JP4603837B2 - Toner, developer using the toner, container with toner, process cartridge, and image forming method - Google Patents

Description

  The present invention relates to a toner, a developer using the toner, a container containing toner, a process cartridge, and an image forming method.

Image formation by electrophotography generally forms an electrostatic latent image on a photosensitive member (electrostatic latent image carrier), and develops the electrostatic latent image with a developer to form a visible image (toner image). After that, the visible image is transferred to an image support (transfer material) such as paper and fixed by heating and pressing to form a fixed image.
The heat and pressure fixing requires the toner to be fixed at a low temperature. In recent years, it is also important to save energy in the fixing device, and the fixing member has a low heat capacity. When such a fixing device is used, it is required to fix the toner at a lower temperature than before, and in order to respond to this, there are many reports of using not only an amorphous resin but also a crystalline polyester as a binder resin. Yes.
However, the crystalline polyester may not be able to achieve low-temperature fixing of the toner depending on the combination with other resins forming the toner. In addition, using only crystalline polyester has a problem that a hot offset phenomenon and a blocking phenomenon occur even though the toner can be fixed at a low temperature. Furthermore, when kneading crystalline polyester having sharp melt properties, if the toner contains too much crystalline polyester, the melt viscosity becomes extremely low, and the colorant and release agent contained in the toner are finely dispersed. Easy to block. The uneven dispersion of the colorant leads to a decrease in the degree of coloration, and it may not be possible to obtain a high density image. In addition, when a full color toner is used, a clear image may not be obtained. In addition, when the colorant is formed of a low-resistance material such as carbon, for example, if the dispersion state of the colorant in the toner is poor, the resistance of the toner is lowered, and the background stain (fogging) of the image due to the deterioration in developability Further, density unevenness in the solid portion may occur due to deterioration in transferability. Further, the non-uniform dispersion of the release agent increases the probability that the release agent is present on the toner surface, and in the same way as the non-uniform dispersion of the colorant, causes a negative effect due to deterioration in developability. Furthermore, over time, when using a two-component developer, when using a one-component developer, the release agent is fused to the charging roller or blade, and the durability deteriorates. is there.

  In addition, there has been an extremely high demand for higher image quality than before. For realizing the high image quality, it is effective to reduce the particle size of the toner. However, as the toner particle size becomes smaller, problems due to deterioration of the dispersibility of each component forming the toner are more likely to occur. Scattering becomes noticeable. For this reason, in consideration of the reduction in particle size, it is necessary to add crystalline polyester to the toner without deteriorating the dispersion state of each component forming the toner.

In order to solve these problems due to the inclusion of the crystalline polyester and obtain a low-temperature fixing toner, the crystalline polyester and the amorphous resin should be appropriately dispersed without being excessively compatible. In addition to being a polyester, a method has been reported in which a raw material monomer having a similar structure is contained in each raw material monomer of crystalline polyester and amorphous polyester (Patent Document 1 and Patent Document 2).
As a combination of such raw material monomers, there are a case where an alcohol component having a similar structure is used and a case where an acid component having a similar structure is used.
It has been reported that a crystalline polyester composed of an aliphatic diol and an aliphatic carboxylic acid is preferable because it has a high sharp melt property, which is the main effect of the crystalline polyester. Therefore, there are cases where the acid component of the amorphous polyester contains an aliphatic carboxylic acid and cases where the alcohol component contains an aliphatic alcohol. As the alcohol component of the amorphous polyester resin, those having a bisphenol A skeleton are often used. On the other hand, there is a report that polyesters using aliphatic alcohols exhibit better fixability and better wax dispersibility than polyesters using aromatic alcohols (Patent Document 3).
The inclusion of an aliphatic alcohol as the alcohol component of the amorphous polyester is effective for suppressing various problems due to poor wax dispersion in the low-temperature fixing toner. However, since there is no aromatic ring charge holding part of the bisphenol A skeleton, there are disadvantages in that the chargeability tends to be inferior and the change in charging due to the environment is large.

Japanese Patent No. 3449995 JP 2004-151535 A JP 2002-287427 A

  The object of the present invention is to have low-temperature fixability, ensure hot offset resistance and blocking resistance, have excellent charging ability, do not cause a dispersion failure of the release agent, and output a large number of sheets, To provide a toner that does not deteriorate developability even under humidity, a developer using the toner, a toner-containing container, a process cartridge, and an image forming method.

As a result of intensive studies, the present inventors have used a salicylic acid metal complex having a specific metal, for example, even in a combination of a crystalline polyester that tends to be poorly charged and an amorphous polyester that does not have a bisphenol A skeleton, It has been found that the charging property is improved.
The invention of claim 1 is a toner containing at least a crystalline polyester and an amorphous polyester as a binder resin, a charge control agent, and a release agent,
As the crystalline polyester, the alcohol component contains an aliphatic diol as a main component (but does not include an aromatic alcohol) , the acid component contains a resin containing an aliphatic dicarboxylic acid as a main component, The alcohol component contains an aliphatic diol as a main component (but does not contain an aromatic alcohol) , the acid component contains a resin containing an aromatic dicarboxylic acid as a main component, and the iron or zirconium complex of salicylic acid as the charge control agent. A toner characterized by comprising
The invention according to claim 2 is the toner according to claim 1, wherein the toner has a glass transition temperature of 35 to 55 ° C.
The invention according to claim 3 is the toner according to claim 1 or 2, wherein the content of the crystalline polyester is 40% by mass or less of the total amount of the binder resin.
According to a fourth aspect of the present invention, in the toner according to any one of the first to third aspects, the melting point of the crystalline polyester is 80 to 130 ° C.
The invention according to claim 5 is the toner according to any one of claims 1 to 4, wherein the glass transition temperature of the amorphous polyester is 40 to 70 ° C.
According to a sixth aspect of the present invention, in the toner according to any one of the first to fifth aspects, the melting point of the release agent is 70 to 90 ° C.
In the invention of claim 7, the mass average particle size is 3 to 6.5 μm, and the ratio (D4 / D1) of the mass average particle size (D4) to the number average particle size (D1) is 1.00 to 1.m. The toner according to claim 1, wherein the toner is in a range of 40.
The invention according to claim 8 is the toner according to claim 1, wherein the toner is a full-color toner.
The invention according to claim 9 is the toner according to claim 8, wherein the amorphous polyester has a tetrahydrofuran (THF) insoluble content of 0 to 5 mass%.
A tenth aspect of the present invention is a developer comprising the toner according to any one of the first to ninth aspects.
An eleventh aspect of the invention is a toner-containing container in which the toner according to any one of the first to ninth aspects is accommodated.
According to a twelfth aspect of the present invention, an electrostatic latent image carrier and the electrostatic latent image formed on the electrostatic latent image carrier are developed using the developer according to the tenth aspect to form a visible image. The process cartridge includes at least a developing unit and is detachable from the main body of the image forming apparatus.
In the invention of claim 13, the electrostatic latent image formed on the image carrier is developed with a developer, the toner image formed on the image carrier is transferred to an image support, and the transferred toner image is transferred to the image carrier. An image forming method including a step of fixing and obtaining a fixed image, wherein the developer is the developer according to claim 10.
The invention according to claim 14 is the image forming method according to claim 13, wherein the image carrier is an amorphous silicon photoconductor.
A fifteenth aspect of the invention is the image forming method according to the thirteenth aspect, wherein an alternating electric field is applied when the electrostatic latent image formed on the image bearing member is developed with a developer.

  According to the present invention, it has low-temperature fixability, secures hot offset resistance and blocking resistance, has excellent charging ability, does not cause poor dispersion of the release agent, and outputs a large number of sheets or at high temperature and high temperature. Provided are a toner that does not deteriorate developability even under humidity, a developer using the toner, a toner-containing container, a process cartridge, and an image forming method.

Hereinafter, the present invention will be described in more detail.
The toner of the present invention contains a crystalline polyester and an amorphous polyester as a binder resin, and further contains a specific charge control agent and release agent, and, if necessary, a colorant, inorganic fine particles, resin fine particles and the like.

  Crystalline polyester has a melting point, and has a sharp melt property that causes a crystal transition at the melting point and at the same time the melt viscosity rapidly decreases from the solid state. In addition to the sharp melt effect of the crystalline polyester, the toner of the present invention has a glass transition temperature (Tg) of the amorphous polyester that is partially compatible with the amorphous polyester. Since the melt viscosity starts to decrease from a low temperature, the temperature becomes low-temperature fixing.

