JP5652125B2 - Toner, image forming apparatus using the same, image forming method, and process cartridge - Google Patents

Description

  The present invention relates to a toner used for forming an electrophotographic image such as a copying machine, electrostatic printing, printer, facsimile, electrostatic recording, and the like, and an image forming apparatus, an image forming method, and a process cartridge using the toner.

In recent years, market demands for energy saving and high speed are increasing for image forming apparatuses such as printers, copiers, and facsimiles. In order to achieve such performance, it is important to improve the thermal efficiency of the fixing unit in the image forming apparatus.
In general, in an image forming apparatus, an unfixed toner image is formed on a recording sheet, printing paper, photosensitive paper, electrostatic recording by an indirect transfer method or a direct transfer method by an image forming process such as electrophotographic recording, electrostatic recording, or magnetic recording. It is formed on a recording medium such as paper. As fixing means for fixing such an unfixed toner image, for example, a contact heating method such as a heat roller method, a film heating method, and an electromagnetic induction heating method is widely adopted.

In general, an electrophotographic image forming method generally uses a developer to develop an electrostatic image formed on a photoreceptor prepared using a photoconductive substance using various means. In this method, the developed image is transferred to paper or the like as necessary, and fixed by heating, pressing, solvent vapor, or the like.
Methods for developing electrostatic images can be broadly divided into liquid development methods that use liquid developers in which various pigments and dyes are dispersed in an insulating organic liquid, cascade methods, magnetic brush methods, powder cloud methods, etc. As described above, there is a dry development method using a dry developer (hereinafter referred to as toner) in which a colorant such as carbon black is dispersed in a natural or synthetic resin, and the dry development method has been widely used in recent years.

  On the other hand, a method for producing a toner used for developing an electrostatic charge image is roughly classified into a pulverization method and a polymerization method. In the pulverization method, a colorant, a charge control agent, an offset preventive agent and the like are melt-mixed in a thermoplastic resin and uniformly dispersed, and the resulting composition is pulverized and classified to produce a toner. When the pulverization method is used, a toner having some excellent characteristics can be produced, but the toner material is limited. For example, the composition obtained by melt mixing must be capable of being pulverized and classified using equipment that can be used economically. For this reason, the composition obtained by melt mixing must be made sufficiently brittle. Further, when the obtained composition is pulverized, the particle size distribution tends to be widened. At this time, in order to obtain a copy image having good resolution and gradation, for example, it is necessary to reduce the weight average particle diameter of the toner, and classify fine powder having a particle diameter of 4 μm or less and coarse powder having a particle diameter of 15 μm or more. If it is removed by this, there is a problem that the yield of toner decreases. Further, in the pulverization method, it is difficult to uniformly disperse the colorant, the charge control agent and the like in the thermoplastic resin. This adversely affects toner fluidity, developability, durability, image quality, and the like.

  In order to overcome these problems in the pulverization method, a toner production method by a polymerization method is known. For example, a suspension polymerization method or an emulsion polymerization aggregation method (for example, see Patent Document 1) is used. Toner is manufactured. Patent Document 2 discloses a toner obtained by spheronizing a toner composed of a polyester-based resin using an organic solvent in water, and Patent Document 3 discloses a toner obtained by reacting an isocyanate group prepolymer with amines. Is disclosed.

  Also, in the process of fixing toner to a paper medium, heat fixing is currently the mainstream because of its high efficiency. In the case of heat fixing, oil is applied to the fixing surface in order to suppress the adhesion between the fixing roller and the toner, but in recent years, toner containing a release agent is mainly used in the toner. And in order to disperse | distribute a mold release agent moderately in the toner obtained by the said polymerization method, use of a mold release agent dispersing agent is proposed (for example, refer patent document 4, 5, 6).

  However, the composition of the release agent dispersant described in these documents is a resin obtained by grafting a vinyl resin to polyolefin, but the performance as a dispersant is not high, so that a large amount of addition is necessary. Further, it has been pointed out that the toner quality is adversely affected due to the large molecular weight of the polyolefin part or due to the influence of the existence of the polyolefin part itself.

  In Patent Documents 7 and 8, in a pulverized toner using a styrene resin as a toner binder, a polyolefin release agent such as low molecular weight polyethylene or low molecular weight polypropylene, or a styrene resin is grafted to the polyolefin resin. It is described that the resin is effective. However, since the styrenic resins used in Patent Documents 7 and 8 are inferior in low-temperature fixability, there is a problem for low-temperature fixing that satisfies the recent demand for energy saving.

  The present invention has been made to solve the above-described problems, and is an image capable of obtaining a good image over a long period of time by uniformly dispersing a release agent with an appropriate dispersion diameter while maintaining good toner quality. An object of the present invention is to provide an image forming apparatus, an image forming method, and a process cartridge capable of forming an extremely high quality image while providing a toner for forming.

  As a result of intensive studies, the inventors of the present invention contain at least a binder resin, a release agent, and a colorant, and the binder resin is selected from a polyester resin, an acrylate ester, and a methacrylate ester. The present invention described below was obtained by finding that a toner characterized by containing at least a vinyl polymer containing at least one kind or two or more kinds as monomer units can obtain a good image over a long period of time. .

(1) Containing at least a binder resin, a release agent, and a colorant, and the binder resin is a monomer of one or more selected from polyester resins, acrylic esters, and methacrylic esters. A monomer comprising at least a vinyl polymer as a unit, wherein at least a part of the acrylic ester and methacrylic ester of the vinyl polymer is obtained by condensing a polyester oligomer having a terminal hydroxyl group with acrylic acid and methacrylic acid. A toner characterized by being a unit.

(2) The toner according to (1), wherein the vinyl polymer has a weight average molecular weight of 3,000 to 30,000.
(3) The toner according to (1) or (2), wherein the vinyl polymer has an SP value (solubility parameter) of 10.0 to 13.0.
(4) The toner according to any one of (1) to (3), wherein the glass transition temperature Tg of the polyester resin is 30 ° C. or higher and 70 ° C. or lower.
(5) The above (1) to (1), wherein the mass ratio [(B) / (A)] of the polyester resin (A) and the vinyl polymer (B) is from 1/99 to 20/80. The toner according to any one of 4).
(6) The toner according to any one of (1) to (5), wherein the addition amount of the vinyl polymer is 5 to 100 parts by mass with respect to 100 parts by mass of the release agent.
(7) Any of (1) to (6) above, wherein a mass ratio of the release agent to the binder resin [(release agent / binder resin) × 100] is 0.1 to 20% by mass. The toner described in 1.

(8) The toner according to any one of (1) to (7), wherein the toner is formed in a liquid medium.
(9) The toner according to (8), wherein the toner particles formed in the liquid medium are obtained by suspending a polymer solution in an aqueous medium.
(10) The toner particles formed in the liquid medium dissolve or dissolve a polymer, a binder resin, a colorant, and a release agent having a site capable of reacting with a compound having an active hydrogen group in at least an organic solvent. Dispersing, dispersing the oil phase consisting of the solution or dispersion in an aqueous medium containing resin fine particles, and reacting or reacting the polymer having a site capable of reacting with the compound having active hydrogen groups, The toner according to (9), which is obtained by removing the organic solvent.
(11) The toner according to any one of (8) to (10), wherein the toner particles formed in the liquid medium are obtained by aggregating resin fine particles in the liquid medium.

(12) The toner according to any one of (8) to (11) above, wherein the toner particles have a weight average particle diameter of 3 to 15 μm.
(13) The ratio (Dv / Dn) between the weight average particle diameter (Dv) and the number average particle diameter (Dn) of the toner particles is 1.25 or less. The toner according to any one of the above.

(14) A developer comprising the toner according to any one of (1) to (13).

(15) A toner-containing container filled with the toner according to any one of (1) to (13).

(16) An electrostatic latent image carrier, charging means for charging the surface of the electrostatic latent image carrier, and exposure means for exposing the charged electrostatic latent image carrier surface to form an electrostatic latent image Developing means for developing the electrostatic latent image with toner to form a visible image; transfer means for transferring the visible image to a recording medium; and fixing the transferred image transferred to the recording medium. An image forming apparatus having at least a fixing unit, wherein the toner is the toner according to any one of (1) to (13).
(17) The above developing means has a magnetic field generating means fixed inside, and has a developer carrier that can rotate by carrying a two-component developer comprising a magnetic carrier and a toner on the surface. The image forming apparatus according to (16).
(18) The image forming apparatus according to (16), wherein the developing unit includes a developer carrier to which toner is supplied and a layer thickness regulating member that forms a thin layer of toner on the surface of the developer carrier.
(19) The fixing unit (16) is a fixing unit that includes at least one of a roller and a belt, and heats and presses a transfer image transferred onto a recording medium by heating from a surface not in contact with the toner. )-(18).
(20) The fixing unit according to (16), wherein the fixing unit includes at least one of a roller and a belt, and is heated from a surface in contact with the toner to fix the transfer image transferred onto the recording medium by heating and pressing. -The image forming apparatus in any one of (18).
(21) A heating roller in which the fixing unit is made of a magnetic metal and heated by electromagnetic induction on a recording medium on which an unfixed image is formed, a fixing roller arranged in parallel with the heating roller, and the heating roller And an endless belt-like toner heating medium which is stretched between the fixing roller and heated by the heating roller and rotated by these rollers, and is pressed against the fixing roller via the toner heating medium, and In a fixing unit having a pressure roller that rotates in the forward direction with respect to the toner heating medium to form a fixing nip portion, the unfixed image is heated and fixed by passing between the toner heating medium and the pressure roller. The image forming apparatus according to any one of (16) to (18).

(22) a charging step for charging the surface of the electrostatic latent image carrier, an exposure step for exposing the charged electrostatic latent image carrier surface to form an electrostatic latent image, and the electrostatic latent image with toner. An image forming method comprising at least a developing step for developing a visible image by using the developing method, a transferring step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium An image forming method, wherein the toner is the toner according to any one of (1) to (13).

(23) At least an electrostatic latent image carrier and development means for developing the electrostatic latent image formed on the electrostatic latent image carrier using toner to form a visible image, and forming an image A process cartridge which is detachable from an apparatus main body, wherein the toner is the toner according to any one of (1) to (13).

  According to the present invention, it is possible to provide an image forming toner capable of obtaining a good image over a long period of time by uniformly dispersing a release agent with an appropriate dispersion diameter while maintaining good toner quality.

The developer of the present invention contains the toner of the present invention. Therefore, the toner of the present invention can be used as a two-component developer toner used by mixing with a magnetic carrier, or as a one-component developer toner not using a magnetic carrier. When an image is formed by electrophotography using this developer, a good image can be obtained over a long period of time.
The toner-containing container of the present invention contains the toner of the present invention in a container. Therefore, when an image is formed by electrophotography using the toner contained in the toner container, a good image can be obtained over a long period of time.

  In the image forming apparatus of the present invention, the charging unit uniformly charges the surface of the electrostatic latent image carrier. The exposure means exposes the surface of the electrostatic latent image carrier to form an electrostatic latent image. The developing means develops the electrostatic latent image formed on the electrostatic latent image carrier with toner to form a visible image. The transfer means transfers the visible image to a recording medium. The fixing unit fixes the transferred image transferred to the recording medium. At this time, since the toner of the present invention is used as the toner, it is possible to form an extremely high-quality image with no change in color tone over a long period of time and no abnormal images such as density reduction and background stains. .

  In the image forming method of the present invention, the surface of the electrostatic latent image carrier is uniformly charged in the charging step. In the exposure step, the surface of the electrostatic latent image carrier is exposed to form an electrostatic latent image. In the developing step, the electrostatic latent image formed on the electrostatic latent image carrier is developed with toner to form a visible image. In the transfer step, the visible image is transferred to a recording medium. In the fixing step, the transferred image transferred to the recording medium is fixed. At this time, since the toner of the present invention is used as the toner, it is possible to form an extremely high-quality image with no change in color tone over a long period of time and no abnormal images such as density reduction and background stains. .

  The process cartridge of the present invention has at least an electrostatic latent image carrier and developing means for developing a latent image formed on the electrostatic latent image carrier using toner to form a visible image. In addition, it is detachable from the main body of the image forming apparatus, is excellent in convenience, and uses the toner of the present invention. An extremely high-quality image that cannot be obtained can be formed.

