain a final filter cake.
The obtained final filter cake was dried at 45 ° C. for 48 hours using a circulating dryer, and sieved with a mesh having a mesh size of 75 μm to obtain [Toner Base Particle 1].
To 100 parts of the obtained toner base particles, hydrophobic silica H2000 as an external additive (manufactured by Clariant): 1.0 part and X-24 (manufactured by Shin-Etsu Chemical Co., Ltd .; large particle diameter silica having an average particle diameter of 120 nm) ): 0.75 part was added and mixed using a Henschel mixer (Mitsui Mining Co., Ltd.) to produce [Toner 1].

(Creation of toner 2)
[Toner 2] was produced in the same manner as (Toner 1) except that the addition amount of Clayton APA was changed from 1.0 part to 2.0 parts.
(Creation of toner 3)
[Toner 3] was produced in the same manner as (Toner 2) except that the amount of X-24 as an external additive was changed from 1.0 part to 0.00 part.
(Creation of toner 4)
In [Toner 2], “Emulsified slurry was added and the solvent was removed for 8 hours at 30 ° C., followed by aging at 45 ° C. for 4 hours to obtain a dispersed slurry”. [Toner 4] was produced in the same manner as [Toner 2] except that the solvent was used, followed by aging at 45 ° C. for 4 hours to obtain a dispersed slurry.
(Creation of toner 5)
[Toner 5] was produced in the same manner as [Toner 1] except that the addition amount of Clayton APA was changed from 1.0 part to 0.3 part.
(Creation of toner 6)
[Toner 6] was prepared in the same manner as (Toner 1) except that 1.0 part of Clayton APA was changed to 40 parts of MEK-ST (manufactured by Nissan Chemical Industries, Ltd .: methyl ethyl ketone solution having a solid content of 20%) as organosilica.

(Creation of toner 7)
Preparation of [Unmodified Polyester Resin 2] In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 229 parts of bisphenol A ethylene oxide 2 mol adduct, 529 parts of bisphenol A propion oxide 3 mol adduct, terephthalic acid 208 Part, 80 parts of isododecenyl succinic anhydride, 44 parts of trimellitic anhydride and 2 parts of dibutyltin oxide were reacted at 230 ° C. for 10 hours under normal pressure to synthesize [Unmodified Polyester Resin 2].
The obtained [unmodified polyester resin 2] had a number average molecular weight of 7200, a weight average molecular weight of 16000, a glass transition temperature of 65 ° C., and an acid value of 15 mgKOH / g.
Preparation of toner [Unmodified polyester resin 2] 85 parts Masterbatch 1 15 parts Clayton APA 4 parts The above materials are sufficiently stirred and mixed with a Henschel mixer, and then kneaded for 1 hour with two rolls having a roll surface of 100 degrees. After rolling and cooling at 5 degrees / min and coarse pulverization, pulverization classification is performed using an I-2 type mill (manufactured by Nippon Pneumatic Kogyo Co., Ltd.) and a DS classifier (manufactured by Nippon Pneumatic Co., Ltd.). Toner mother particles 6 of 1 μm were obtained.
To 100 parts of the toner base particles obtained, 0.5 part of hydrophobic silica H2000 (manufactured by Clariant) as an external additive and 1.0 part of X-24 (manufactured by Shin-Etsu Chemical) are added, [Toner 7] was produced by mixing using a Henschel mixer (Mitsui Mining Co., Ltd.).

(Creation of toner 8)
[Toner 8] was prepared in the same manner as [Toner 7] except that the addition amount of Clayton APA was changed from 4.0 parts to 2.0 parts.

(Evaluation of physical properties of toner)
The toner was evaluated.
(Measurement of surface atom concentration by XPS)
Equipment used: 1600S X-ray photoelectron spectrometer manufactured by PHI Use conditions: X-ray source MgKα (100 W)
Analysis area: 0.8 × 2.0mm
The sample was measured by placing a toner on a carbon sheet on a sample holder.
The kneaded product was measured by roughly crushing the block after melt-kneading the toner for 30 minutes at 130 ° C. and 70 rpm using a lab plast mill, and similarly placing it on a carbon sheet.
The surface atomic concentration was calculated from the peak intensity of each atomic concentration measured using a relative sensitivity factor provided by PHI, and the surface atomic concentration was estimated.
In this measurement, since the layered inorganic compound contains Al, the atomic concentration% of Al was measured.