Crystalline polyester is synthesized with aliphatic diol (but not containing aromatic alcohol) and aliphatic dicarboxylic acid as the main components in order to form a crystal structure and to obtain a high sharp melt property which is the main effect. An aliphatic polyester resin is preferred. Moreover, it is preferable that the crystalline polyester and the amorphous polyester have a similar structure so that the decrease in melt viscosity starts at a low temperature.

The toner of the present invention includes an amorphous polyester containing an alcohol component containing an aliphatic diol as a main component (but not including an aromatic alcohol) , and an acid component containing a resin synthesized using an aromatic dicarboxylic acid as a main component. It is a feature. Such a resin is preferably contained in the binder resin in an amount of 50 to 97% by mass.
Thereby, the dispersion | distribution defect of a mold release agent can be improved. In addition, as described above, if the crystalline polyester and the amorphous polyester have a similar structure, they are easily compatible with each other, and can be efficiently fixed at a low temperature according to the content of the crystalline polyester. preferable. According to this aspect, there is no need to worry about deterioration of blocking resistance or offset resistance due to an excessive content of crystalline polyester.
In order to make the crystalline polyester and the amorphous polyester have a similar structure, there is a combination in which the acid component is similar, but in the present invention, from the viewpoint of improving the dispersibility of the release agent, the alcohol component It is preferable to resemble. By using an aliphatic diol as the alcohol component of the crystalline polyester and the amorphous polyester, it is possible to suppress the adverse effects caused by filming and spent compared to the case of acid content similarity.
The main component of the alcohol component is an aliphatic diol (but not including an aromatic alcohol) , which is particularly effective for a full-color toner having a low melt viscosity and a low release agent dispersion effect due to shearing force during kneading. .

The diol component of the crystalline polyester and the amorphous polyester of the present invention is preferably an alcohol component containing a diol compound having 2 to 20 carbon atoms and derivatives thereof.
In addition to the above, as an alcohol component, there are alkylene oxide adducts of bisphenol A, other dihydric alcohol compounds, trihydric or higher polyhydric alcohols, etc., but they exhibit good compatibility due to having similar structures, In order to suppress various problems due to the inclusion of the crystalline polyester, the aliphatic diol in the alcohol component is 60 mol% or more, more preferably 80 mol% or more, and particularly preferably 98 mol% or more.

  The acid components of the crystalline polyester and the amorphous polyester of the present invention include polycarboxylic acid compounds such as aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and alicyclic dicarboxylic acids, and acids containing these derivatives. Ingredients are preferred.

  The crystalline polyester of the present invention can be appropriately selected from the above alcohol component and acid component, but ethylene glycol, 1,4-butanediol, 1,6- Alcohol components containing linear alkylene glycols having 2 to 6 carbon atoms such as hexanediol and their derivatives, and aliphatic dicarboxylic acid compounds such as maleic acid, fumaric acid and succinic acid, and acid components containing these derivatives An aliphatic polyester resin represented by the following general formula (1) is preferred.

In the general formula (1), ^{R 1} and ^{R 2} represents a hydrocarbon group. n and m represent the number of repeating units.

  In order to synthesize a non-linear polyester resin, a trihydric or higher polyhydric alcohol such as glycerin may be added to the alcohol component, or a trivalent or higher polyhydric acid such as trimellitic anhydride may be added to the acid component. Polycondensation may be performed by adding a polyvalent carboxylic acid or the like.

The melting point of the crystalline polyester has a large influence on the minimum fixing temperature when the sharp melt property is high. The melting point is preferably low as long as blocking or the like does not occur. Specifically, the melting point is preferably 80 to 130 ° C. 80 to 120 ° C. is more preferable. When the melting point is lower than 80 ° C., it may be difficult to synthesize a crystalline resin having sharp melt properties and excellent low-temperature fixability. When the melting point exceeds 130 ° C., the minimum fixing temperature is increased. Therefore, good low-temperature fixability may not be obtained. The melting point of the crystalline polyester is, for example, raised to 20 to 150 ° C. at 10 ° C./min using a differential scanning calorimeter (“DSC-60”; manufactured by Shimadzu Corporation), and lowered without holding time. After cooling to the measurement start temperature at a rate of 10 ° C./min and then measuring at a rate of temperature increase of 10 ° C./min, it can be determined by calculating the endothermic peak temperature at the second temperature increase.
The crystallinity of the crystalline polyester can be confirmed by a diffraction pattern by a powder X-ray diffractometer. The diffraction pattern has a diffraction peak at a position of at least 2θ = 20 to 25 °, and any of 2θ = 19 to 20 °, 21 to 22 °, 23 to 25 °, and 29 to 31 °. More preferably, a diffraction peak exists at the position.

The diffraction pattern can be confirmed, for example, by measuring powder using an XRD standard material holder under the following conditions using an X-ray diffractometer (“RINT-1100”; manufactured by Rigaku Electric Co., Ltd.). it can.
Tube: Cu
Tube voltage / current: 50kV-30mA
Goniometer: Wide angle goniometer Sampling width: 0.020 °
Scanning speed: 2.0 ° / min
Scanning range: 5-50 °
In addition, the presence of the diffraction peak was subjected to a peak search for those processed with a smoothing point of 11, and the presence or absence was determined from the detected peak.

The content of the crystalline polyester in the binder resin is preferably 50% by mass or less, more preferably 40% by mass or less, and particularly preferably 3 to 35% by mass. When the content exceeds 50% by mass, the crystalline polyester and the amorphous polyester tend to have a phase separation structure, and the dispersibility of these resins in the toner may deteriorate. In addition, when the combination of the crystalline polyester and the amorphous polyester of the present invention has a lot of compatible parts, it can be efficiently fixed at a low temperature with respect to the content. It may be inferior in hot offset property. In the present invention, by suppressing the content to 40% by mass or less, it is easy to obtain a toner having a sufficient margin for blocking and hot offset occurrence.
In addition, unevenness of the colorant and release agent in the toner may deteriorate the chargeability of the toner, causing fogging of the image and in-machine contamination due to toner scattering. When the content is less than 3% by mass, the low-temperature fixability may be inferior.

  The amorphous polyester of the present invention can be appropriately selected from the above-mentioned alcohol component and acid component, but those having an acid component as a main component of an aromatic dicarboxylic acid such as terephthalic acid or isophthalic acid are preferred. By making the main component of the acid component dissimilar to the main component of the crystalline polyester, the crystallinity of the crystalline polyester is maintained without being too compatible with the crystalline polyester and the amorphous polyester. , And can be dispersed in the toner.

  Each of the alcohol component and the acid component may be used alone or in combination of two or more. Moreover, crystalline polyester and amorphous polyester may be used individually by 1 type, respectively, and may use 2 or more types together, respectively.

  In addition to the above polyester, styrene, α-methylstyrene, chlorostyrene, styrene-propylene copolymer, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, styrene-vinyl acetate copolymer, styrene-maleic acid copolymer. Styrene resins such as polymers, styrene-acrylic acid ester copolymers, styrene-methacrylic acid ester copolymers, styrene-acrylonitrile-acrylic acid ester copolymers, polyester resins, vinyl chloride resins, rosin modified maleic acid resins, A phenol resin, an epoxy resin, a polyethylene resin, a polypropylene resin, an ionomer resin, a polyurethane resin, a silicone resin, a ketone resin, a xylene resin, a petroleum resin, a petroleum resin to which hydrogen is added, and the like can also be used. These are preferably added to such an extent that the quality of toner by combining the crystalline polyester and the amorphous polyester is not impaired, and is within 20% by mass, more preferably within 10% by mass in the binder resin.

The glass transition temperature of the amorphous polyester is preferably 40 to 70 ° C. When the glass transition temperature is less than 40 ° C., the heat-resistant storage stability of the toner is remarkably deteriorated and blocking may occur, and when it exceeds 70 ° C., the low-temperature fixability of the toner may be deteriorated.
The glass transition temperature of the amorphous polyester is, for example, increased to 20 to 150 ° C. at 10 ° C./min using a differential scanning calorimeter (“DSC-60”; manufactured by Shimadzu Corporation), and then the holding time. Without cooling, after cooling to the measurement start temperature at a temperature drop rate of 10 ° C./min, when measured at a temperature rise rate of 10 ° C./min, it can be determined by the tangential method at the second temperature rise.