FIG. 3 is a schematic cross-sectional view illustrating an example of a charging roller in the image forming apparatus. 1 is a schematic diagram illustrating an example in which a contact-type charging roller in an image forming apparatus is applied to an image forming apparatus. 1 is a schematic diagram illustrating an example in which a non-contact type corona charger in an image forming apparatus is applied to an image forming apparatus. FIG. 3 is a schematic diagram illustrating an example of a non-contact charging roller in the image forming apparatus. FIG. 2 is a schematic diagram illustrating an example of a one-component developing unit in an image forming apparatus. FIG. 2 is a schematic diagram illustrating an example of a two-component developing unit in an image forming apparatus. 1 is a schematic diagram illustrating an example of a direct transfer method in a tandem type image forming apparatus of the present invention. 1 is a schematic diagram illustrating an example of an indirect transfer method in a tandem type image forming apparatus of the present invention. FIG. 3 is a schematic diagram illustrating an example of a belt-type fixing unit in the image forming apparatus of the present invention. FIG. 3 is a schematic diagram illustrating an example of a heat roller type fixing unit in the image forming apparatus of the present invention. FIG. 3 is a schematic diagram illustrating an example of an electromagnetic induction heating type fixing unit in the image forming apparatus of the present invention. FIG. 5 is a schematic diagram illustrating another example of an electromagnetic induction heating type fixing unit in the image forming apparatus of the present invention. FIG. 3 is a schematic diagram illustrating an example of a cleaning blade in the image forming apparatus of the present invention. 1 is a schematic diagram illustrating an example of a cleaningless type image forming apparatus in an image forming apparatus of the present invention. 1 is a schematic diagram illustrating an example of an image forming apparatus of the present invention. It is the schematic which shows another example of the image forming apparatus of this invention. 1 is a schematic diagram illustrating an example of a tandem type image forming apparatus of the present invention. FIG. 18 is an enlarged view of each image forming element in FIG. 17. FIG. 2 is a schematic diagram illustrating an example of a process cartridge for an image forming apparatus according to the present invention. It is the schematic which shows another example of the image forming apparatus of this invention. It is the schematic which shows another example of the image forming apparatus of this invention.

<Toner>
The toner of the present invention contains at least a binder resin, a release agent, and a colorant. External additives and other components as necessary (components that can be contained in toner particles: inorganic fine particles, resin fine particles) A charge control agent, an unmodified polyester resin, polymer polymer particles, a fluidity improver, a cleaning property improver, a magnetic material, and the like.

[Binder resin]
The binder resin contains at least a polyester resin and a vinyl polymer containing, as a monomer unit, one or more selected from acrylic acid ester and methacrylic acid ester, and acrylic acid of the vinyl polymer. At least a part of the ester or methacrylic acid ester is a monomer unit obtained by condensing a polyester oligomer having a hydroxyl group at the terminal to acrylic acid or methacrylic acid.

[Polyester resin]
The polyester resin imparts good low-temperature fixability to the toner, but more preferably contains an unmodified polyester resin (an unmodified polyester resin).

Examples of the monomer constituting the polyester resin (polyester polymer) include the following.
Examples of the divalent alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, or diol obtained by polymerizing cyclic ethers such as ethylene oxide and propylene oxide to bisphenol A, etc. Is mentioned.

  In order to crosslink the polyester resin, it is preferable to use a trihydric or higher alcohol together. Examples of the trihydric or higher polyhydric alcohol include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, such as dipentaerythritol, tripentaerythritol, 1,2,4- Butanetriol, 1,2,5-pentatriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxybenzene , Etc.

  Examples of the acid component forming the polyester-based resin include benzene dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrides thereof, and alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or the like. Unsaturated dibasic acids such as anhydride, maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride, etc. And unsaturated dibasic acid anhydrides. Examples of the trivalent or higher polyvalent carboxylic acid component include trimet acid, pyromet acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, tetra (methylene Carboxy) methane, 1,2,7,8-octanetetracarboxylic acid, empol trimer acid, or anhydrides thereof, partial lower alkyl esters, and the like.

  The condensation polymerization of the alcohol component and the carboxylic acid component is preferably performed in the presence of an esterification catalyst. Examples of the esterification catalyst include Lewis acids such as p-toluenesulfonic acid, titanium compounds, and tin (II) compounds having no Sn-C bond, and these are used alone or in combination. . Among these, a titanium compound and a tin (II) compound having no Sn—C bond are particularly preferable.

As the titanium compound, a titanium compound having a Ti—O bond is preferable, and a compound having an alkoxy group having 1 to 28 carbon atoms, an alkenyloxy group, or an acyloxy group is more preferable.
Examples of the titanium compound include titanium diisopropylate bistriethanolamate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₃ H ₇ O) ₂ ], titanium diisopropylate bisdiethanolamate [Ti (C ₄ H ₁₀ O ₂ N) ₂ (C ₃ H ₇ O) ₂ ], titanium dipentylate bistriethanolamate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₅ H ₁₁ O) ₂ ], titanium diethylate bis triethanolaminate _{[Ti (C 6 H 14 O 3} N) 2 (C 2 H 5 O) 2 ], titanium dihydroxy octylate bis triethanolaminate _{[Ti (C 6 H 14 O 3} N) 2 (OHC 8 H ₁₆ O) _2], titanium distearate bis triethanolaminate _{[Ti (C 6 H 14 O 3} N) 2 (C 18 H 37 O) 2 ], Chitanto Isopropylate triethanolaminate _{[Ti (C 6 H 14 O 3} N) 1 (C 3 H 7 O) 3 ], titanium monopropylate tris (triethanolaminate) _{[Ti (C 6 H 14 O 3} N) ₃ (C ₃ H ₇ O) ₁ ] and the like. Among these, titanium diisopropylate bistriethanolamate, titanium diisopropylate bisdiethanolamate, and titanium dipentylate bistriethanolamate are particularly preferred, and these are also available as, for example, commercially available products from Matsumoto Trading Co., Ltd. .

Other preferred titanium compounds include, for example, tetra-n-butyl titanate [Ti (C ₄ H ₉ O) ₄ ], tetrapropyl titanate [Ti (C ₃ H ₇ O) ₄ ], tetrastearyl titanate [Ti (C ₁₈ H ₃₇ O) ₄ ], tetramyristyl titanate [Ti (C ₁₄ H ₂₉ O) ₄ ], tetraoctyl titanate [Ti (C ₈ H ₁₇ O) ₄ ], dioctyl dihydroxyoctyl titanate [Ti (C ₈ H ₁₇ O) ₂ (OHC ₈ H ₁₆ O) ₂ ], dimyristyl dioctyl titanate [Ti (C ₁₄ H ₂₉ O) ₂ (C ₈ H ₁₇ O) ₂ ] and the like. Among these, tetrastearyl titanate, tetramyristyl titanate, tetraoctyl titanate, and dioctyl dihydroxy octyl titanate are preferable. These can be obtained by reacting, for example, titanium halide with a corresponding alcohol. It is also available as a product.
The abundance of the titanium compound is preferably 0.01 parts by mass to 1.0 part by mass, and 0.1 parts by mass to 0.7 parts by mass with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. Is more preferable.

  The acid value of the polyester-based resin is preferably 0.1 mgKOH / g to 100 mgKOH / g, more preferably 0.1 mgKOH / g to 70 mgKOH / g, and 0.1 mgKOH / g to 50 mgKOH / g. Most preferably it is.

  The polyester resin preferably has a glass transition temperature (Tg) of 30 ° C. or higher and 70 ° C. or lower. If it is out of this range, the fixing characteristics may be deteriorated and the heat resistant storage stability may be deteriorated.

[Unmodified polyester resin]
The unmodified polyester resin can be contained in the toner particles for the purpose of improving low-temperature fixability, glossiness, and the like. The unmodified polyester resin is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, the same as the urea bond-forming group-containing polyester resin, that is, polyol (PO) and poly And a polycondensate with carboxylic acid (PC). The unmodified polyester resin is partially compatible with the urea bond-forming group-containing polyester resin (RMPE), that is, has a similar structure compatible with each other. It is preferable in terms of hot offset.

  There is no restriction | limiting in particular as a mass mean molecular weight of the said unmodified polyester resin, According to the objective, it can select suitably, For example, it is 1000-30000 by the measured value by GPC (gel permeation chromatography), 1500-500 10,000 is more preferable, and 2000-8000 is particularly preferable. When the mass average molecular weight is less than 1000, the heat resistant storage stability may be deteriorated, and when it exceeds 30000, the low temperature fixability may be deteriorated.

The hydroxyl value of the unmodified polyester resin is preferably 5 or more, more preferably 10 to 120, and still more preferably 20 to 80. When the hydroxyl value is less than 5, 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 to 40, and more preferably 4 to 30. Generally, it becomes easy to be negatively charged by giving the toner an acid value.

  When the unmodified polyester resin is contained in the toner, the mixing mass ratio between the urea bond-forming group-containing polyester resin and the unmodified polyester resin is preferably 5/95 to 50/50. When the mixing mass ratio of the unmodified polyester resin is more than 95, the hot offset resistance is deteriorated, and it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability. Deterioration may be seen.

[Vinyl polymer]
The vinyl polymer is preferably an acrylic ester or a methacrylic ester. By using an acrylic ester or a methacrylic ester, a repulsive force can be given between the release agent particles. Acrylic acid esters and methacrylic acid esters are compatible with the polyester resin and show a good fixed image. As for the ester groups of acrylic acid ester and methacrylic acid ester, at least a part of the acrylic acid ester and methacrylic acid ester of the vinyl polymer has a hydroxyl group at the terminal in acrylic acid and methacrylic acid as described in claim 2. A monomer unit obtained by condensing a polyester oligomer is preferable. For example, when an acrylic ester or methacrylic ester vinyl resin containing only methyl ester is used, the repulsive force between the release agent particles is insufficient and aggregation occurs.

The vinyl polymer preferably has a weight average molecular weight of 3,000 to 30,000. When the weight average molecular weight is 3000 or less, the adsorption to the release agent is insufficient, and when it is 30000 or more, the fixing characteristics of the toner are adversely affected.
The SP value of the vinyl polymer is preferably between 10.0 and 13.0. When the SP value is less than 10.0 or more than 13.0, the compatibility with the polyester resin is lowered.

  The addition amount of the vinyl polymer is preferably 5 parts by mass to 100 parts by mass with respect to 100 parts by mass of the release agent. When the amount is 5 parts by weight or less, the release agent is not sufficiently dispersed, and when the amount is 100 parts by weight or more, the fixing characteristics and charging characteristics are adversely affected.

(Mixing ratio of polyester resin and vinyl resin)
The mixing ratio of the polyester resin (A) and the vinyl resin (B) is a mass ratio [(B) / (A)], and 1/99 to 20/80 is appropriate. If it is out of this range, fixing characteristics and heat-resistant storage stability may be deteriorated.

  In addition, the binder resin is used in combination with a known binder resin, for example, a vinyl resin such as styrene-acrylic resin, an epoxy resin, a polycarbonate, a polyurethane, or the like, as long as the effects of the present invention are not impaired. However, the total content of the polyester resin (A) and the vinyl resin (B) is preferably 80% by mass or more in the binder resin.

〔Release agent〕
There is no restriction | limiting in particular as a mold release agent, According to the objective, it can select suitably from well-known things, For example, waxes etc. are mentioned suitably. Examples of the waxes include low molecular weight polyolefin waxes, synthetic hydrocarbon waxes, natural waxes, petroleum waxes, higher fatty acids and metal salts thereof, 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 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, 40-160 degreeC is preferable, 50-120 degreeC is more preferable, 60-90 degreeC is especially preferable. If the melting point is less than 40 ° C., the wax may adversely affect the heat-resistant storage stability. If the melting point exceeds 160 ° C., it may easily cause a cold offset when fixing at a low temperature. May occur.
Here, the melting point is the temperature of an endothermic peak at which the endothermic amount is maximized in a differential thermal curve obtained by differential scanning calorimetry (DSC).

  There is no restriction | limiting in particular as content in the toner particle (toner base particle) of the said mold release agent, Although it can select suitably according to the objective, 1-40 mass% is preferable and 3-30 mass% is more preferable. . When the content exceeds 40% by mass, the low-temperature fixability may be impaired or the image quality may be deteriorated (glossiness is too high).