(Measurement of circularity)
In the present invention, a flow type particle image analyzer (“FPIA-2100”; manufactured by Sysmex Corporation) is used to measure ultrafine toner, and analysis software (FPIA-2100 Data Processing Program for FPIA version 00-10) is used. And analyzed. Specifically, 0.1 to 0.5 ml of 10 wt% surfactant (alkylbenzene sulfonate Neogen SC-A; Daiichi Kogyo Seiyaku) is added to a glass 100 ml beaker, and each toner 0.1 to 0 is added. 0.5 g was added and stirred with a microspatel, and then 80 ml of ion-exchanged water was added. The obtained dispersion was subjected to a dispersion treatment for 3 minutes with an ultrasonic disperser (manufactured by Honda Electronics Co., Ltd.). The shape and distribution of the toner were measured using the FPIA-2100 until the density of the dispersion was 5000 to 15000 / μl. In this measurement method, it is important that the concentration of the dispersion liquid is 5000 to 15000 / μl from the viewpoint of measurement reproducibility of the average circularity. In order to obtain the dispersion concentration, it is necessary to change the conditions of the dispersion, that is, the amount of surfactant to be added and the amount of toner. The amount of the surfactant varies depending on the hydrophobicity of the toner as in the measurement of the toner particle diameter described above. If it is added in a large amount, noise due to bubbles is generated. If the amount is too small, the toner cannot be sufficiently wetted. It becomes insufficient. Further, the toner addition amount differs from the particle size, and it is necessary to decrease the small particle size and increase the large particle size. When the toner particle size is 3 to 7 μm, the toner amount is 0.1 to 0. By adding 0.5 g, the dispersion concentration can be adjusted to 5000 to 15000 / μl.

(Measurement of particle size)
The ratio of the volume average particle diameter to the volume average particle diameter and the number average particle diameter can be measured as follows using a particle size measuring device Multisizer III (manufactured by Beckman Coulter, Inc.).
First, 0.1 to 5 ml of a surfactant such as alkyl benzene sulfonate is added as a dispersant to 100 to 150 ml of an aqueous electrolyte solution such as an about 1 wt% sodium chloride aqueous solution. Next, about 2 to 20 mg of a measurement sample is added. The aqueous electrolyte solution in which the sample is suspended is subjected to a dispersion treatment for about 1 to 3 minutes using an ultrasonic disperser, and then the volume and number of toners are measured using a 100 μm aperture to determine the volume distribution and number distribution. calculate. From the obtained distribution, the volume average particle diameter and the number average particle diameter of the toner can be obtained.
Table 1 shows the evaluation results of the toner.

[Examples 1-7, Comparative Examples 1-5]
Next, the cleaning properties of the image forming apparatuses of Examples 1 to 7 and Comparative Examples 1 to 5 were evaluated using the toners 1 to 7. The evaluation results are shown in Table 2.
Evaluation was performed as follows.
(Cleanability evaluation)
1. All toners and devices used for evaluation were left in an environmental room at 25 ° C. and 50% for one day.
2. All the toner of the Imageo neo C600 commercial product PCU was removed, leaving only the carrier in the developing device.
3. In a developing device having only a carrier, 28 g of black toner serving as a sample was charged, and 400 g of a developer having a toner concentration of 7% was prepared.
4). A developing device was mounted on the Imageo neo C600 main body, and only the developing device was idled for 5 minutes at a developing sleeve linear velocity of 300 mm / s.
5. Both the developing sleeve and the photosensitive member were rotated at 300 mm / s trailing, and the charging potential and the developing bias were adjusted so that the toner on the photosensitive member would be 0.6 ± 0.05 mg / cm ² .
6). The cleaning blade was only one cleaning blade mounted on a commercially available Imagio neo C600 PCU, its elastic modulus was 70%, the thickness was 2 mm, and the contact angle with the image carrier at the counter was 20 °.
7). Under the above development conditions, the transfer current was adjusted so that the transfer rate was 96 ± 2%.
8). A fibrous tape was attached in front of the charging roller so that the toner after the cleaning process (toner that passed through the cleaning blade) could be collected.
9. Using the set values, 2000 charts showing the concentrations of 100%, 25%, 5%, and 0% shown in FIG. 1 were output.
10. The weight of the toner adhering to the tape attached in the above 8 was measured, and the amount of slipping through the cleaning blade was evaluated. The cleaning property is good when the weight of the slipped toner is less than 0.25 g.
11. After completion of the above 9, all solid images were created and evaluated for the presence of white spots in the images.
A case where there was no white spot in the image was indicated by ◯, and a case where the image was generated was indicated by ×.
If filming has occurred on the image bearing member, this portion is not developed and appears as a white spot on the image.