The softening point (F _1/2 ) of the amorphous polyester is preferably 120 to 160 ° C. If the F1 _{/ 2} temperature is less than 120 ° C, the hot offset property may be deteriorated, and if it exceeds 160 ° C, it tends to be highly elastic, and the share when the material forming the toner is dispersed increases. The load on the kneading apparatus increases. In addition, the low-temperature fixability may be deteriorated.
The F1 _{/ 2} temperature of the amorphous polyester can be obtained from a flow curve measured using, for example, an elevated flow tester CFT500 type (manufactured by Shimadzu Corporation). The _{F 1/2} temperature die diameter 1 mm, pressure 10 kgf / cm ^2, under the conditions of heating rate 3 ° C. / min, stroke when the sample of 1 cm ² was melted flowing out, the flow ending the flow starting point This is the temperature at which the stroke change amount up to a point is ½.

The amorphous polyester may contain tetrahydrofuran (THF) insoluble matter, and when the content of THF-free matter is 10% by mass or more, more preferably 10 to 40% by mass, low temperature fixability and hot offset resistance are obtained. Easy to balance. However, in a full-color toner in which two or more colors need to be mixed to express each color, the THF-insoluble content is preferably less than 10% by mass in order to sufficiently melt the toner. More preferably, it is 0-5 mass%.
The amount of the THF-insoluble matter in the amorphous resin was calculated by extracting the THF-soluble matter with a Soxhlet extractor. Extraction of THF solubles with a Soxhlet extractor was performed as follows. 5 g of resin was precisely weighed and placed in a cylindrical filter paper having an inner diameter of 24 mmφ and set in an extraction tube, and 100 g of THF was placed in the flask. A set of flask portions with a condenser tube attached was placed in a mantle heater, and THF was refluxed at 80 ° C., so that THF from the condenser tube was dropped onto the resin, and THF solubles were extracted into the flask. After extraction for 10 hours, THF in the extract was distilled off under reduced pressure to obtain a residue. From the exact balance value (A) of 5 g of resin and the residual mass (B) of the extract, the THF-insoluble matter is calculated as (1-B / A) × 100.

The toner of the present invention preferably has a glass transition temperature of 55 ° C. or lower in order to obtain a low-temperature fixability higher than that of the conventional toner. With such a temperature, a conventional toner containing no crystalline polyester may have insufficient blocking resistance, but a toner containing crystalline polyester can ensure blocking resistance even at such a temperature. Since the toner of the present invention has a low glass transition temperature due to a compatible portion near the interface between the crystalline polyester and the amorphous polyester, the combination of the crystalline polyester and the amorphous polyester of the present invention, which tends to increase the compatible portion, is It is easy to obtain a toner having a glass transition temperature of 55 ° C. or lower. However, since the blocking resistance tends to be insufficient if it becomes too low, the glass transition temperature of the toner is preferably 35 ° C. or higher.
The glass transition temperature of the toner is, for example, tangential from an endothermic curve when the temperature is raised to 20 to 150 ° C. at 10 ° C./min using a differential scanning calorimeter (“DSC-60”; manufactured by Shimadzu Corporation). It can be determined by law.

  The toner of the present invention exhibits a low-temperature fixing effect due to the sharp melt property inherent to the crystalline polyester, in addition to the low-temperature fixing effect due to the above-mentioned compatible portion. It is preferable to have dispersed. Due to the presence of the crystalline polyester dispersion, a portion having a high melting point exists on the particle surface, and it becomes easy to ensure blocking resistance even when the glass transition temperature of the toner is low. The presence or absence of crystallinity of the crystalline polyester in the toner can be determined by confirming the presence of a peak derived from the crystalline polyester from the diffraction pattern of the toner by a powder X-ray diffractometer. The diffraction pattern can be confirmed as in the case of crystalline polyester.

The toner of the present invention contains a salicylic acid metal complex containing a divalent or higher valent transition metal as a charge control agent, whereby a toner having better chargeability than a conventional charge control agent can be obtained. Further, by containing a salicylic acid metal complex having a trivalent or higher transition metal capable of taking a 6-coordinate structure, not only the charging ability of the salicylic acid metal complex is increased, but the complex can react with a resin or a release agent. By reacting with highly functional parts to form a light cross-linked structure, the melt viscosity at the time of kneading is increased, and the effect of improving the chargeability by improving the dispersibility of the release agent and other constituent materials is also obtained.
Examples of the transition metal having a valence of 2 or more include Zn, Fe, Cr, Zr and the like, and Fe, Cr, and Zr which are transition metals having a valence of 3 or more that can take a hexacoordinate configuration are particularly preferable. These may be used alone or in combination of two or more.
It is most preferable that the charge control agent contains only the above-mentioned ones. However, when two or more kinds are used in combination, other known ones may be appropriately selected. For example, salicylic acid metal complex having a metal other than the above, nigrosine dye, triphenylmethane dye, molybdate chelate pigment, rhodamine dye, alkoxy amine, quaternary ammonium salt (including fluorine-modified quaternary ammonium salt), Examples thereof include alkylamide, phosphorus alone or a compound thereof, tungsten alone or a compound thereof, and a fluorine-based activator. These are preferably less than 30% by mass of the charge control agent.

  The content of the charge control agent in the toner varies depending on the type of the binder resin, the presence / absence of an additive, a dispersion method, and the like, and cannot be generally specified. On the other hand, 0.1-10 mass parts is preferable, and 1-5 mass parts is more preferable. When the content is less than 0.1 parts by mass, the charging characteristics of the toner may be deteriorated. When the content exceeds 10 parts by mass, the chargeability of the toner becomes too high, and the electrostatic charge between the developing roller and the developing roller may be increased. The attractive suction force may increase, leading to a decrease in developer fluidity and a decrease in image density.

Examples of the release agent of the present invention include low molecular weight polyolefin waxes, synthetic hydrocarbon waxes, natural waxes, petroleum waxes, higher fatty acids and their metal salts, higher fatty acid amides, and various modified waxes thereof. These may be used individually by 1 type and may use 2 or more types together.
Examples of the low molecular weight polyolefin wax include low molecular weight polyethylene wax and low molecular weight polypropylene wax.
Examples of the synthetic hydrocarbon wax include ester wax and Fischer-Tropsch wax.
Examples of the natural waxes include beeswax, carnauba wax, candelilla wax, rice wax, and montan wax.
Examples of the petroleum waxes include paraffin wax and microcrystalline wax.
Examples of the higher fatty acid include stearic acid, palmitic acid, myristic acid, and the like.
There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, 65-110 degreeC is preferable and 70-90 degreeC is especially preferable.
If the melting point is less than 65 ° C., the release agent may adversely affect blocking resistance. If the melting point exceeds 110 ° C., it may easily cause a cold offset when fixing at a low temperature. Such as paper wrapping may occur.
There is no restriction | limiting in particular as content in the said toner of the said mold release agent, Although it can select suitably according to the objective, 1-20 mass% is preferable and 3-10 mass% is more preferable. When the content exceeds 20% by mass, the fluidity of the toner is deteriorated, and problems such as contamination of other members may be observed.

  There is no restriction | limiting in particular as another component, According to the objective, it can select suitably, For example, a coloring agent, an inorganic fine particle, a resin fine particle, a fluidity improver, a cleaning property improver, a magnetic material etc. are mentioned.

There is no restriction | limiting in particular as said coloring agent, According to the objective, it can select suitably from well-known dyes and pigments. As the black colorant, for example, carbon black, aniline black, furnace black, lamp black and the like can be used. Examples of cyan colorants include phthalocyanine blue, methylene blue, Victoria blue, methyl violet, aniline blue, and ultramarine blue. As the magenta colorant, for example, rhodamine 6G lake, dimethylquinacridone, watching red, rose bengal, rhodamine B, alizarin lake and the like can be used. Examples of yellow colorants include chrome yellow, benzidine yellow, hansa yellow, naphthol yellow, molybdenum orange, quinoline yellow, and tartrazine. These may be used individually by 1 type and may use 2 or more types together. The content of the colorant in the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 to 15% by mass, and more preferably 3 to 10% by mass. When the content is less than 1% by mass, a reduction in the coloring power of the toner is observed, and when the content exceeds 15% by mass, a poor dispersion of the pigment in the toner occurs. The characteristics may be degraded.
The colorant may be used as a master batch combined with a resin. There is no restriction | limiting in particular as this resin, According to the objective, it can select suitably from well-known things. The masterbatch can be produced by mixing or kneading the masterbatch resin and the colorant under high shear. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the colorant and the resin. The so-called flushing method is also preferable in that the wet cake of the colorant can be used as it is, and it does not need to be dried. This flushing method is a method of mixing or kneading an aqueous paste containing water of a colorant together with a resin and an organic solvent, and transferring the colorant to the resin side to remove moisture and organic solvent components. For the mixing or kneading, for example, a high shear dispersion device such as a three-roll mill is preferably used.
The coloration of the toner of the present invention is not particularly limited and can be appropriately selected according to the purpose, and can be at least one selected from black toner, cyan toner, magenta toner and yellow toner. This toner can be obtained by appropriately selecting the type of the colorant.