As the particle diameter of the release agent particles in the release agent dispersion, the median diameter in the volume-based particle size distribution is preferably 0.2 μm or more and 3.0 μm or less, more preferably 0.2 μm or more and 1.0 μm or less. preferable. When the median diameter is 3.0 μm or more, the toner surface exposure amount of the release agent increases, so that the photosensitive member is contaminated, the fixability is deteriorated, the heat resistant storage stability is deteriorated, and the granulation behavior is not good when used for a chemical toner. May cause problems such as stability.
As the coarse particle ratio of the release agent particles in the release agent dispersion liquid, it is preferable that the cumulative frequency of the particle size of 5.0 μm or more in the volume-based particle size distribution is 5.0% or less. When the integration frequency is 5.0% or more, the toner surface exposure amount of the release agent increases, so that the photosensitive member is contaminated, the fixing property is deteriorated, the heat resistant storage stability is deteriorated, and the toner becomes coarse when used for a chemical toner. May cause problems.

[Colorant]
The colorant is not particularly limited and may 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, Isoindolinone Yellow, Bengala, Lead Red, Lead Red, Cadmium Red, Cadmium Mummer Curry Red, Antimony Zhu, Permanent Red 4R, Parare , Phi Sae Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake B, rhodamine lake Y, alizarin lake, thioindigo red B, thioindigo maroon, oil Quinacridone red, pyrazolone red, polyazo red, chrome vermilion, benzidine orange, 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, Chrome oxide, pyridian, emerald green, pigment green B, naphthol green B, green gold, acid Lean lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, ritbon, and the like. These may be used individually by 1 type and may use 2 or more types together.

There is no restriction | limiting in particular as a color of the said coloring agent, According to the objective, it can select suitably, For example, the thing for black, the thing for color, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.
Examples of the black material include carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, and channel black, copper, iron (CI pigment black 11), and titanium oxide. And organic pigments such as aniline black (CI Pigment Black 1).

  Examples of the magenta color pigment include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 48: 1, 49, 50, 51, 52, 53, 53: 1, 54, 55, 57, 57: 1, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 163, 177, 179, 202, 206, 207, 209, 211; C.I. I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, etc. are mentioned.

  Examples of the color pigment for cyan include C.I. I. Pigment Blue 2, 3, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 60; I. Bat Blue 6; C.I. I. Acid Blue 45, copper phthalocyanine pigments having 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton, green 7 and green 36, and the like.

  Examples of the color pigment for yellow include C.I. I. Pigment Yellow 0-16, 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 55, 65, 73, 74, 83, 97, 110, 151, 154, 180; C.I. I. Bat yellow 1, 3, 20, orange 36 and the like.

  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% by mass to 15% by mass, and more preferably 3% by mass to 10% by mass. When the content is less than 1% by mass, a reduction in the coloring power of the toner is observed. When the content exceeds 15% by mass, poor pigment dispersion in the toner occurs, the coloring power decreases, The characteristics may be degraded.

  The colorant used in the present invention can also be used as a master batch combined with a resin. As the binder resin to be kneaded with the master batch, the same resin as the binder resin can be used. Moreover, binder resin may be used individually by 1 type, and 2 or more types may be mixed and used for it.

The masterbatch can be obtained by mixing and kneading a resin for preparing a masterbatch and a colorant under high shear. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. Also, there is a method of removing the water and organic solvent components by mixing and kneading an aqueous paste containing water, which is a so-called flushing method, together with a resin and an organic solvent, and transferring the colorant to the resin side. Since the wet cake can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shearing dispersion device such as a three-roll mill is preferably used.
As the usage-amount of the said masterbatch, 0.1-20 mass parts is preferable with respect to 100 mass parts of binder resin.

  The resin for preparing the masterbatch preferably has an acid value of 30 mgKOH / g or less, an amine value of 1 to 100, and a colorant dispersed therein. The acid value is 20 mgKOH / g or less and the amine value is 10 to 50, and it is more preferable to use the colorant dispersed. When the acid value exceeds 30 mgKOH / g, the chargeability under high humidity may be lowered, and the pigment dispersibility may be insufficient. Further, when the amine value is less than 1 and when the amine value exceeds 100, the pigment dispersibility may be insufficient. The acid value can be measured by the method described in JIS K0070, and the amine value can be measured by the method described in JIS K7237.

  Further, a dispersant can be used in order to enhance the dispersibility of the pigment. The dispersant is preferably highly compatible with the binder resin in terms of pigment dispersibility. Specific examples of commercially available products include “Ajisper PB821”, “Azisper PB822” (manufactured by Ajinomoto Fine Techno Co., Ltd.), “ Disperbyk-2001 "(manufactured by Big Chemie)," EFKA-4010 "(manufactured by EFKA), and the like.

  The mass average molecular weight of the dispersant is the maximum molecular weight of the main peak in terms of styrene in gel permeation chromatography, and is preferably 500 to 100,000, and from the viewpoint of pigment dispersibility, 3,000 to 100 1,000 is more preferable. In particular, 5,000 to 50,000 are preferable, and 5,000 to 30,000 are most preferable. When the molecular weight is less than 500, the polarity increases and the dispersibility of the colorant may decrease. When the molecular weight exceeds 100,000, the affinity with the solvent increases and the dispersibility of the colorant decreases. There are things to do. The dispersant is preferably blended in the toner at a ratio of 0.1 to 10% by mass with respect to the colorant. When the blending ratio is less than 0.1% by mass, the pigment dispersibility may be insufficient, and when it is more than 10% by mass, the chargeability under high humidity may be deteriorated.

(Charge control agent)
The charge control agent is not particularly limited and may be appropriately selected from known ones according to the purpose. However, since a color tone may change when a colored material is used, a colorless or nearly white material is preferable. For example, nigrosine dye, triphenylmethane dye, chromium-containing metal complex dye, molybdate chelate pigment, rhodamine dye, alkoxy amine, quaternary ammonium salt (including fluorine-modified quaternary ammonium salt), alkylamide, Examples thereof include phosphorus alone or a compound thereof, tungsten alone or a compound thereof, a fluorine-based activator, a metal salt of salicylic acid, and a metal salt of a salicylic acid derivative. Among these, salicylic acid metal salts and metal salts of salicylic acid derivatives are preferred. There is no restriction | limiting in particular as said metal, According to the objective, it can select suitably, For example, aluminum, zinc, titanium, strontium, boron, silicon, nickel, iron, chromium, zirconium etc. are mentioned.
These may be used individually by 1 type and may use 2 or more types together.

  Commercially available products may be used as the charge control agent. Examples of the commercially available products include quaternary ammonium salt Bontron P-51, oxynaphthoic acid metal complex E-82, and salicylic acid metal complex. E-84, E-89 of a phenol-based condensate (above, manufactured by Orient Chemical Industries), TP-302, TP-415 of a quaternary ammonium salt molybdenum complex (above, manufactured by Hodogaya Chemical Co., Ltd.), Fourth Copy charge PSY VP2038 of quaternary ammonium salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR which is a boron complex -147 (manufactured by Nippon Carlit), quinacridone, azo pigment, other sulfonic acid groups, carbo Sill group, polymer compounds having a functional group such as quaternary ammonium salts, and the like.

The charge control agent may be melted and kneaded with the master batch and then dissolved or dispersed, or may be added when directly dissolving or dispersing in the organic solvent together with the components of the toner particles. Alternatively, the toner particles may be fixed on the surface after the toner particles are manufactured.
The content of the charge control agent in the toner particles varies depending on the type of the binder resin, the presence / absence of an additive, a dispersion method, and the like, and cannot be specified in general. 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 particles becomes too large, and the effect of the main charge control agent And the electrostatic attraction force with the developing roller increases, leading to a decrease in developer fluidity and a decrease in image density.

[Inorganic fine particles]
The inorganic fine particles are not particularly limited and can be appropriately selected from known materials according to the purpose. For example, 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, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, And silicon nitride. These may be used alone or in combination of two or more.

The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and more preferably 5 nm to 500 nm. Moreover, as a specific surface area by BET method of the said inorganic fine particle, 20-500 m < ² > / g is preferable. 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.

[Resin fine particles]
The resin fine 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. It may be a thermosetting resin, for example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate resin, Etc.
These may be used alone or in combination of two or more. Among these, at least one selected from vinyl resins, polyurethane resins, epoxy resins, and polyester resins is preferable because an aqueous dispersion of fine spherical resin resin particles can be easily obtained.

  The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer. For example, a styrene- (meth) acrylic ester resin, a styrene-butadiene copolymer, or a (meth) acrylic acid-acrylic ester polymer. Styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- (meth) acrylic acid copolymer, and the like.

  Moreover, as the resin fine particles, a copolymer comprising a monomer having at least two unsaturated groups can be used. The monomer having at least two unsaturated groups is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a sodium salt of ethylene oxide methacrylate adduct sulfate (“Eleminol RS-30”). "; Manufactured by Sanyo Chemical Industries Ltd.), divinylbenzene, 1,6-hexanediol acrylate, and the like.

  The volume average particle diameter of the resin fine particles is preferably 20 to 400 nm, and more preferably 30 to 350 nm. If the volume average particle size is less than 20 nm, the resin fine particles remaining on the surface of the toner particles may be filmed or the entire surface of the toner particles may be covered densely. As a result, the resin The fine particles may interfere with the adhesion between the binder resin inside the toner particles and the fixing paper as a transfer material, and the fixing minimum temperature may increase. Occurrence of bleeding may be hindered, sufficient release properties may not be obtained, and offset may occur.

The resin particle coverage of the resin fine particles is preferably 75 to 100%, more preferably 80 to 100%. When the toner particle coverage is less than 75%, the storage stability of the toner particles is deteriorated, and blocking may occur during storage or use.
The content of the resin fine particles in the toner particles is preferably 0.5 to 8.0% by mass, and more preferably 0.6 to 7.0% by mass. When the content is less than 0.5% by mass, the storability of the toner deteriorates, and blocking may be observed during storage or use. When the content exceeds 8.0% by mass, The resin fine particles hinder the seepage of the wax, so that sufficient releasability cannot be obtained and offset may occur.

(Polymer polymer particles)
The polymer particles are not particularly limited and may be appropriately selected from known ones according to the purpose. For example, polystyrene, methacrylic acid obtained by soap-free emulsion polymerization, suspension polymerization, dispersion polymerization, etc. Examples thereof include particles formed of acid ester, acrylate copolymer, silicone resin, polycondensation resin such as benzoguanamine, nylon, thermosetting resin, and the like.

[Flowability improver]
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 fluoroalkyl group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, and modified silicone oil.

[Cleaning improver]
The cleaning property improver is added to the toner in order to remove the developer after transfer remaining on the electrostatic latent image carrier or the intermediate transfer member. For example, fatty acid such as zinc stearate, calcium stearate, stearic acid, etc. Examples thereof include polymer fine particles produced by soap-free emulsion polymerization such as metal salts, polymethyl methacrylate fine particles, and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and those having a weight average particle size of 0.01 to 1 μm are suitable.

[Magnetic material]
There is no restriction | limiting in particular as said magnetic material, According to the objective, it can select suitably from well-known things, For example, iron powder, a magnetite, a ferrite etc. are mentioned. Among these, white is preferable in terms of color tone.

(External additive)
In order to improve the fluidity, storage stability, developability, transferability and durability of the toner, inorganic fine particles such as oxide fine particles and hydrophobic silica fine powder, and polymer resins as external additives to the toner base particles Fine particles may be added and mixed. This effect can be obtained by covering the wax that lowers transferability and durability with these external additives and reducing the contact area due to the toner surface being covered with fine particles. The surface of these inorganic fine particles is preferably subjected to a hydrophobic treatment, and metal oxide fine particles such as silica and titanium oxide subjected to the hydrophobic treatment are preferably used. Toner with improved toner transfer rate and good filming resistance by increasing the external addition amount of hydrophobized titanium oxide compared to the external addition amount of hydrophobized silica to improve charging stability against humidity It can be.