  According to the image forming apparatus of the present invention, filming does not occur, cleaning performance can be ensured over a long period of time, and high image quality excellent in fine dot reproducibility can be obtained. It is suitable as a toner used for an image forming apparatus.

It is a figure which shows the printing pattern used for the cleaning property evaluation test.

Claims (19)

  An image bearing member; a charging unit that charges the surface of the image bearing member; an exposure unit that writes a latent image by exposing the image bearing member; and a toner that has a toner and that is written on the image bearing member. Developing means for developing a visible image, transfer means for transferring the visible image to a recording medium directly or via an intermediate transfer member, and fixing means for fixing the transferred image transferred to the recording medium; The cleaning unit is a blade-like elastic member that abuts the tip of the image carrier with a cleaning unit that cleans transfer residual toner on the image carrier that has not been completely transferred. The contact portion between the image carrier and the elastic member has a surface pressure of 2 MPa to 8 MPa, and the toner contains at least a binder resin, a colorant, a release agent, and at least part of ions between layers. Image formation characterized in that the toner has a layered inorganic mineral modified with ions, and the atomic concentration% of the specific element constituting the layered inorganic mineral when the toner is measured by XPS is 0.5 atomic% or more apparatus.   The toner is a toner obtained by granulating by dispersing and / or emulsifying an oil phase and / or a monomer phase containing at least a toner composition and / or a toner composition precursor in an aqueous medium. The image forming apparatus according to claim 1.   2. The toner according to claim 1, wherein in the distribution of the modified layered inorganic mineral in the toner, the abundance in the 0.5 μm region from the layer on the toner surface is higher than the abundance of the blended toner composition ratio. The image forming apparatus according to 1 or 2.   The image forming apparatus according to claim 1, wherein the toner has an average circularity of 0.930 to 0.970. 2. The toner according to claim 1, wherein the toner is obtained by externally adding fine particles having an average primary particle size of 50 to 500 nm and a bulk density of 0.3 g / cm ³ or more on the surface of toner base particles. The image forming apparatus according to any one of?   The image-forming according to any one of claims 1 to 5, wherein the modified layered inorganic mineral is a layered inorganic mineral obtained by modifying at least a part of metal cations between layers of the layered inorganic mineral with an organic cation. apparatus.   The toner is obtained by dispersing and / or emulsifying, in an aqueous medium, an oil phase which is a solution and / or a dispersion obtained by dissolving and / or dispersing a toner composition containing at least a binder resin and / or a binder resin precursor. The image forming apparatus according to claim 1, wherein the toner is obtained by granulation.   In the solution or dispersion, 0.05 to 2% by weight of a layered inorganic mineral obtained by modifying at least part of ions between layers with organic ions is contained in the solid content of the solution or dispersion. The image forming apparatus according to claim 7.   The image forming apparatus according to claim 1, wherein the binder resin contained in the toner contains at least two kinds of binder resins.   The image forming apparatus according to claim 9, wherein the first binder resin contained in the binder resin is a resin having a polyester skeleton.   The image forming apparatus according to claim 10, wherein the first binder resin is a polyester resin.   The image forming apparatus according to claim 11, wherein the polyester resin is an unmodified polyester resin.   The image forming apparatus according to claim 7, wherein the binder resin precursor is a modified polyester resin.   The toner dissolves at least a first binder resin, the binder resin precursor, a compound that extends or crosslinks with the binder resin precursor, a colorant, a release agent, and the modified layered inorganic mineral in at least an organic solvent. Alternatively, it is obtained by dispersing, dissolving or dispersing the solution or dispersion in an aqueous medium, and removing the solvent from the obtained solution or dispersion. The image forming apparatus according to claim 10.   The ratio Dv / Dn between the volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner is 1.00 to 1.30, according to any one of claims 1 to 14. Image forming apparatus.   The image forming apparatus according to claim 1, wherein 1 to 20% by number of particles of 2 μm or less of the toner are included.   The image forming apparatus according to claim 1, wherein the content of the polyester resin component contained in the binder resin of the toner is 50 to 100% by weight.   The image forming apparatus according to claim 1, wherein the toner has a glass transition point of 40 to 70 ° C.   The image forming apparatus according to claim 1, wherein toner is used as a two-component developer.

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