The inorganic fine particles are not particularly limited and may be appropriately selected from known ones according to the purpose. For example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, titanate Strontium, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, carbonized Examples thereof include silicon and silicon nitride. These may be used individually by 1 type and may use 2 or more types together.
The content of the inorganic fine particles in the toner is preferably 0.01 to 5.0% by mass, and more preferably 0.01 to 2.0% by mass. The inorganic fine particles can be suitably used as an external additive for the toner.

  The resin fine particles are not particularly limited and can be appropriately selected from known resins according to the purpose, and may be a thermoplastic resin or a thermosetting resin, such as a vinyl resin, Examples thereof include polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, and polycarbonate resin. These may be used individually by 1 type and may use 2 or more types together.

  The fluidity improver means a material that can be surface treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, a silane coupling agent, a silylating agent, Examples thereof include a silane coupling agent having a fluorinated alkyl group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, and modified silicone oil.

  The cleaning improver is added to the toner in order to remove the developer after transfer remaining on the photoreceptor or the primary transfer medium, and includes, for example, fatty acid metal salts such as zinc stearate, calcium stearate, stearic acid, and the like. Examples thereof include polymer fine particles produced by soap-free emulsion polymerization such as methyl methacrylate fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and those having a volume average particle size of 0.01 to 1 μm are suitable.

Magnetic materials include iron oxides such as magnetite, hematite, and ferrite, metals such as iron, cobalt, and nickel, or aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, Examples thereof include alloys of metals such as calcium, manganese, selenium, titanium, tungsten, vanadium, and mixtures thereof.
These magnetic materials preferably have an average particle size of about 0.1 to 2 μm, and the amount of toner contained in the toner is about 20 to 200 parts by weight, particularly preferably 100 parts by weight of the resin component, relative to 100 parts by weight of the resin component. On the other hand, it is 40 to 150 parts by mass.

  The method for producing the toner of the present invention is not particularly limited and may be appropriately selected from known methods according to the purpose. For example, a pulverization method in which the material forming the toner is melt-kneaded and then pulverized and classified. And polymerization methods.

The toner of the present invention is not particularly limited in terms of various physical properties such as shape and size, and can be appropriately selected according to the purpose, but has the following thermal characteristics, mass average particle diameter, and the like. It is preferable.
The thermal characteristics are also called flow tester characteristics, and are evaluated as, for example, a softening temperature (Ts), an outflow start temperature (Tfb), a _1/2 method softening point (F _1/2 ), and the like. These thermal characteristics can be measured by an appropriately selected method. For example, the thermal characteristics can be obtained from a flow curve measured using an elevated flow tester CFT500 type (manufactured by Shimadzu Corporation). Although there is no particular limitation on these temperatures, the following ranges are preferable because the blocking resistance, low-temperature fixability, hot offset resistance and the like may deteriorate. As said softening temperature (Ts), 30 degreeC or more is preferable, for example, and 50-120 degreeC is more preferable. As said outflow start temperature (Tfb), 50 degreeC or more is preferable, for example, and 60-150 degreeC is more preferable. The 1/2 method softening point (F _1/2 ) is, for example, preferably 60 ° C. or more, and more preferably 80 to 170 ° C. Note that the _1/2 method softening point (F _1/2 ) is, as described above, when the elevated flow tester CFT500 type (manufactured by Shimadzu Corporation) is used, the die diameter is 1 mm, the pressure is 10 kgf / cm ² , This is the temperature at which the stroke when the sample of 1 cm ² is melted and flowed out under the condition of the temperature rate of 3 ° C./min becomes 1/2 of the stroke change amount from the outflow start point to the outflow end point.

The mass average particle diameter (D4) of the toner is preferably 3 to 8 μm and particularly preferably 3 to 6.5 μm in order to reproduce minute dots of 600 dpi or more. In this range, since the toner particles have a sufficiently small particle size with respect to the minute latent image dots, the dot reproducibility is excellent. When the mass average particle diameter (D4) is less than 3 μm, phenomena such as a decrease in transfer efficiency and a decrease in blade cleaning properties tend to occur. When the mass average particle diameter (D4) exceeds 8 μm, it is difficult to suppress scattering of characters and lines.
The ratio (D4 / D1) of the mass average particle diameter (D4) to the number average particle diameter (D1) is preferably in the range of 1.00 to 1.40. The closer (D4 / D1) is to 1.00, the sharper the particle size distribution. With such a toner having a small particle size and a narrow particle size distribution, the toner charge amount distribution is uniform, a high-quality image with little background fogging can be obtained, and the electrostatic transfer method has a high transfer rate. can do.

Examples of the measuring device for the particle size distribution of the toner particles include Coulter Counter TA-II and Coulter Multisizer II (both manufactured by Coulter). The measurement method is described below. First, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of an aqueous electrolytic solution. Here, the electrolytic solution is a solution prepared by preparing a 1% NaCl aqueous solution using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the measurement device is used to measure the mass and number of toner particles or toner using a 100 μm aperture as an aperture. Calculate mass distribution and number distribution. From the obtained distribution, the mass average particle diameter (D4) and the number average particle diameter (D1) of the toner can be obtained.
As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 .35 to less than 8.00 μm; 8.00 to less than 10.08 μm; 10.08 to less than 12.70 μm; 12.70 to less than 16.00 μm; 16.00 to less than 20.20 μm; Uses 13 channels of less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm, and targets particles having a particle size of 2.00 μm to less than 40.30 μm.

The developer of the present invention contains at least the toner of the present invention, and other components such as a carrier selected as appropriate. The developer may be a one-component developer or a two-component developer. However, when it is used for a high-speed printer or the like corresponding to the recent improvement in information processing speed, the life is improved. In view of the above, the two-component developer is preferable.
There is no restriction | limiting in particular as said carrier, Although it can select suitably according to the objective, What has a core material and the resin layer which coat | covers this core material is preferable. There is no restriction | limiting in particular as a material of the said core material, It can select suitably from well-known things, For example, 50-90 emu / g manganese-strontium (Mn-Sr) type material, manganese-magnesium (Mn-) Mg) -based materials and the like are preferable, and highly magnetized materials such as iron powder (100 emu / g or more) and magnetite (75 to 120 emu / g) are preferable in terms of securing image density. Further, a weakly magnetized material such as a copper-zinc (Cu—Zn) -based (30 to 80 emu / g) is advantageous in that it can weaken the contact with the photoconductor in which the toner is in a spiked state and is advantageous in improving the image quality. Is preferred. These may be used alone or in combination of two or more. The core material has a volume average particle diameter of preferably 10 to 150 μm, more preferably 40 to 100 μm. When the average particle diameter (volume average particle diameter (D ₅₀ )) is less than 10 μm, the distribution of carrier particles may increase the number of fine powders, lower the magnetization per particle, and cause carrier scattering. If the thickness exceeds 150 μm, the specific surface area may decrease and toner scattering may occur. In the case of a full color having a large solid portion, the reproduction of the solid portion may be deteriorated. The material of the resin layer is not particularly limited and can be appropriately selected from known resins according to the purpose. For example, amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, Polyester resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, vinylidene fluoride And a copolymer of vinyl fluoride, a fluoroterpolymer such as a terpolymer of tetrafluoroethylene, vinylidene fluoride, and a non-fluorinated monomer, and a silicone resin. These may be used individually by 1 type and may use 2 or more types together. The resin layer may contain conductive powder or the like as necessary. Examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. The average particle diameter of these conductive powders is preferably 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control electric resistance. For example, the resin layer is prepared by dissolving the silicone resin or the like in a solvent to prepare a coating solution, and then uniformly coating the coating solution on the surface of the core material by a known coating method, drying, and baking. It can be formed by doing. Examples of the application method include an immersion method, a spray method, and a brush coating method. The amount of the resin layer in the carrier is preferably 0.01 to 5.0% by mass. When the amount is less than 0.01% by mass, the uniform resin layer may not be formed on the surface of the core material. When the amount exceeds 5.0% by mass, the resin layer becomes thick. In some cases, granulation of carriers occurs, and uniform carrier particles may not be obtained.
When the developer is the two-component developer, the content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 90 to 98% by mass Is preferable, and 93-97 mass% is more preferable.
Since the developer of the present invention contains the toner of the present invention, the chargeability during image formation and the fixability can be balanced and a high-quality image can be stably formed.
The developer of the present invention can be suitably 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. It can be particularly suitably used for containers, process cartridges, and image forming methods.