  The primary particle diameter of the inorganic fine particles or the resin fine particles is preferably 5 nm to 2 μm. Although the proportion of the inorganic fine particles used depends on the type, it is used in the range of 0.01 to 5% by mass with respect to the toner particles. Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, Examples thereof include diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. These can be used singly or in combination of two or more. The polymer resin fine particles include, for example, polycondensation systems such as polystyrene, methacrylic acid ester, acrylic acid ester copolymer, silicone, benzoguanamine, nylon obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization. And polymer particles made of a thermosetting resin.

  Typical examples of the hydrophobizing agent include the following. Dimethyldichlorosilane, trimethylchlorosilane, methyltrichlorosilane, allyldimethyldichlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, p-chloroethyltrichlorosilane, Chloromethyldimethylchlorosilane, chloromethyltrichlorosilane, p-chlorophenyltrichlorosilane, 3-chloropropyltrichlorosilane, 3-chloropropyltrimethoxysilane, vinyltriethoxysilane, vinylmethoxysilane, vinyl-tris (β-methoxyethoxy) ) Silane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, divinyldichlorosilane, dimethylvinylchlorosilane, octyl Trichlorosilane, decyl-trichlorosilane, nonyl-trichlorosilane, (4-t-propylphenyl) -trichlorosilane, (4-t-butylphenyl) -trichlorosilane, dipentyl-dichlorosilane, dihexyl-dichlorosilane, dioctyl-dichlorosilane, dinonyl -Dichlorosilane, didecyl-dichlorosilane, didodecyl-dichlorosilane, dihexadecyl-dichlorosilane, (4-t-butylphenyl) -octyl-dichlorosilane, dioctyl-dichlorosilane, didecenyl-dichlorosilane, dinonenyl-dichlorosilane, di-2-ethylhexyl-dichlorosilane, di- 3,3-dimethylpentyl-dichlorosilane, trihexyl-chlorosilane, trioctyl-chlorosilane, tridecyl-chlorosilane Dioctyl-methyl-chlorosilane, octyl-dimethyl-chlorosilane, (4-t-propylphenyl) -diethyl-chlorosilane, octyltrimethoxysilane, hexamethyldisilazane, hexaethyldisilazane, diethyltetramethyldisilazane, hexaphenyldisilazane , Hexatolyl disilazane and the like. In addition, titanate coupling agents and aluminum coupling agents can also be used.

  For mixing the external additives described above, a general powder mixer is used, but it is preferable to equip a jacket or the like to adjust the internal temperature. For example, a V-type mixer, a rocking mixer, a Laedige mixer, a Nauter mixer, a Henschel mixer and the like are preferably used.

  The above-mentioned inorganic fine particles and resin fine particles are contained (internally added) in the toner, but the effect is reduced as compared with the case of external addition, but the effect of improving transferability and durability can be obtained and the pulverization property of the toner can be improved. Can do. In addition, since external addition and internal addition can be used together to suppress embedding of externally added fine particles, excellent transferability can be stably obtained and durability can be improved.

[Physical properties of toner particles]
The toner particles in the present invention are not particularly limited in shape, size, etc., and can be appropriately selected according to the purpose. However, the following thermal characteristics, image density, average circularity, volume average It is preferable to have a particle size, a ratio of volume average particle size to number average particle size (volume average particle size / number average particle size), and the like.

(Thermal characteristics)
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 (T1 / 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).
There is no restriction | limiting in particular as said softening temperature (Ts), According to the objective, it can select suitably, For example, 50 degreeC or more is preferable and 80-120 degreeC is more preferable. When the softening temperature (Ts) is less than 50 ° C., at least one of heat resistant storage stability and low temperature storage stability may deteriorate.
There is no restriction | limiting in particular as said outflow start temperature (Tfb), According to the objective, it can select suitably, For example, 60 degreeC or more is preferable and 70-150 degreeC is more preferable. If the outflow start temperature (Tfb) is less than 60 ° C., at least one of heat resistant storage stability and low temperature storage stability may deteriorate.
The 1/2 method softening point (T1 / 2) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 60 ° C. or higher is preferable, and 80 to 170 ° C. is more preferable. When the 1/2 method softening point (T1 / 2) is less than 60 ° C., at least one of heat-resistant storage property and low-temperature storage property may deteriorate.

(Image density)
The image density is preferably 1.90 or more, more preferably 2.00 or more, and particularly preferably 2.10 or more, as measured by a spectrometer (X-Light, 938 Spectrodensitometer). preferable.
If the image density is less than 1.90, the image density may be low and high image quality may not be obtained.
The image density is, for example, a solid image having an adhesion amount of developer of 1.00 ± 0.05 mg / cm ^{2 on} copy paper (TYPE6000 <70W>; manufactured by Ricoh) using imagio Neo450 (manufactured by Ricoh). The surface temperature of the fixing roller was formed at 160 ± 2 ° C., and the image density at any six locations in the obtained solid image was measured using a spectrometer (X-Light Corp., 938 Spectrodensitometer). It can be measured by calculating the average value.

(Average circularity)
The average circularity is a value obtained by dividing the perimeter of an equivalent circle having the same projected shape as the toner shape by the perimeter of the actual particles, and is preferably 0.900 to 0.980, for example, 0.950 to 0 .975 is more preferred. In addition, it is preferable that the particles having an average circularity of less than 0.94 are 15% or less.
If the average circularity is less than 0.900, satisfactory transferability and a high-quality image free from dust may not be obtained. If the average circularity exceeds 0.980, image formation employing blade cleaning or the like is employed. In the system, defective cleaning occurs on the photoconductor and transfer belt, and in the case of image formation with a high image area ratio such as a photographic image, an untransferred image is formed due to poor paper feed The accumulated toner may become a transfer residual toner on the photoconductor, resulting in background smearing of the image, or it may contaminate the charging roller for charging the photoconductor in contact with the original charging ability. It may become impossible to demonstrate.
The average circularity is measured by, for example, an optical detection band method in which a suspension containing toner particles is passed through an imaging unit detection band on a flat plate, and a particle image is optically detected and analyzed by a CCD camera. It can be measured using, for example, a flow type particle image analyzer FPIA-3000 Sysmex).

(Volume average particle size)
There is no restriction | limiting in particular as a volume average particle diameter of the said toner, Although it can select suitably according to the objective, For example, 3-8 micrometers is preferable.
When the volume average particle size is less than 3 μm, in the case of a two-component developer, the toner may be fused to the surface of the carrier during long-term agitation in the developing device, and the charging ability of the carrier may be reduced. In the developer, toner filming on the developing roller and toner thinning are likely to cause toner fusion to a member such as a blade. On the other hand, when the thickness exceeds 8 μm, it becomes difficult to obtain a high-resolution and high-quality image, and when the balance of the toner in the developer is performed, the fluctuation of the toner particle size may increase.

The ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) in the toner is preferably 1.00 to 1.25, more preferably 1.10 to 1.25.
When the ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) exceeds 1.25, the two-component developer causes the surface of the carrier to be agitated for a long period of time in the developing device. The toner may be fused to reduce the charging ability of the carrier. In the case of a one-component developer, the toner filming on the developing roller or the toner is thinned so that the toner is fused to a member such as a blade. May occur easily, and it becomes difficult to obtain a high-resolution and high-quality image, and when the balance of the toner in the developer is performed, the fluctuation of the toner particle size may increase. is there.
The volume average particle diameter and the ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) are, for example, a particle size measuring device “Coulter Counter TAII” manufactured by Coulter Electronics Co., Ltd. Can be measured.

<Two-component developer>
The toner of the present invention can be used in combination with a carrier to form a two-component developer.
There is no restriction | limiting in particular as a 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. In addition, the copper-zinc (Cu-Zn) system (30 to 80 emu / g) or the like is advantageous in that it can weaken the contact with the electrostatic latent image carrier in which the toner is in a spiked state, and is advantageous in improving the image quality. The weakly magnetized material is preferred. These may be used alone or in combination of two or more.

  The particle diameter of the core material is preferably an average particle diameter (weight average particle diameter (D50)) of 10 to 200 μm, and more preferably 40 to 100 μm. When the average particle diameter (weight average particle diameter (D50)) is less than 10 μm, in the distribution of carrier particles, the fine powder system increases, the magnetization per particle is lowered, and carrier scattering may occur. If it exceeds 200 μm, the specific surface area may decrease and toner scattering may occur, and in the case of a full color with many solid portions, reproduction of the solid portions may be particularly poor.

  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 fluorinated terpolymers (triple fluorinated (multiple) copolymers) such as terpolymers of tetrafluoroethylene, vinylidene fluoride and non-fluorinated monomers, silicone resins, etc. It is done. These may be used individually by 1 type and may use 2 or more types together. Among these, a silicone resin is particularly preferable.

The silicone resin is not particularly limited and can be appropriately selected according to the purpose from generally known silicone resins. For example, a straight silicone resin consisting only of an organosilosan bond; an alkyd resin; Examples thereof include polyester resins, epoxy resins, acrylic resins, silicone resins modified with urethane resins, and the like.
Commercially available products can be used as the silicone resin. Examples of straight silicone resins include KR271, KR255, and KR152 manufactured by Shin-Etsu Chemical Co., Ltd .; SR2400, SR2406, and SR2410 manufactured by Toray Dow Corning Silicone. Can be mentioned.

  Commercially available products can be used as the modified silicone resin, such as KR206 (alkyd modified), KR5208 (acrylic modified), ES1001N (epoxy modified), KR305 (urethane modified) manufactured by Shin-Etsu Chemical Co., Ltd .; Toray Dow Examples include SR2115 (epoxy-modified), SR2110 (alkyd-modified) manufactured by Corning Silicone. In addition, although a silicone resin can be used alone, it is also possible to simultaneously use a component that undergoes a crosslinking reaction, a charge amount adjusting component, and the like.

  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.
There is no restriction | limiting in particular as said solvent, Although it can select suitably according to the objective, For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cellosolve, butyl acetate, etc. are mentioned.
The baking method is not particularly limited, and may be an external heating method or an internal heating method. For example, a stationary electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace Etc., a method using a microwave, and the like.

  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 a 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 mass. % Is preferable, and 93 to 97% by mass is more preferable.
In general, the mixing ratio of the toner and the carrier of the two-component developer is preferably 1 to 10.0 parts by mass of the toner with respect to 100 parts by mass of the carrier.

<Toner production method>
The method for producing the toner is not particularly limited and can be appropriately selected from conventionally known toner production methods according to the purpose. For example, a kneading / pulverizing method, a suspension polymerization method, a dispersion polymerization method, Examples thereof include an emulsion aggregation method, a polymer solution suspension method, and a polymer elongation method. Among them, a method of obtaining toner particles by suspending a polymer solution in an aqueous medium and a method of obtaining toner particles by a polymer stretching method are preferable.

[Kneading and grinding method]
The kneading and pulverization method includes, for example, melt-kneading a toner material containing at least a binder resin, a release agent, and a colorant, and pulverizing and classifying the obtained kneaded material, whereby the base particles of the toner are obtained. It is a method of manufacturing.
In the melt kneading, the toner materials are mixed, and the mixture is charged into a melt kneader and melt kneaded. As the melt kneader, for example, a uniaxial or biaxial continuous kneader or a batch kneader using a roll mill can be used. For example, a KTK type twin screw extruder manufactured by Kobe Steel, a TEM type extruder manufactured by Toshiba Machine Co., Ltd., a twin screw extruder manufactured by Casey Kay Co., Ltd., a PCM type twin screw extruder manufactured by Ikegai Co., Ltd. Used. This melt-kneading is preferably performed under appropriate conditions so as not to cause the molecular chains of the binder resin to be broken. Specifically, the melt-kneading temperature is determined with reference to the softening point of the binder resin. If the temperature is higher than the softening point, cutting is severe, and if the temperature is too low, dispersion may not proceed.

  In the pulverization, the kneaded product obtained by the kneading is pulverized. In this pulverization, it is preferable that the kneaded material is first coarsely pulverized and then finely pulverized. At this time, a method of pulverizing by colliding with a collision plate in a jet stream, pulverizing particles by colliding with each other in a jet stream, or pulverizing with a narrow gap between a mechanically rotating rotor and a stator is preferably used.