(Toner container)
The toner-containing container of the present invention contains the toner or the developer of the present invention in a container.
There is no restriction | limiting in particular as said container, It can select suitably from well-known things, For example, what has a container main body and a cap containing a toner etc. are mentioned suitably.
The size, shape, structure, material and the like of the container body containing toner are not particularly limited and can be appropriately selected according to the purpose. For example, the shape is preferably cylindrical. A spiral irregularity is formed on the peripheral surface, and the toner as the contents can be transferred to the discharge port side by rotating, and part or all of the spiral part has a bellows function, etc. Is particularly preferred.
The material of the toner-containing container body is not particularly limited, and those having good dimensional accuracy are preferable. For example, a resin is preferable, and among them, for example, polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, Preferable examples include vinyl chloride resin, polyacrylic acid, polycarbonate resin, ABS resin, and polyacetal resin.
The toner-containing container of the present invention is easy to store and transport, has excellent handleability, and is preferably used for replenishing toner by being detachably attached to the process cartridge and image forming apparatus of the present invention described later. Can do.

(Process cartridge)
The process cartridge of the present invention develops an electrostatic latent image carrier carrying an electrostatic latent image and the electrostatic latent image carried on the electrostatic latent image carrier using the developer of the present invention. And at least developing means for forming a visible image, and further having other means appropriately selected as necessary.
The developing means includes a developer container that contains the toner or developer of the present invention, and a developer carrier that carries and transports the toner or developer contained in the developer container. And a layer thickness regulating member for regulating the thickness of the toner layer to be carried.
The process cartridge of the present invention can be detachably provided in various electrophotographic apparatuses, and is preferably detachably provided in the electrophotographic apparatus of the present invention described later.
FIG. 1 is a schematic view for explaining a process cartridge of the present invention.
In FIG. 1, in an image forming apparatus having a process cartridge 450 of the present invention, a photoconductor 451 is rotationally driven at a predetermined peripheral speed. In the rotating process, the photosensitive member 451 is uniformly charged with a predetermined positive or negative potential on its peripheral surface by the charging means 452, and then image exposure such as slit exposure or laser beam scanning exposure (not shown). In this way, an electrostatic latent image is sequentially formed on the peripheral surface of the photosensitive member in response to image exposure light from the means, and the formed electrostatic latent image is then toner developed by the developing means 453, and the developed toner image is developed. The transfer material, which is sequentially transferred by the transfer means to the transfer material fed in synchronization with the rotation of the photoconductor between the photoconductor and the transfer means from a paper supply unit (not shown) and has undergone image transfer, The image is separated from the surface of the photosensitive member, introduced into an image fixing means, where the image is fixed, and printed out as a copy (copy). The surface of the photoconductor after the image transfer is cleaned by removing the transfer residual toner by the cleaning means 454, and after being further neutralized, it is repeatedly used for image formation.

(Image forming method)
In the image forming method of the present invention, an electrostatic latent image formed on an image carrier is developed with a developer, a toner image formed on the image carrier is transferred to an image support, and the transferred toner image is transferred. And fixing the image to obtain a fixed image. Hereinafter, an image forming apparatus suitable for carrying out the image forming method of the present invention will be described.

  The image forming apparatus includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing unit, and other units appropriately selected as necessary. For example, it comprises a static elimination means, a cleaning means, a recycling means, a control means and the like.

-Electrostatic latent image forming step and electrostatic latent image forming means-
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier.
There are no particular restrictions on the material, shape, structure, size, etc. of the electrostatic latent image carrier (sometimes referred to as “photoconductive insulator” or “photoconductor”), and among the known ones The shape is preferably a drum shape, and examples of the material include inorganic photoconductors such as amorphous silicon and selenium, and organic photoconductors such as polysilane and phthalopolymethine. It is done. Among these, amorphous silicon or the like is preferable in terms of long life.

As the photosensitive member having amorphous silicon, a conductive support is heated to 50 ° C. to 400 ° C., and a vacuum deposition method, a sputtering method, an ion plating method, a thermal CVD method, a photo CVD method, a plasma is formed on the support. An amorphous silicon photoconductor (hereinafter referred to as “a-Si photoconductor”) having a photoconductive layer made of amorphous silicon can be used by a film forming method such as a CVD method. Among them, a plasma CVD method, that is, a method in which a source gas is decomposed by direct current, high frequency or microwave glow discharge to form an a-Si deposited film on a support is preferably used.
The layer structure of the amorphous silicon photoconductor is, for example, as follows. FIG. 2 is a schematic configuration diagram for explaining a layer configuration. A photoconductor 500 shown in FIG. 2A is provided with a photoconductive layer 502 made of a-Si: H and having photoconductivity on a support 501. A photoreceptor 500 shown in FIG. 2B includes a photoconductive layer 502 made of a-Si: H and having photoconductivity, and an amorphous silicon-based surface layer 503 on a support 501. A photoconductor 500 shown in FIG. 2C has a photoconductive layer 502 made of a-Si: H and having photoconductivity, an amorphous silicon based surface layer 503, and an amorphous silicon based charge injection on a support 501. And a blocking layer 504. In the photoconductor 500 shown in FIG. 2D, a photoconductive layer 502 is provided on a support 501. The photoconductive layer 502 includes a charge generation layer 505 and a charge transport layer 506 made of a-Si: H, and an amorphous silicon-based surface layer 503 is provided thereon.
The support for the photoreceptor may be conductive or electrically insulating. Examples of the conductive support include metals such as Al, Cr, Mo, Au, In, Nb, Te, V, Ti, Pt, Pd, and Fe, and alloys thereof such as stainless steel. Also, at least the surface on the side where the photosensitive layer is to be formed of an electrically insulating support such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polystyrene, polyamide or other synthetic resin film or sheet, glass or ceramic. A conductively treated support can also be used.
The shape of the support can be a cylindrical or plate-like or endless belt with a smooth or uneven surface, and the thickness thereof is appropriately determined so that a desired photoreceptor for an image forming apparatus can be formed. When flexibility as a photoreceptor for an image forming apparatus is required, it can be made as thin as possible within a range where the function as a support can be sufficiently exhibited. However, the support is usually 10 μm or more from the viewpoints of manufacturing and handling, such as mechanical strength.
The amorphous silicon photosensitive member that can be used in the present invention has a charge injection blocking function that functions to prevent charge injection from the conductive support side between the conductive support 511 and the photoconductive layer 502 as necessary. It is more effective to provide the layer 504 (FIG. 2C). That is, the charge injection blocking layer 504 has a function of blocking charge injection from the support 501 side to the photoconductive layer 502 side when the photoconductive layer 502 is subjected to a charging process with a certain polarity on its free surface. However, it has a so-called polarity dependency in which such a function is not exhibited when it is charged with the opposite polarity. In order to provide such a function, the charge injection blocking layer 504 contains a relatively large number of atoms for controlling conductivity as compared with the photoconductive layer 502.
The thickness of the charge injection blocking layer 504 is preferably 0.1 to 5 [mu] m, more preferably 0.3 to 4 [mu] m, and most preferably 0.5 in view of obtaining desired electrophotographic characteristics and economic effects. It is desirable that the thickness be ˜3 μm.
The photoconductive layer 502 is formed on the undercoat layer as necessary, and the layer thickness of the photoconductive layer 502 is appropriately determined as desired from the viewpoints of obtaining desired electrophotographic characteristics and economic effects. Is preferably 1 to 100 μm, more preferably 20 to 50 μm, and most preferably 23 to 45 μm.
The charge transport layer 506 is a layer mainly having a function of transporting charges when the photoconductive layer 502 is functionally separated. The charge transport layer 506 includes at least silicon atoms, carbon atoms, and fluorine atoms as constituent elements, and is formed of a-SiC (H, F, O) including hydrogen atoms and oxygen atoms as required. Photoconductive properties, particularly charge retention properties, charge generation properties, and charge transport properties. In the present invention, it is particularly preferable to contain an oxygen atom.
The layer thickness of the charge transport layer 506 is appropriately determined as desired from the viewpoint of obtaining desired electrophotographic characteristics and economic effects. The charge transport layer 506 is preferably 5 to 50 μm, more preferably 10 to 10 μm. It is desirable that the thickness is 40 μm, optimally 20 to 30 μm.
The charge generation layer 505 is a layer mainly having a function of generating charges when the photoconductive layer 502 is functionally separated. This charge generation layer 505 is composed of a-Si: H containing at least silicon atoms as components and substantially not containing carbon atoms, and if necessary containing hydrogen atoms, and has desired photoconductive properties, particularly charge generation. Characteristics and charge transport characteristics.
The layer thickness of the charge generation layer is appropriately determined as desired from the viewpoint of obtaining desired electrophotographic characteristics and economic effects, etc., preferably 0.5 to 15 μm, more preferably 1 to 10 μm, optimally 1 ˜5 μm.
If necessary, the amorphous silicon photoconductor that can be used in the present invention can be further provided with an amorphous silicon-based surface layer 503 on the photoconductive layer 502 formed on the support as described above. It is preferable to form an amorphous silicon-based surface layer. This surface layer has a free surface, and is provided to achieve the object of the present invention mainly in moisture resistance, continuous repeated use characteristics, electrical pressure resistance, use environment characteristics, and durability.
The thickness of the surface layer 503 in the present invention is usually 0.01 to 3 μm, preferably 0.05 to 2 μm, and most preferably 0.1 to 1 μm. If the layer thickness is less than 0.01 μm, the surface layer is lost due to wear or the like during use of the photoreceptor, and if it exceeds 3 μm, electrophotographic characteristics such as an increase in residual potential are observed.
The amorphous silicon photoconductor as described above has a high surface hardness, a high sensitivity to long wavelength light such as a semiconductor laser (770 to 800 nm) and the like, and is hardly deteriorated by repeated use. And an electrophotographic photoreceptor such as a laser beam printer (LBP).

The formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then performing imagewise exposure, and is performed by the electrostatic latent image forming unit. be able to. The electrostatic latent image forming means includes, for example, at least a charger that uniformly charges the surface of the electrostatic latent image carrier and an exposure device that exposes the surface of the electrostatic latent image carrier imagewise. Prepare.
The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charger. The charger is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charging device including a conductive or semiconductive roll, brush, film, rubber blade, etc. And non-contact chargers using corona discharge such as corotrons and corotrons.
The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure device. The exposure device is not particularly limited as long as it can expose the surface of the electrostatic latent image carrier charged by the charger so as to form an image to be formed, and is appropriately selected according to the purpose. For example, various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system can be used. In the present invention, a back light system in which imagewise exposure is performed from the back side of the electrostatic latent image carrier may be employed.

-Development process and development means-
The developing step is a step of developing the electrostatic latent image using the toner or the developer of the present invention to form a visible image. The visible image can be formed, for example, by developing the electrostatic latent image using the toner or the developer of the present invention, and can be performed by the developing unit. The developing unit is not particularly limited as long as it can be developed using, for example, the toner or the developer of the present invention, and can be appropriately selected from known ones. For example, the toner of the present invention Preferably, a developer containing at least a developer and having at least a developing unit capable of contacting or non-contacting the toner or the developer to the electrostatic latent image is provided, and includes the toner-containing container of the present invention. More preferred is a developing device.
The developing unit may be a dry developing type, a wet developing type, a single color developing unit, or a multi-color developing unit. For example, a toner having a stirrer for charging the toner or the developer by frictional stirring and a rotatable magnet roller is preferable.
In the developing device, for example, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier (photoconductor), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted. It moves to the surface of the electrostatic latent image carrier (photoconductor) by force. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier (photoconductor).
The developer accommodated in the developing device is a developer containing the toner of the present invention, but the developer may be a one-component developer or a two-component developer. The toner contained in the developer is the toner of the present invention.

Note that it is preferable to apply an alternating electric field during the development step.
FIG. 3 is a diagram for explaining means for applying an alternating electric field during the development process. In the developing device 600 shown in FIG. 3, during development, an oscillating bias voltage in which an AC voltage is superimposed on a DC voltage is applied to the developing sleeve 601 as a developing bias by the power source 602. The background portion potential and the image portion potential are located between the maximum value and the minimum value of the vibration bias potential. As a result, an alternating electric field whose direction changes alternately is formed in the developing unit 603. In this alternating electric field, the developer toner and the carrier vibrate vigorously, and the toner flies off the photosensitive drum 604 by shaking off the electrostatic binding force to the developing sleeve 601 and the carrier. And adhere.
The difference (maximum peak voltage) between the maximum value and the minimum value of the vibration bias voltage is preferably 0.5 to 5 kV, and the frequency is preferably 1 to 10 kHz. As the waveform of the vibration bias voltage, a rectangular wave, a sine wave, a triangular wave, or the like can be used. As described above, the DC voltage component of the vibration bias is a value between the background part potential and the image part potential, but the value closer to the background part potential than the image part potential is more likely to cover the background part potential region. This is preferable for preventing toner adhesion.
When the vibration bias voltage waveform is a rectangular wave, the duty ratio is preferably 50% or less. Here, the duty ratio is a ratio of time during which the toner is directed to the photoconductor in one cycle of the vibration bias. By doing so, the difference between the peak value at which the toner is directed to the photoreceptor and the time average value of the bias can be increased, so that the movement of the toner is further activated and the potential of the latent image surface is increased. It can adhere to the distribution and improve the roughness and resolution. In addition, since the difference between the peak value of the carrier having a charge opposite to that of the toner and the time average value of the bias toward the photosensitive member can be reduced, the movement of the carrier is reduced, and the background portion of the latent image is reduced. The probability of carriers adhering to the substrate can be greatly reduced.

-Transfer process and transfer means-
The transfer step is a step of transferring the visible image onto a recording medium. After the primary transfer of the visible image onto the intermediate transfer member using an intermediate transfer member, the visible image is transferred onto the recording medium. A primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer body using two or more colors, preferably full color toner as the toner, and a composite transfer image; A mode including a secondary transfer step of transferring the transfer image onto the recording medium is more preferable.
The transfer can be performed, for example, by charging the electrostatic latent image carrier (photoconductor) with a transfer charger using the visible image, and can be performed by the transfer unit. The transfer means includes a primary transfer means for transferring a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. Embodiments are preferred. The intermediate transfer member is not particularly limited and may be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.
The transfer means (the primary transfer means and the secondary transfer means) is a transfer for peeling and charging the visible image formed on the electrostatic latent image carrier (photoconductor) to the recording medium side. It is preferable to have at least a vessel. There may be one transfer means or two or more transfer means. Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device. The recording medium is not particularly limited and can be appropriately selected from known recording media (recording paper).

-Fixing process and fixing means-
The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing device, and may be performed each time the toner of each color is transferred to the recording medium, or for the toner of each color. You may perform this simultaneously in the state which laminated | stacked this. There is no restriction | limiting in particular as said fixing device, Although it can select suitably according to the objective, A well-known heating-pressing means is suitable. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt. The heating in the heating and pressing means is usually preferably 80 ° C to 200 ° C.
In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing step and the fixing unit depending on the purpose.

-Static elimination process and static elimination means-
The neutralization step is a step of performing neutralization by applying a neutralization bias to the electrostatic latent image carrier, and can be suitably performed by a neutralization unit. The neutralization means is not particularly limited, and may be appropriately selected from known neutralizers as long as it can apply a neutralization bias to the electrostatic latent image carrier. Preferably mentioned.