In the classification, the pulverized product obtained by the pulverization is classified and adjusted to particles having a predetermined particle diameter. The classification can be performed, for example, by removing the fine particle portion with a cyclone, a decanter, a centrifuge, or the like.
After the pulverization and classification are completed, the pulverized product is classified into an air stream by centrifugal force or the like, and toner base particles having a predetermined particle diameter can be produced.

  Next, the external additive is externally added to the toner base particles. By mixing and stirring the toner base particles and the external additive using a mixer, the surface of the toner base particles is coated while being crushed. At this time, it is important from the viewpoint of durability that the external additives such as inorganic fine particles and resin fine particles are uniformly and firmly attached to the toner base particles.

[Polymer elongation method]
In the production of the toner of the present invention, in the polymer elongation method, the active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound are reacted at least to produce an adhesive substrate in an aqueous medium. It is preferable to form particles, and to make toner particles containing components such as resin fine particles, a colorant, a release agent, a non-reactive polyester resin, and a charge control agent as necessary.

[Active hydrogen group-containing compound and polymer capable of reacting with the active hydrogen group-containing compound]
The polymer capable of reacting with the active hydrogen group-containing compound is not particularly limited as long as it has at least a site capable of reacting with the active hydrogen group-containing compound, and is appropriately selected from known resins and the like. Examples thereof include polyol resins, polyacrylic resins, polyester resins, epoxy resins, and derivative resins thereof.
These may be used alone or in combination of two or more. Among these, a polyester resin is particularly preferable in terms of high fluidity and transparency during melting.

  The site capable of reacting with the active hydrogen group-containing compound is not particularly limited and may be appropriately selected from known substituents. For example, an isocyanate group, an epoxy group, a carboxylic acid, a chloride group, etc. Is mentioned. These may be included singly or in combination of two or more. Among these, an isocyanate group is particularly preferable.

The mass average molecular weight of the active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound is not particularly limited and may be appropriately selected depending on the intended purpose. ˜1000000 is more preferable, and 8000 to 100,000 is particularly preferable.
When the mass average molecular weight is less than 1000, the hot offset resistance may be deteriorated. Moreover, there is no restriction | limiting in particular as glass transition temperature (Tg), According to the objective, it can select suitably, For example, 30-70 degreeC is preferable and 40-65 degreeC is more preferable.
When the glass transition temperature (Tg) 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.

  The isocyanate group-containing polyester prepolymer (A) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is a polycondensate of a polyol (PO) and a polycarboxylic acid (PC), And those obtained by reacting the active hydrogen group-containing polyester resin with polyisocyanate (PIC).

  There is no restriction | limiting in particular as said polyol (PO), According to the objective, it can select suitably, For example, diol (DIO), trihydric or more polyol (TO), diol (DIO), and trihydric or more polyol ( TO) and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, the diol (DIO) alone or a mixture of the diol (DIO) and a small amount of the trivalent or higher polyol (TO) is preferable.

Examples of the diol (DIO) include alkylene glycols, alkylene ether glycols, alicyclic diols, alkylene oxide adducts of alicyclic diols, bisphenols, alkylene oxide adducts of bisphenols, and the like.
The alkylene glycol is preferably one having 2 to 12 carbon atoms, such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, and the like. Can be mentioned.
Examples of the alkylene ether glycol include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and the like.
Examples of the alicyclic diol include 1,4-cyclohexanedimethanol, hydrogenated bisphenol A and the like.
Examples of the alkylene oxide adduct of the alicyclic diol include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the alicyclic diol.
Examples of the bisphenols include bisphenol A, bisphenol F, and bisphenol S.
Examples of the alkylene oxide adduct of the bisphenol include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the bisphenol. Among these, alkylene glycols having 2 to 12 carbon atoms, alkylene oxide adducts of bisphenols and the like are preferable, and alkylene oxide adducts of bisphenols, alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. Mixtures are particularly preferred.

The trivalent or higher polyol (TO) is preferably 3 to 8 or higher, for example, a trivalent or higher polyhydric aliphatic alcohol, a trivalent or higher polyphenol, a trivalent or higher polyphenol. And alkylene oxide adducts.
Examples of the trihydric or higher polyhydric aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol and the like.
Examples of the trihydric or higher polyphenols include trisphenol PA, phenol novolak, cresol novolak, and the like. Examples of the trivalent or higher polyphenols alkylene oxide adducts include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the trivalent or higher polyphenols.

  The mixture mass ratio (DIO: TO) of the diol (DIO) and the trivalent or higher polyol (TO) in the mixture of the diol (DIO) and the trivalent or higher polyol (TO) is 100: 0.01-10 are preferable and 100: 0.01-1 are more preferable.

There is no restriction | limiting in particular as said polycarboxylic acid (PC), Although it can select suitably according to the objective, For example, dicarboxylic acid (DIC), trivalent or more polycarboxylic acid (TC), dicarboxylic acid (DIC) ) And a tricarboxylic or higher polycarboxylic acid (TC).
These may be used individually by 1 type and may use 2 or more types together. Among these, dicarboxylic acid (DIC) alone or a mixture of DIC and a small amount of trivalent or higher polycarboxylic acid (TC) is preferable. Examples of the dicarboxylic acid include alkylene dicarboxylic acid, alkenylene dicarboxylic acid, aromatic dicarboxylic acid, and the like.

Examples of the alkylene dicarboxylic acid include succinic acid, adipic acid, and sebacic acid. As said alkenylene dicarboxylic acid, a C4-C20 thing is preferable, For example, a maleic acid, a fumaric acid, etc. are mentioned. As said aromatic dicarboxylic acid, a C8-C20 thing is preferable, For example, a phthalic acid, an isophthalic acid, a terephthalic acid, naphthalene dicarboxylic acid etc. are mentioned.
Among these, alkenylene dicarboxylic acid having 4 to 20 carbon atoms and aromatic dicarboxylic acid having 8 to 20 carbon atoms are preferable.

The trivalent or higher polycarboxylic acid (TC) is preferably 3 to 8 or higher, and examples thereof include aromatic polycarboxylic acids.
The aromatic polycarboxylic acid preferably has 9 to 20 carbon atoms, and examples thereof include trimellitic acid and pyromellitic acid.

Examples of the polycarboxylic acid (PC) include the dicarboxylic acid (DIC), the trivalent or higher polycarboxylic acid (TC), and a mixture of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid. Any acid anhydride or lower alkyl ester selected from can also be used.
Examples of the lower alkyl ester include methyl ester, ethyl ester, isopropyl ester and the like.

  Mixing mass ratio (DIC: TC) of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid (TC) in the mixture of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid (TC) There is no restriction | limiting in particular, According to the objective, it can select suitably, For example, 100: 0.01-10 are preferable and 100: 0.01-1 are more preferable.

  The mixing ratio for the polycondensation reaction between the polyol (PO) and the polycarboxylic acid (PC) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, in the polyol (PO) The equivalent ratio ([OH] / [COOH]) of the hydroxyl group [OH] to the carboxyl group [COOH] in the polycarboxylic acid (PC) is usually preferably 2/1 to 1/1. More preferably, it is 0.5 / 1 to 1/1, and particularly preferably 1.3 / 1 to 1.02 / 1.

There is no restriction | limiting in particular as content in the said isocyanate group containing polyester prepolymer (A) of the said polyol (PO), Although it can select suitably according to the objective, For example, 0.5-40 mass% is preferable. 1-30 mass% is more preferable, and 2-20 mass% is especially preferable.
When the content is less than 0.5% by mass, the hot offset resistance deteriorates, 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 mass. In some cases, the low-temperature fixability may deteriorate.

  The polyisocyanate (PIC) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic diisocyanates, araliphatic diisocyanates, and isocyanurates. And those blocked with phenol derivatives, oximes, caprolactams, and the like.

Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, Examples include tetramethylhexane diisocyanate.
Examples of the alicyclic polyisocyanate include isophorone diisocyanate and cyclohexylmethane diisocyanate.
Examples of the aromatic diisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, diphenylene-4,4′-diisocyanate, 4,4′-diisocyanato-3,3′-dimethyldiphenyl, 3- Examples include methyldiphenylmethane-4,4′-diisocyanate and diphenyl ether-4,4′-diisocyanate.
Examples of the araliphatic diisocyanate include α, α, α ′, α′-tetramethylxylylene diisocyanate.
Examples of the isocyanurates include tris-isocyanatoalkyl-isocyanurate and triisocyanatocycloalkyl-isocyanurate.
These can be used alone or in combination of two or more.

As a mixing ratio when the polyisocyanate (PIC) and the active hydrogen group-containing polyester resin (for example, a hydroxyl group-containing polyester resin) are reacted, the isocyanate group [NCO] in the polyisocyanate (PIC) and the hydroxyl group-containing component are used. The mixing equivalent ratio ([NCO] / [OH]) with the hydroxyl group [OH] in the polyester resin is usually preferably 5/1 to 1/1, and preferably 3/1 to 1.2 / 1. Is more preferable, and 1.5 / 1 to 1.1 / 1 is particularly preferable.
If the mixing equivalent ratio ([NCO] / [OH]) exceeds 5, offset resistance may be deteriorated, and if it is less than 1, gelation may occur during synthesis.

There is no restriction | limiting in particular as content in the said isocyanate group containing polyester prepolymer (A) of the said polyisocyanate (PIC), Although it can select suitably according to the objective, For example, 0.5-40 mass% is Preferably, 1-30 mass% is more preferable, and 2-20 mass% is still more preferable. When the content is less than 0.5% by mass, the hot offset resistance is deteriorated, and it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability. When the content exceeds 40% by mass, Low temperature fixability may deteriorate.
The average number of isocyanate groups contained in one molecule of the isocyanate group-containing polyester prepolymer (A) is preferably 2 or more, more preferably 2.0 to 2.5, and more preferably 2.0 to 2.2. preferable.
When the average number of isocyanate groups is less than 2, hot offset resistance may be deteriorated.

(Active hydrogen group-containing compound)
The active hydrogen group-containing compound acts as an elongation agent, a crosslinking agent, or the like when a polymer capable of reacting with the active hydrogen group-containing compound undergoes an elongation reaction, a crosslinking reaction, or the like in the aqueous medium. The active hydrogen group-containing compound is not particularly limited as long as it has an active hydrogen group, and can be appropriately selected depending on the purpose. For example, the polymer capable of reacting with the active hydrogen group-containing compound is In the case of the isocyanate group-containing polyester prepolymer (A), the amines (B) can be increased in molecular weight by a reaction such as an elongation reaction or a crosslinking reaction with the isocyanate group-containing polyester prepolymer (A). Is preferred. There is no restriction | limiting in particular as said active hydrogen group, According to the objective, it can select suitably, For example, a hydroxyl group (alcoholic hydroxyl group or phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, alcoholic hydroxyl groups are particularly preferable.

  The amines (B) are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diamine (BI), trivalent or higher polyamine (B2), amino alcohol (B3), and amino mercaptan. (B4), amino acid (B5), and those obtained by blocking the amino groups of B1 to B5 (B6). These may be used individually by 1 type and may use 2 or more types together. Among these, diamine (B1), a mixture of diamine (B1) and a small amount of a trivalent or higher polyamine (B2) are particularly preferable.

Examples of the diamine (B1) include aromatic diamines, alicyclic diamines, and aliphatic diamines. Examples of the aromatic diamine include phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, and the like. Examples of the alicyclic diamine include 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, diaminecyclohexane, and isophoronediamine. Examples of the aliphatic diamine include ethylene diamine, tetramethylene diamine, and hexamethylene diamine.
Examples of the trivalent or higher polyamine (B2) include diethylenetrimine and triethylenetetramine.
Examples of the amino alcohol (B3) include ethanolamine and hydroxyethylaniline.
Examples of the amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.
Examples of the block (B6) obtained by blocking the amino group of B1 to B5 include ketimines obtained from any of the amines (B1) to (B5) and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Compounds, oxazolyzone compounds, and the like.

As a mixing ratio of the amines (B) and the isocyanate group-containing polyester prepolymer (A), the isocyanate group [NCO] in the isocyanate group-containing prepolymer (A) and the amines (B) The mixed equivalent ratio ([NCO] / [NH _X ]) of the amino group [NH _X ] is preferably 1/3 to 3/1, more preferably 1/2 to 2/1. A ratio of 1 / 1.5 to 1.5 / 1 is particularly preferable.
If the mixing equivalent ratio ([NCO] / [NH _X ]) is less than 1/3, the low-temperature fixability may be deteriorated. If it exceeds 3/1, the molecular weight becomes low and hot offset resistance is reduced. May get worse.