-Cleaning process and cleaning means-
The cleaning step is a step of removing the toner remaining on the electrostatic latent image carrier, and can be suitably performed by a cleaning unit. The cleaning unit is not particularly limited, and may be selected from known cleaners as long as it can remove the toner remaining on the electrostatic latent image carrier. For example, a magnetic brush cleaner Suitable examples include electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, web cleaners, and the like.
In the present invention, a cleaning device for performing cleaning includes two blades of a first cleaning blade and a second cleaning blade in order from the upstream side in the image carrier rotation direction, and the second cleaning blade includes a blade base layer. And a polishing blade having a two-layer structure of an abrasive particle-containing layer.

-Recycling process and recycling means-
The recycling step is a step of recycling the toner removed by the cleaning step to the developing unit, and can be suitably performed by the recycling unit.
There is no restriction | limiting in particular as said recycling means, A well-known conveyance means etc. are mentioned.

-Control process and control means-
The control means is a process for controlling the respective steps, and can be suitably performed by the control means.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

Examples of the present invention and comparative examples will be described below, but the present invention is not limited to the following examples. In the examples, “parts” are based on mass.
Resins 1 to 9 were prepared as materials for forming the toner of the present invention. It shows to Tables 1-2 about the composition and physical property of this resin 1-9.
In Tables 1 and 2, the presence of the powder X-ray diffraction peak was measured by an X-ray diffraction apparatus (“PINT-1100”; manufactured by Rigaku Electric Co., Ltd.), and the presence or absence of the peak was evaluated based on the following criteria.
〔Evaluation criteria〕
Yes: There is a peak at least at 2θ = 20-25 ° No: No peak at 2θ = 20-25 °

Example 1
Toner base material resin 1 55 parts resin 5 45 parts ester wax (melting point 85 ° C.) 4 parts iron salicylate 2 parts carbon black 10 parts

The toner forming material having the above composition was charged into a Henschel mixer “MF20C / I type” (manufactured by Mitsui Miike Processing Co., Ltd.), sufficiently stirred and mixed, then kneaded with a twin-screw extruder manufactured by Toshiba Machine Co., Ltd. and cooled. Next, the mass average particle diameter (D4) is 5.8 ± 0.5 μm, and the ratio (D4 / D1) of the mass average particle diameter to the number average particle diameter (D1) is 1.2 to 1.3. Crushing and classification were performed to prepare a toner base. Here, the kneading was performed such that the temperature of the kneaded product at the exit of the twin-screw extruder was about 120 ° C.
To the toner base thus obtained, 1.0% by mass of hydrophobic silica and 0.5% by mass of acid value titanium were added and mixed to prepare a toner of Example 1.

--- Development of developer--
Next, 5 parts by mass of the obtained toner and 95 parts by mass of a silicone-coated ferrite carrier having an average particle size of 45 μm coated with a silicone resin were stirred with a tumbler mixer to prepare a developer having an appropriate charge amount.

Table 5 shows the evaluation results of the toner and developer of Example 1. The resulting toner has low-temperature fixing higher than before and has no problem in hot offset resistance and blocking resistance. The image quality was also satisfactory.
The toner and developer were evaluated as follows.

Blocking resistance Approximately 20 g of toner was placed in a 20 ml glass bottle and tapped 50 times to harden the toner tightly. Subsequently, after putting it in a 50 degreeC thermostat and leaving it to stand for 24 hours, the penetration (%) was measured by the penetration test (JIS K2235-1991). The blocking resistance was evaluated based on the following criteria from the penetration (%) with respect to the toner after being solidified.
〔Evaluation criteria〕
5: 90-100%
4: 75-90%
3: 60-75%
2: 30-60%
1: 30% or less Here, if the evaluation criteria is 3 to 5, it is recognized that there is no problem in blocking resistance.

Fixing characteristics The Ricoh copier IMAGEIO NEO350 was modified so that the set temperature and linear velocity of the fixing device could be changed. The toner, developer, and Ricoh type 6200 paper shown in the examples were set in this, and a copy test was conducted.
The cold offset generation temperature and the hot offset generation temperature were measured while changing the fixing temperature, and the low temperature fixability (cold offset generation temperature) and the hot offset resistance (hot offset generation temperature) were evaluated based on the following criteria. The linear speed of paper feed was set to 180 mm / sec for evaluation of low-temperature fixability, and set to 50 mm / sec, which is a severe condition for hot offset generation, for evaluation of hot offset resistance.
Cold offset generation temperature (Rank 2 is the level of conventional low-temperature fixing toner)
5 ... below 120 ° C, 4 ... 120-130 ° C, 3 ... 130-140 ° C, 2 ... 140-150 ° C, 1 ... 150 ° C or higher Hot offset occurrence temperature (other than ranks 1 and 2 has offset resistance) )
5 ... 210 ° C or higher, 4 ... 200-210 ° C, 3 ... 190-200 ° C, 2 ... 180-190 ° C, 1 ... less than 180 ° C

Image density A solid image was formed on transfer paper (“Type 6200”; manufactured by Ricoh Co., Ltd.) using a Ricoh copier IMAGEIO NEO350. For the obtained image, arbitrary 6 positions were selected, and the image density at the position was measured using a spectrometer (938 Spectrodensitometer, manufactured by X-Light Corporation). Based on this, the image density was evaluated.
〔Evaluation criteria〕
5: 1.5 or more 4: 1.45-1.5
3: 1.40-1.45
2: 1.35 to 1.40
Less than 1: 1.35 Here, it is recognized that if the evaluation criterion is 3 to 5, an excellent image density can be obtained.

Background stains A RICOH copier IMAGEIO NEO350 was used, "Type 6200" (manufactured by Ricoh Co., Ltd.) was used as the transfer paper, and a solid white image was output after outputting 20,000 images. For the obtained image, arbitrary six positions are selected, and the image density at the position is measured with a spectrometer (938 Spectrodensitometer, manufactured by X-Light Co.). The background dirt was evaluated.
〔Evaluation criteria〕
5: Same as paper reflection density 4: Paper reflection density + less than 0.02 3: Paper reflection density + 0.02 to 0.04
2: Reflection density of paper +0.04 to 0.06
1: Reflection density of paper +0.06 or more Here, in a state where there is no background stain, the reflection density of the image shows a value equivalent to the reflection density of paper, and the higher the reflection density, the worse the background stain. It is recognized that

Toner scattering After outputting 20,000 images on transfer paper ("Type 6200"; manufactured by Ricoh Co., Ltd.) using a copier ("IMAGE AG NEO350"; manufactured by Ricoh Co., Ltd.), contamination due to toner scattering inside the copier The state of was evaluated based on the following evaluation criteria.
〔Evaluation criteria〕
5: Very good 4: Good 3: Normal 2: Bad 1: Very bad Here, if the evaluation criteria are 3 to 5, the toner scattering is required to be at a level that does not cause a problem.

Fine line reproducibility Using a copier (“IMAGIO NEO350”; manufactured by Ricoh Co., Ltd.), the transfer paper (“Type 6200”; manufactured by Ricoh Co., Ltd.) is 600 dots / inch and 150 line / inch in both the main scanning and sub-scanning directions. A 1-dot grid line image was output, and the cut and blur of the line image were visually evaluated in 5 stages. 5 ... very good, 4 ... good, 3 ... normal, 2 ... bad, 1 ... very bad

  In Table 5, the high temperature and high humidity environment means a temperature of 30 ° C. and a humidity of 90% RH.

Comparative Example 1
Using the same material as in Example 1 except that the resin 5 in Example 1 was changed to the resin 6, the same processing as in Example 1 was performed to obtain a toner and a developer.
This toner and developer were evaluated in the same manner as in Example 1. The results are shown in Table 5. Even when the same amount of the same crystalline polyester was contained, a low-temperature fixing toner more than the conventional one could not be obtained. Further, the poor dispersibility of the toner constituent material appeared in the image.

Example 2
Toner component resin 1 30 parts Resin 7 70 parts Polyethylene wax (melting point 95 ° C.) 4 parts Iron salicylate 1.5 parts Carbon black 10 parts

Using the toner constituent material, the same processing as in Example 1 was performed to obtain a toner and a developer.
This toner and developer were evaluated in the same manner as in Example 1. The results are shown in Table 5. The glass transition temperature of the amorphous polyester was lowered, so that the crystalline polyester content was lower than that in Example 1, but a low-temperature fixing toner was obtained. It also improved hot offset resistance and image quality.