(Aqueous medium)
There is no restriction | limiting in particular as said aqueous medium, It can select suitably from well-known things, For example, water, the solvent miscible with this water, these mixtures, etc. are mentioned.

(Manufacture of toner)
The method for producing the toner includes a step of obtaining a particulate toner while producing an adhesive substrate in an aqueous medium by at least reacting an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound. It includes at least other processes that are appropriately selected as necessary.
In the step, for example, preparation of an aqueous medium phase, preparation of an organic solvent phase, emulsification / dispersion, etc. (synthesis of a polymer (prepolymer) capable of reacting with the active hydrogen group-containing compound, synthesis of the active hydrogen group-containing compound, etc.) )I do.

The aqueous medium phase can be prepared, for example, by dispersing the resin fine particles in the aqueous medium. There is no restriction | limiting in particular as the addition amount in this aqueous medium of this resin fine particle, According to the objective, it can select suitably, For example, 0.5-10 mass% is preferable.
The organic solvent phase is prepared by the active hydrogen group-containing compound in the organic solvent, the polymer capable of reacting with the active hydrogen group-containing compound, the colorant, the release agent, the charge control agent, the unmodified It can be carried out by dissolving or dispersing a toner raw material such as polyester resin.

  It should be noted that components other than the polymer (prepolymer) capable of reacting with the active hydrogen group-containing compound in the toner raw material are added when the resin fine particles are dispersed in the aqueous medium in the aqueous medium phase preparation. You may add and mix in an aqueous medium, or when adding the said organic solvent phase to the said aqueous medium phase, you may add to the said aqueous medium phase with this organic solvent phase.

The organic solvent is not particularly limited as long as it is a solvent that can dissolve or disperse the toner raw material, and can be appropriately selected according to the purpose, and has a boiling point of less than 150 ° C. in terms of ease of removal. For example, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, Examples thereof include methyl ethyl ketone and methyl isobutyl ketone. Among these, ethyl acetate, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride and the like are particularly preferable. These may be used alone or in combination of two or more.
There is no restriction | limiting in particular as the usage-amount of the said organic solvent, According to the objective, it can select suitably, For example, 40-300 mass parts is preferable with respect to 100 mass parts of said toner raw materials, and 60-140 mass parts is. More preferably, 80-120 mass parts is still more preferable.

  The emulsification / dispersion can be performed by emulsifying / dispersing the previously prepared organic solvent phase in the previously prepared aqueous medium phase. In the emulsification / dispersion, when the active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound are subjected to an extension reaction or a crosslinking reaction, the adhesive base material is generated.

  The adhesive substrate (for example, the urea-modified polyester resin is, for example, (1) the organic containing the polymer that can react with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)). The solvent phase is emulsified and dispersed in the aqueous medium phase together with the active hydrogen group-containing compound (for example, the amines (B)) to form a dispersion, and both are subjected to an extension reaction or the like in the aqueous medium phase. (2) The organic solvent phase is emulsified and dispersed in the aqueous medium to which the active hydrogen group-containing compound has been added in advance to form a dispersion, and the aqueous medium phase Or may be produced by subjecting both to an extension reaction or a crosslinking reaction, or (3) the organic solvent phase is added to and mixed with the aqueous medium, and then the active hydrogen group is contained. In the case of (3), the dispersion may be formed by adding a product to form a dispersion and subjecting both to an extension reaction or a crosslinking reaction from the particle interface in the aqueous medium phase. A modified polyester resin is preferentially produced, and a concentration gradient can be provided in the toner particles.

  The reaction conditions for producing the adhesive substrate by the emulsification / dispersion are not particularly limited, depending on the combination of the polymer capable of reacting with the active hydrogen group-containing compound and the active hydrogen group-containing compound. The reaction time is preferably 10 minutes to 40 hours, more preferably 2 hours to 24 hours, and the reaction temperature is preferably 0 to 150 ° C, more preferably 40 to 98 ° C.

  In the aqueous medium phase, as a method for stably forming the dispersion containing a polymer capable of reacting with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)), for example, Polymer capable of reacting with the active hydrogen group-containing compound dissolved or dispersed in the organic solvent in the aqueous medium phase (for example, the isocyanate group-containing polyester prepolymer (A)), the colorant, and the release agent And a method of adding the toner raw materials such as the charge control agent and the unmodified polyester resin and dispersing them by shearing force.

The dispersion is not particularly limited as a method thereof, and can be appropriately selected using a known disperser. Examples of the disperser include a low-speed shear disperser, a high-speed shear disperser, and a friction type. Examples thereof include a disperser, a high-pressure jet disperser, and an ultrasonic disperser. Among these, a high-speed shearing disperser is preferable in that the particle size of the dispersion can be controlled to 2 to 20 μm.
When the high-speed shearing disperser is used, the rotation speed, dispersion time, dispersion temperature and other conditions are not particularly limited and can be appropriately selected according to the purpose. For example, the rotation speed is 1000 -30000 rpm is preferable, 5000-20000 rpm is more preferable, and the dispersion time is preferably 0.1-5 minutes in the case of a batch system, and the dispersion temperature is preferably 0-150 ° C. under pressure, 98 ° C. is more preferable. The dispersion temperature is generally easier when the temperature is higher.

In the emulsification / dispersion, the amount of the aqueous medium used is preferably 50 to 2000 parts by mass, more preferably 100 to 1000 parts by mass with respect to 100 parts by mass of the toner raw material. When the amount of the aqueous medium used is less than 50 parts by mass, the toner raw material is in a poorly dispersed state, and toner particles having a predetermined particle size may not be obtained. May be high.
In the emulsification / dispersion, it is preferable to use a dispersant as necessary from the viewpoint of sharpening the particle size distribution and performing stable dispersion. There is no restriction | limiting in particular as said dispersing agent, According to the objective, it can select suitably, For example, surfactant, a sparingly water-soluble inorganic compound dispersing agent, a polymeric protective colloid, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, surfactants are preferable.

  Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.

  Examples of the anionic surfactant include alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters and the like, and those having a fluoroalkyl group are preferable. Examples of the anionic surfactant having a fluoroalkyl group include a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, disodium perfluorooctanesulfonyl glutamate, 3- [omega-fluoroalkyl (carbon number 6 -11) oxy] -1-alkyl (3 to 4 carbon atoms) sodium sulfonate, 3-omega-fluoroalkanoyl (6 to 8 carbon atoms) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl ( Carbon number 11-20) carboxylic acid or metal salt thereof, perfluoroalkyl carboxylic acid (carbon number 7-13) or metal salt thereof, perfluoroalkyl (carbon number 4-12) sulfonic acid or metal salt thereof, perfluorooctane Sulfonic acid diethanolamide, N-propyl-N- (2-hydride Xylethyl) perfluorooctanesulfonamide, perfluoroalkyl (carbon number 6-10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (carbon number 6-10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (carbon number) 6-16) Ethyl phosphate and the like. Examples of 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 (manufactured by Sumitomo 3M); Unidyne DS-101, DS-102 (manufactured by Daikin Industries); Megafac F-110, F-120, F-113, F-191, F-812, F-833 (large) Nihon Ink Co., Ltd.); Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products); Manufactured) and the like.

  Examples of the cationic surfactant include amine salt type surfactants and quaternary ammonium salt type cationic surfactants. Examples of the amine salt type surfactant include alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazolines, and the like. Examples of the quaternary ammonium salt type cationic surfactant include alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride and the like. . Among the cationic surfactants, aliphatic quaternary ammonium such as aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, perfluoroalkyl (6 to 10 carbon atoms) sulfonamidopropyltrimethylammonium salt, etc. Salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, and the like. Commercially available products of the cationic surfactant include, for example, Surflon S-121 (manufactured by Asahi Glass Co., Ltd.); Florard FC-135 (manufactured by Sumitomo 3M Co.); F-824 (manufactured by Dainippon Ink, Inc.); Xtop EF-132 (manufactured by Tochem Products); and Footgent F-300 (manufactured by Neos).

  Examples of the nonionic surfactant include fatty acid amide derivatives and polyhydric alcohol derivatives.

  Examples of the amphoteric surfactant include alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine, N-alkyl-N, N-dimethylammonium betaine and the like.

  Examples of the poorly water-soluble inorganic compound dispersant include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite. Examples of the polymeric protective colloid include acids, (meth) acrylic monomers containing hydroxyl groups, vinyl alcohol or ethers of vinyl alcohol, esters of vinyl alcohol and compounds containing carboxyl groups, amides Examples thereof include homopolymers or copolymers such as compounds or their methylol compounds, chlorides, those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylenes, and celluloses.

  Examples of the acids include acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, and the like.

  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 Glycerin monomethacrylate, N-methylol acrylamide, N-methylol methacrylamide and the like.

  Examples of the vinyl alcohol or ethers with vinyl alcohol include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, and the like.

  Examples of the esters of the compound containing vinyl alcohol and a carboxyl group include vinyl acetate, vinyl propionate, vinyl butyrate and the like.

  Examples of the amide compound or these methylol compounds include acrylamide, methacrylamide, diacetone acrylamide acid, or these methylol compounds.

  Examples of the chlorides include acrylic acid chloride and methacrylic acid chloride.

  Examples of the homopolymer or copolymer such as those having a nitrogen atom or a heterocyclic ring thereof include vinyl pyridine, vinyl pyrrolidone, vinyl imidazole and ethylene imine.

  Examples of the polyoxyethylene are polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene Examples thereof include oxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, and polyoxyethylene nonyl phenyl ester.

  Examples of the celluloses include methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.

In the emulsification / dispersion, a dispersion stabilizer can be used as necessary.
Examples of the dispersion stabilizer include acids that are soluble in acids and alkalis such as calcium phosphate salts. When the dispersion stabilizer is used, the calcium phosphate salt can be removed from the fine particles by a method of dissolving the calcium phosphate salt with an acid such as hydrochloric acid and then washing with water or a method of decomposing with an enzyme.
In the emulsification / dispersion, a catalyst for the elongation reaction or the crosslinking reaction can be used. Examples of the catalyst include dibutyltin laurate and dioctyltin laurate.

The organic solvent is removed from the emulsified slurry obtained in the emulsification / dispersion. The organic solvent is removed by (1) a method in which the entire reaction system is gradually heated to completely evaporate and remove the organic solvent in the droplets, and (2) the emulsion dispersion is sprayed in a dry atmosphere. For example, a method of completely removing the water-insoluble organic solvent in the droplets to form toner fine particles and evaporating and removing the aqueous dispersant together.
When the organic solvent is removed, toner particles are formed. In this method, the toner particles can be collected as a wet cake, washed, dried, etc., and then classified as desired. The classification can be performed, for example, by removing fine particle portions by a cyclone, a decanter, centrifugation, or the like in a liquid, and the classification operation may be performed after obtaining a powder after drying.

Thus, the obtained toner particles are mixed with particles of the colorant, release agent, charge control agent, etc., and further, a mechanical impact force is applied to the release agent from the surface of the toner particles. And the like can be prevented from being detached.
Examples of the method of applying the mechanical impact force include a method of applying an impact force to the mixture by a blade rotating at a high speed, an appropriate collision between particles or composite particles by introducing the mixture into a high-speed air stream and accelerating the mixture. The method of making it collide with a board etc. are mentioned. As an apparatus used for this method, for example, an ong mill (manufactured by Hosokawa Micron), an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) to reduce the pulverization air pressure, and a hybridization system (Nara Machinery Co., Ltd.) Product), kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar, and the like.
Through the above steps, the toner particles are formed.

<Image forming apparatus and image forming method>
An image forming apparatus (full-color image forming apparatus) according to the present invention includes at least a photosensitive member, a charging unit that uniformly charges the surface of the photosensitive member, and image exposure on the surface of the uniformly charged photosensitive member to perform electrostatic latent. Image formation comprising at least image exposure means for forming an image, development means for developing the formed electrostatic latent image using toner, and transfer means for transferring the developed toner image to a recording medium A full color image forming apparatus in which a plurality of elements are arranged, wherein the toner used is the color image forming toner of the present invention.
The full-color image forming apparatus according to the present invention further includes at least a photosensitive member, a charging unit, an image exposing unit, a developing unit, and a transferring unit, and the developing unit includes a plurality of developing units filled with toners of different colors. A tandem type full-color image forming apparatus comprising a plurality of photoconductors corresponding to the plurality of developing sections, wherein the toner used is the color image forming toner of the present invention. It is.
Hereinafter, only the basic components of each means provided in the full-color image forming apparatus in which the color image forming toner of the present invention is used will be described (FIGS. 1 to 6). Thereafter, a full-color image forming apparatus will be described (FIGS. 7 to 19). FIG. 19 is a schematic view for explaining a process cartridge for a full-color image forming apparatus.

The image forming apparatus includes at least an electrostatic latent image carrier (photoconductor), a charging unit, an exposure unit (image exposure unit), a development unit, a transfer unit, and a fixing unit, and a cleaning unit. In addition, other means appropriately selected as necessary, for example, static elimination means, recycling means, control means, and the like are provided. The charging unit and the exposure unit may be collectively referred to as an electrostatic latent image forming unit.
According to the full-color image forming apparatus of the present invention, low-temperature fixability, hot offset resistance, heat-resistant storage stability are excellent, toner aggregation and adhesion hardly occur between toners, and high glossy color image forming toner is used. Even in the image formation, an abnormal image is not generated and a stable image can be output. If the full-color image forming method and the full-color image forming apparatus of the present invention are used, it can be widely applied to electrophotographic application fields using electrophotography (for example, laser printers, copiers, facsimiles, etc.).

The image forming method includes at least a charging step, an exposure step, a development step, a transfer step, and a fixing step, and includes a cleaning step, and other steps appropriately selected as necessary, for example, a static elimination step and a recycling step. , Including control steps. The charging process and the exposure process may be collectively referred to as an electrostatic latent image forming process.
The image forming method can be preferably performed by the image forming apparatus, the charging step can be performed by the charging unit, the exposure step can be performed by the exposing unit, and the developing step can be performed by the developing unit. The transfer step can be performed by the transfer unit, the fixing step can be performed by the fixing unit, the cleaning step can be performed by the cleaning unit, and the other steps. Can be performed by the other means.
According to the full-color image forming method of the present invention, low-temperature fixability, hot offset resistance, heat-resistant storage stability are excellent, toner agglomeration between toners hardly occurs, and high-gloss color image forming toner is used. Even in the image formation, an abnormal image is not generated and a high-quality image can be output stably.

[Electrostatic latent image carrier (photoconductor)]
The material, shape, structure, size, etc. of the electrostatic latent image carrier (photoconductor) are not particularly limited and can be appropriately selected according to the purpose. Examples of the shape include: Examples include a drum shape, a sheet shape, and an endless belt shape. The structure may be a single-layer structure or a laminated structure, and the size may be appropriately selected according to the size and specifications of the image forming apparatus. Examples of the material include inorganic photoreceptors such as amorphous silicon, selenium, CdS, and ZnO; organic photoreceptors (OPC) such as polysilane and phthalopolymethine, and the like.

  For example, the amorphous silicon photosensitive member is heated to 50 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 CVD method, or the like is applied on the support. A photosensitive layer made of a-Si is formed by a film forming method. Among these, the plasma CVD method is particularly preferable, and specifically, a method in which the source gas is decomposed by direct current, high frequency, or microwave glow discharge to form a photosensitive layer made of a-Si on the support is preferable. .

  The organic photoreceptor (OPC) has (1) optical characteristics such as a wide light absorption wavelength range and a large amount of light absorption, (2) electrical characteristics such as high sensitivity and stable charging characteristics, (3) In general, it is widely applied because of the wide selection range of materials, (4) ease of production, (5) low cost, and (6) non-toxicity. The layer structure of such an organic photoreceptor is roughly divided into a single layer structure and a laminated structure.

  The single-layered photoreceptor has a support and a single-layer type photosensitive layer provided on the support, and further includes a protective layer, an intermediate layer, and other layers as necessary. The laminated structure of the photosensitive member comprises a support and a laminated photosensitive layer having at least a charge generation layer and a charge transport layer in this order on the support, and further includes a protective layer and an intermediate layer as necessary. And other layers.

[Charging process and charging means]
The charging step is a step of charging the surface of the electrostatic latent image carrier (photoconductor), and is performed by the exposure unit. The charging means is not particularly limited as long as it can apply a voltage to the surface of the photoconductor to be uniformly charged, and can be appropriately selected according to the purpose. As such charging means, (1) a contact-type charging means that contacts and charges the electrostatic latent image carrier (photoconductor), and (2) a non-contact-type charging that charges non-contactly with the photoreceptor. Broadly divided into means.

[Contact charging means]
Examples of the contact type charging means (1) include a conductive or semiconductive charging roller, a magnetic brush, a fur brush, a film, and a rubber blade. Among these, the charging roller can significantly reduce the amount of ozone generated compared to corona discharge, and is excellent in stability during repeated use of the electrostatic latent image carrier, and effective in preventing image quality deterioration. It is.
The magnetic brush includes, for example, a non-magnetic conductive sleeve that supports various ferrite particles such as Zn—Cu ferrite, and a magnet roll included in the sleeve. The fur brush is formed by, for example, winding or pasting a fur subjected to a conductive treatment with carbon, copper sulfide, metal, metal oxide or the like around a metal or a conductive metal core.

  FIG. 1 is a cross-sectional view illustrating an example of a charging roller. The charging roller 310 includes a cored bar 311 as a conductive support having a cylindrical shape, a resistance adjustment layer 312 formed on the outer peripheral surface of the cored bar 311 with a uniform thickness, and the resistance adjustment layer 312. A protective layer 313 that covers the surface of the substrate and prevents leakage. The resistance adjusting layer 312 is formed by providing a thermoplastic resin composition on the peripheral surface of the core metal 311 by extrusion molding or injection molding. The thermoplastic resin used for the resistance adjusting layer 312 is not particularly limited and may be appropriately selected depending on the intended purpose. For example, polyethylene (PE), polypropylene (PP), polymethyl methacrylate (PMMA), Examples thereof include polystyrene (PS) and copolymers thereof (AS, ABS, etc.).

The resistance adjusting layer 312 is formed of a thermoplastic resin composition in which a polymer type ionic conductive agent is dispersed. The volume resistivity value of the resistance adjustment layer 312 is preferably 10 ⁶ to 10 ⁹ Ω · cm. When the volume resistivity value exceeds 10 ⁹ Ω · cm, the charge amount is insufficient, and the photosensitive drum may not be able to obtain a sufficient charging potential to obtain a uniform image. If the value is less than 10 ⁶ Ω · cm, there is a risk of leakage to the entire photosensitive drum.

As the polymer-type ion conductive agent, one having a resistance value of about 10 ⁶ to 10 ¹⁰ Ω · cm as a simple substance and easily reducing the resistance of the resin is used. One example is a compound containing a polyether ester amide component. In order to set the resistance value of the resistance adjusting layer 312 to the above value, the blending amount is preferably 30 to 70 parts by mass with respect to 100 parts by mass of the thermoplastic resin.

  In addition, a quaternary ammonium base-containing polymer compound can also be used as the polymer type ion conductive agent. Examples of the quaternary ammonium base-containing polymer compound include quaternary ammonium base-containing polyolefin. In order to set the resistance value of the resistance adjusting layer 312 to the above value, the blending amount is preferably 10 to 40 parts by mass with respect to 100 parts by mass of the thermoplastic resin.

  The polymer type ion conductive agent can be dispersed in the thermoplastic resin by a biaxial kneader, a kneader or the like. Since the polymer type ionic conductive agent is uniformly dispersed at the molecular level in the thermoplastic resin composition, the resistance adjusting layer 312 has a conductive material dispersed as seen in the resistance adjusting layer in which a conductive pigment is dispersed. There is no variation in resistance value due to defects. In addition, since the polymer type ion conductive agent is a polymer compound, it is uniformly dispersed and fixed in the thermoplastic resin composition, and bleedout hardly occurs.

The protective layer 313 is formed such that its resistance value is larger than that of the resistance adjustment layer 312. As a result, leakage to the defective portion of the photosensitive drum is avoided. However, if the resistance value of the protective layer 313 is too high, charging efficiency is lowered. Therefore, the difference between the resistance value of the protective layer 313 and the resistance value of the resistance adjustment layer 312 is preferably 10 ³ Ω · cm or less. .

  As a material for forming the protective layer 313, a resin material is preferable from the viewpoint of good film formability. As the resin material, for example, a fluororesin, a polyamide resin, a polyester resin, a polyvinyl acetal resin and the like are preferable from the viewpoint of excellent non-adhesiveness and preventing toner adhesion. In addition, since the resin material generally has electrical insulation, if the protective layer 313 is formed of the resin material alone, the characteristics of the charging roller are not satisfied. Therefore, the resistance value of the protective layer 313 is adjusted by dispersing various conductive agents in the resin material. In order to improve the adhesion between the protective layer 303 and the resistance adjustment layer 302, a reactive curing agent such as isocyanate may be dispersed in the resin material.

  The charging roller 310 is connected to a power source and is applied with a predetermined voltage. The voltage may be only a direct current (DC) voltage, but is preferably a voltage obtained by superimposing an alternating current (AC) voltage on a DC voltage. By thus applying the AC voltage, the surface of the photosensitive drum can be more uniformly charged.

FIG. 2 is a schematic diagram showing an example in which a contact-type charging roller 310 as shown in FIG. 1 is applied to an image forming apparatus as a charging unit. In FIG. 2, around a photosensitive drum 321 as an electrostatic latent image carrier, a charging roller 310 for charging the surface of the photosensitive drum, an exposure unit 323 for forming a latent image on a charging processing surface, Developing means 324 for forming a visible image by attaching toner to the latent image on the surface of the photosensitive drum, transfer means 325 for transferring the visible image on the formed photosensitive drum onto the recording medium 326, on the recording medium A fixing means 327 for fixing the visible image, a cleaning means 330 for removing and collecting the residual toner on the photosensitive drum, and a static eliminating device 331 for removing the residual potential on the photosensitive drum are arranged in this order. ing.
As the charging unit 310, a contact type charging roller 310 shown in FIG. 1 is provided, and the surface of the photosensitive drum 321 is uniformly charged by the charging roller 310.

[Non-contact charging means]
As the non-contact charging means (2), for example, a non-contact charger utilizing a corona discharge, a needle electrode device, a solid discharge element, or a electrostatic latent image carrier (photoconductor) with a small gap. Examples thereof include a conductive or semiconductive charging roller provided.
The corona discharge is a non-contact charging method that gives positive or negative ions generated by corona discharge in the air to the surface of the electrostatic latent image carrier, and gives a constant amount of charge to the electrostatic latent image carrier. There are a coroton charger having characteristics and a scorotron charger having characteristics that give a constant potential.

The coroton charger is composed of a casing electrode that occupies a half space around the discharge wire, and a discharge wire placed almost at the center thereof.
The scorotron charger is obtained by adding a grid electrode to the corotron charger, and the grid electrode is provided at a position 1.0 to 2.0 mm away from the surface of the electrostatic latent image carrier.

FIG. 3 is a schematic diagram illustrating an example in which a non-contact type corona charger is applied to an image forming apparatus as a charging unit. In FIG. 3, the same components as those in FIG. 2 are denoted by the same reference numerals.
As the charging means, a non-contact type corona charger 314 is provided, and the surface of the photosensitive drum 321 is uniformly charged by the corona charger 314. The charging roller provided with a minute gap with respect to the electrostatic latent image carrier is an improvement of the charging roller so as to have a minute gap with respect to the electrostatic latent image carrier. The fine gap is preferably 10 to 200 μm, and more preferably 10 to 100 μm.

  FIG. 4 is a schematic diagram illustrating an example of a non-contact charging roller. In FIG. 4, the charging roller 310 is disposed with a minute gap H with respect to the photosensitive drum 321. The minute gap H is set by causing the spacer member surface to contact the surface of the photosensitive drum 321 by, for example, winding a spacer member having a certain thickness around the non-image forming regions at both ends of the charging roller 310. can do. In FIG. 4, 304 is a power source.