Reference example 3
Toner constituent material Resin 2 20 parts Resin 6 20 parts Resin 7 60 parts Carnauba wax (melting point 83 ° C) 4 parts Zirconium salicylate 1 part Carbon black 10 parts

Using the toner constituent material, the same processing as in Example 1 was performed to obtain a toner and a developer.
This toner and developer were evaluated in the same manner as in Example 1. The results are shown in Table 5. The use of crystalline polyester having a melting point lower than that of Example 2 and a wax having a lower melting point improved the low-temperature fixability.

Example 4
A toner and a developer were obtained by performing the same processing as in Example 3 except that the resin 2 of Example 3 was changed from 20 parts to 15 parts and the resin 7 was changed from 60 parts to 85 parts without using the resin 6. .
This toner and developer were evaluated in the same manner as in Example 1. The results are shown in Table 5. By making all the alcohol components of the amorphous polyester into aliphatic diols, the same low-temperature fixability was obtained even when the crystalline polyester content was lower than in Example 3. Also, the dispersibility of the wax was good and the image quality was improved.

Example 5
Using the same toner constituent material as in Example 4, the same processing as in Example 4 was carried out except for pulverization and classification, to obtain a toner and a developer. In the pulverization and classification, the mass average particle diameter (D4) is 5.8 ± 0.5 μm, and the ratio (D4 / D1) of the mass average particle diameter to the number average particle diameter (D1) is 1.45 to 1.55. It was done as follows.
The toner and developer were evaluated in the same manner as in Example 1. The results are shown in Table 5. When D4 / D1 is large and the particle size distribution is wide, it is easy for toner to scatter due to the output of a large number of images. Therefore, it was confirmed that D4 / D1 is preferably in the range as in Example 4.

Comparative Example 2
A toner and a developer were obtained in the same manner as in Example 4 except that 1 part of zirconium salicylate in Example 4 was changed to 1 part of aluminum salicylate, using the same materials as in Example 4.
This toner and developer were evaluated in the same manner as in Example 1. The results are shown in Table 5. The image quality decreased under normal temperature and humidity, and the deterioration of image quality under high temperature and high humidity was more remarkable.

Reference Example 6
Resin 3 15 parts Resin 8 40 parts Resin 9 45 parts Ester wax (melting point 85 ° C) 5 parts Zinc salicylate 1 part Disazo yellow pigment 7 parts

Using the toner constituent material, the same processing as in Example 1 was performed to obtain a yellow toner and a developer.
Of the toner constituent materials, 7 parts of disazo yellow pigment was changed to 4 parts of copper phthalocyanine blue pigment, and the same treatment as in Example 1 was performed to obtain a cyan toner and a developer.
Of the toner constituent materials, 7 parts of disazo yellow pigment was changed to 5 parts of naphthol-based magenta pigment, and the same treatment as in Example 1 was performed to obtain a magenta toner and a developer.
Of these toners and developers, cyan toner and cyan developer were evaluated. The results are shown in Table 5. For evaluation of image density, background stain, toner scattering, and fine line reproducibility, the evaluation apparatus was changed from imagio Neo 350 to imagio Color 4000. Otherwise, the same evaluation as in Example 1 was performed.
Even full-color toners had no problems with low-temperature fixability, hot offset resistance, and blocking resistance. Although the melt viscosity is lower than that of the monochromatic toner and the dispersibility of the constituent materials tends to be inferior, there was no problem in image quality.
Next, the yellow, magenta, and cyan toners and developer, and Ricoh type 7000 70W paper were set in an imagio Color 4000 to obtain a two-color superimposed image of blue, green, and red. These arbitrary solid portions were measured with a spectrometer (X-Light, 938 Spectrodensitometer). As shown in Table 3, a toner having good color reproducibility was obtained.

Example 7
Of the toner constituent materials of Example 6, the same process as in Example 6 was performed except that resin 8 was changed from 40 parts to 85 parts without using resin 9, and 1 part of zinc salicylate was changed to 1 part of zirconium salicylate. Then, yellow, magenta and cyan toners and developers were obtained.
About these, evaluation similar to Example 6 was performed. Table 4 shows the color measurement results, and Table 5 shows the other evaluation results. By using a resin containing no THF-insoluble matter, a toner having good color reproducibility was obtained.

Comparative Example 3
Except that 1 part of zirconium salicylate in Example 7 was changed to 1 part of calcium salicylate, the same material as in Example 7 was used and the same processing as in Example 7 was performed to obtain a toner and a developer.
This toner and developer were evaluated in the same manner as in Example 1. The results are shown in Table 5. The image quality was worse than that in Example 7. In particular, the deterioration under high temperature and high humidity was remarkable.

Example 8
Resin 4 3 parts Resin 9 97 parts Carnauba wax (melting point 83 ° C) 4 parts Iron salicylate 1 part Carbon black 10 parts

Using the toner constituent material, the same processing as in Example 1 was performed to obtain a toner and a developer.
This toner and developer were evaluated in the same manner as in Example 1. The results are shown in Table 5. Since crystalline polyester and amorphous polyester have similar structures, low-temperature fixability was obtained although the content of crystalline polyester was small. On the other hand, when the melting point of the crystalline polyester is too low, the storage stability tends to be deteriorated. Therefore, it was confirmed that the melting point of the crystalline polyester is preferably not lower.

  According to the present invention, it has low-temperature fixability, secures hot offset resistance and blocking resistance, has excellent charging ability, does not cause poor dispersion of the release agent, and outputs a large number of sheets or at high temperature and high temperature. Provided are a toner that does not deteriorate developability even under humidity, a developer using the toner, a toner-containing container, a process cartridge, and an image forming method.

It is the schematic for demonstrating the process cartridge of this invention. It is a typical block diagram for demonstrating the layer structure of the amorphous silicon photoreceptor used for this invention. It is a figure for demonstrating the application means of the alternating electric field at the time of a image development process.

Explanation of symbols

450 Process cartridge 451 Photoconductor 452 Charging means 453 Development means 500 Support body 502 Photoconductive layer 503 Amorphous silicon surface layer 504 Charge injection blocking layer 505 Charge generation layer 506 Charge transport layer 600 Developer 601 Development sleeve 602 Power supply 603 Development section 604 Photosensitive drum

Claims (15)

A toner containing at least a crystalline polyester and an amorphous polyester as a binder resin, a charge control agent, and a release agent, wherein the alcohol component is an aliphatic diol as a main component (however, the aromatic An alcohol component containing a resin having an aliphatic dicarboxylic acid as a main component, and the amorphous polyester having an alcohol component having an aliphatic diol as a main component (but not including an aromatic alcohol). A toner, wherein the acid component contains a resin mainly composed of an aromatic dicarboxylic acid, and an iron or zirconium complex of salicylic acid as the charge control agent.   The toner according to claim 1, wherein the toner has a glass transition temperature of 35 to 55 ° C.   The toner according to claim 1, wherein the content of the crystalline polyester is 40% by mass or less of the total amount of the binder resin.   The toner according to claim 1, wherein the crystalline polyester has a melting point of 80 to 130 ° C.   The toner according to claim 1, wherein the amorphous polyester has a glass transition temperature of 40 to 70 ° C.   The toner according to claim 1, wherein the releasing agent has a melting point of 70 to 90 ° C.   The mass average particle diameter is 3 to 6.5 μm, and the ratio (D4 / D1) of the mass average particle diameter (D4) to the number average particle diameter (D1) is in the range of 1.00 to 1.40. The toner according to claim 1, wherein the toner is a toner.   The toner according to claim 1, wherein the toner is a full-color toner.   The toner according to claim 8, wherein the amorphous polyester has a tetrahydrofuran (THF) insoluble content of 0 to 5% by mass.   A developer comprising the toner according to claim 1.   A toner-containing container containing the toner according to claim 1.   An electrostatic latent image carrier and at least developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier using the developer according to claim 10 to form a visible image. A process cartridge which is detachable from the image forming apparatus main body.   The electrostatic latent image formed on the image carrier is developed with a developer, the toner image formed on the image carrier is transferred to an image support, and the transferred toner image is fixed to obtain a fixed image. An image forming method comprising a step, wherein the developer is the developer according to claim 10.   14. The image forming method according to claim 13, wherein the image carrier is an amorphous silicon photoconductor.   The image forming method according to claim 13, wherein an alternating electric field is applied when the electrostatic latent image formed on the image carrier is developed with a developer.

Images