  In FIG. 4, as a method for maintaining the minute gap H, a film 302 is wound around both ends of the charging roller 310 to form a spacer member. The spacer 302 is brought into contact with the photosensitive surface of the electrostatic latent image carrier to obtain a certain minute gap H in the image area of the charging roller and the electrostatic latent image carrier. The applied bias applies an AC superposition type voltage, and charges the electrostatic latent image carrier by a discharge generated in a small gap between the charging roller and the electrostatic latent image carrier. As shown in FIG. 4, the accuracy of maintaining the minute gap H is improved by pressing the shaft 311 of the charging roller with the spring 303.

The spacer member may be integrally formed with the charging roller. At this time, at least the surface of the gap portion is an insulator. As a result, the discharge at the gap portion is eliminated, and the discharge product is deposited on the gap portion, and the adhesion of the discharge product prevents the toner from adhering to the gap portion and spreading the gap.
Moreover, as the spacer member, a heat shrinkable tube may be used. Examples of such heat-shrinkable tubes include Sumitubes (trade name: F105 ° C, manufactured by Sumitomo Chemical Co., Ltd.) for 105 ° C.

[Exposure process and exposure means]
The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure unit. The optical system in the exposure is roughly classified into an analog optical system and a digital optical system. The analog optical system is an optical system that projects an original directly onto an electrostatic latent image carrier by an optical system, and the digital optical system receives image information as an electrical signal and converts it into an optical signal. It is an optical system that exposes an electrostatic latent image carrier to form an image. The exposure means is not particularly limited as long as the surface of the latent electrostatic image bearing member charged by the charging means can be exposed like 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, a liquid crystal shutter optical system, and an LED optical system can be used. In addition, you may employ | adopt the light back system which performs imagewise exposure from the back surface side of the said electrostatic latent image carrier.

[Development process and development means]
The developing step is a step of developing the electrostatic latent image using a toner or a developer 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, and can be performed by the developing unit.
The developing means is not particularly limited as long as it can be developed using toner or developer, for example, and can be appropriately selected from known ones. For example, the toner or developer is accommodated, and Preferable examples include those having at least developing means capable of bringing the toner or developer into contact or non-contact with the electrostatic latent image.

In general, the developing unit may be of a dry development type or a wet development type, but since the present invention is intended for color image forming toner, Developing means is selected. Suitable examples of the developing unit include a stirrer that charges the toner or the developer by frictional stirring and a rotatable magnet roller.
In the developing means, for example, the toner and the carrier are mixed and stirred, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state, thereby forming 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 photoreceptor by force. As a result, the electrostatic latent image is developed with the toner to form a visible image with the toner on the surface of the photoreceptor.
The developer accommodated in the developing device is a developer containing the toner, but the developer may be a one-component developer or a two-component developer.

[One-component developer]
As the one-component developing means, a one-component developing device having a developer carrier to which toner is supplied and a layer thickness regulating member that forms a thin layer of toner on the surface of the developer carrier is preferably used.
FIG. 5 is a schematic diagram illustrating an example of a one-component developing device. This one-component developing device uses a one-component developer made of toner, forms a toner layer on a developing roller 402 as a developer carrying member, and uses the toner layer on the developing roller 402 as an electrostatic latent image carrying member. The photosensitive drum 1 is conveyed so as to be in contact with the photosensitive drum 1 to perform contact one-component development for developing the electrostatic latent image on the photosensitive drum 1.

  In FIG. 5, the toner in the casing 401 is agitated by the rotation of an agitator 411 as agitation means and mechanically supplied to a supply roller 412 as a toner supply member. The supply roller 412 is formed of foamed polyurethane or the like, has flexibility, and has a structure in which toner can be easily held in a cell having a diameter of 50 to 500 μm. Further, the supply roller has a relatively low JIS-A hardness of 10 to 30 °, and can be brought into contact with the developing roller 402 uniformly.

  The supply roller 412 is driven to rotate in the same direction as the developing roller 402, that is, the surface of the supply roller 412 moves in the opposite direction at the opposing portion of both rollers. The linear speed ratio (supply roller / developing roller) of both rollers is preferably 0.5 to 1.5. Further, the supply roller 412 may be rotated so that the surfaces of the supply roller 412 move in the same direction as the developing roller 402, that is, at the opposite portions of the two rollers. In this embodiment, the supply roller 412 rotates in the same direction as the developing roller 402, and the linear speed ratio is set to 0.9. The biting amount of the supply roller 412 with respect to the developing roller 402 is set to 0.5 to 1.5 mm. In this embodiment, when the unit effective width is 240 mm (A4 size vertical), the necessary torque is 14.7 to 24.5 N · cm.

  The developing roller 402 has a surface layer made of a rubber material on a conductive substrate, has a diameter of 10 to 30 mm, and appropriately roughens the surface to have a surface roughness Rz of 1 to 4 μm. The value of the surface roughness Rz is 13 to 80% with respect to the average particle diameter of the toner, whereby the toner is conveyed without being buried in the surface of the developing roller 402. In particular, the surface roughness Rz of the developing roller 402 is preferably in the range of 20 to 30% of the average particle size of the toner so as not to retain a remarkably low charged toner.

  Examples of the rubber material include silicone rubber, butadiene rubber, NBR rubber, hydrin rubber, EPDM rubber, and the like. Further, it is preferable to coat the surface of the developing roller 402 with a coating layer in order to stabilize the quality with time. Examples of the material for the coating layer include silicone materials and Teflon (registered trademark) materials. The silicone material is excellent in toner chargeability, and the Teflon (registered trademark) material is excellent in releasability. In order to obtain conductivity, a conductive material such as carbon black can be appropriately contained. The thickness of the coat layer is preferably 5 to 50 μm. If it is out of this range, problems such as easy cracking may occur.

Toner having a predetermined polarity (negative polarity in the case of the present embodiment) existing on or inside the supply roller 412 is pinched by the developing roller 402 that rotates in the opposite direction at the contact point due to the rotation. A negatively charged charge is obtained by the charging effect and is held on the developing roller 402 by an electrostatic force and by a conveying effect by the surface roughness of the developing roller 402. However, the toner layer on the developing roller 402 at this time is not uniform and is considerably excessively attached (1 to 3 mg / cm ² ). Accordingly, a toner thin layer having a uniform layer thickness is formed on the developing roller 402 by bringing a regulating blade 413 as a layer thickness regulating member into contact with the developing roller 402. The restriction blade 413 is a so-called belly contact where the tip is directed downstream with respect to the rotation direction of the developing roller 402 and the central portion of the restriction blade 413 comes into contact, but it can also be set in the reverse direction. It is also possible to realize edge contact.

  As the material of the regulating blade, a metal such as SUS304 is preferable, and the thickness is 0.1 to 0.15 mm. In addition to the metal, a rubber material such as polyurethane rubber having a thickness of 1 to 2 mm or a resin material having a relatively high hardness such as a silicone resin can be used. In addition, since the resistance can be reduced by mixing carbon black or the like other than metal, it is possible to form an electric field between the developing roller 402 by connecting a bias power source.

  The regulating blade 413 as the layer thickness regulating member is preferably 10 to 15 mm as a free end length from the holder. If the free end length exceeds 15 mm, the developing means becomes large and cannot be stored compactly in the image forming apparatus. If it is less than 10 mm, vibration occurs when the regulating blade comes into contact with the surface of the developing roller 402. In some cases, an abnormal image such as unevenness in the horizontal direction is likely to occur on the image.

  The contact pressure of the regulating blade 413 is preferably in the range of 0.049 to 2.45 N / cm. If the contact pressure exceeds 2.45 N / cm, the toner adhesion amount on the developing roller 402 decreases and the toner charge amount increases excessively, so the development amount may decrease and the image density may decrease. If it is less than 0.049 N / cm, a thin layer may not be formed uniformly, and the toner mass may pass through the regulating blade, and the image quality may be significantly lowered. In this embodiment, the developing roller 402 has a JIS-A hardness of 30 °, the regulating blade 413 is a SUS plate having a thickness of 0.1 mm, and the contact pressure is set to 60 gf / cm. At this time, the target toner adhesion amount on the developing roller could be obtained.

Further, the contact angle of the regulating blade 413 as the layer thickness regulating member is preferably 10 to 45 ° with respect to the tangent line of the developing roller 402 in the direction in which the tip faces the downstream side of the developing roller 402. A portion unnecessary for forming a thin layer of toner sandwiched between the regulating blade 413 and the developing roller 402 is peeled off from the developing roller 402 and is 0.4 to 0.8 mg / cm ² per unit area which is a target range. A thin layer having a uniform thickness is formed. The toner charge at this time is finally in the range of −10 to −30 μC / g in this embodiment, and is developed to face the electrostatic latent image on the photosensitive drum 1.
Therefore, according to the one-component developing device of this embodiment, the distance between the surface of the photosensitive drum 1 and the surface of the developing roller 402 is further narrower than that in the case of the conventional two-component developing unit, the developing ability is increased, and the further low potential is achieved. But development is possible.

[Two-component developing means]
The two-component developing means has a magnetic field generating means fixed inside, and a two-component development having a rotatable developer carrier carrying a two-component developer comprising a magnetic carrier and toner on the surface. A device is preferred.

  FIG. 6 is a schematic view showing an example of a two-component developing device using a two-component developer composed of toner and a magnetic carrier. In the two-component developing device 424 of FIG. 6, the two-component developer is stirred and conveyed by the screw 441 and supplied to the developing sleeve 442 as a developer carrying member. The two-component developer supplied to the developing sleeve 442 is regulated by a doctor blade 443 as a layer thickness regulating member, and the amount of developer supplied is controlled by a doctor gap which is a distance between the doctor blade 443 and the developing sleeve 442. The If the doctor gap is too small, the developer amount is too small and the image density is insufficient. Conversely, if the doctor gap is too large, the developer amount is excessively supplied and the photosensitive drum as an electrostatic latent image carrier. There arises a problem that carrier adhesion occurs on 1. Therefore, the developing sleeve 442 is provided with a magnet as a magnetic field generating means for generating a magnetic field so that the developer is sprinkled on the peripheral surface thereof, so as to follow a normal magnetic field line generated from the magnet. Then, the developer is spiked in a chain shape on the developing sleeve 442 to form a magnetic brush.

  The developing sleeve 442 and the photosensitive drum 1 are disposed so as to be close to each other with a certain gap (developing gap) therebetween, and a developing region is formed in a portion facing both. The developing sleeve 442 is formed of a non-magnetic material such as aluminum, brass, stainless steel, or conductive resin in a cylindrical shape, and is rotated by a rotation drive mechanism (not shown). The magnetic brush is transferred to the developing area by the rotation of the developing sleeve 442. A developing voltage is applied to the developing sleeve 442 from a developing power source (not shown), and the toner on the magnetic brush is separated from the carrier by the developing electric field formed between the developing sleeve 442 and the photosensitive drum 1, and the photosensitive drum 1. It is developed on the upper electrostatic latent image. An alternating current may be superimposed on the development voltage.

The development gap is preferably about 5 to 30 times the particle size of the developer, and is preferably set to 0.5 to 1.5 mm if the developer particle size is 50 μm. If the development gap is wider than this, the desired image density may be difficult to achieve.
The doctor gap is preferably the same as or slightly larger than the development gap. The drum diameter and drum linear speed of the photosensitive drum 1 and the sleeve diameter and sleeve linear speed of the developing sleeve 442 are determined by restrictions such as the copying speed and the size of the apparatus. The ratio of the sleeve linear velocity to the drum linear velocity is preferably 1.1 or more in order to obtain a necessary image density. It is also possible to control the process conditions by installing a sensor at a position after development and detecting the toner adhesion amount from the optical reflectance.

[Transfer process and transfer means]
The transfer step is a step of transferring the visible image to a recording medium, and is performed using a transfer unit. As the transfer means. Using a transfer unit that directly transfers a visible image on the electrostatic latent image carrier to a recording medium, or an intermediate transfer member, after the primary transfer of the visible image onto the intermediate transfer member, the visible image is It is roughly divided into secondary transfer means for secondary transfer onto a recording medium.
The transfer can be performed, for example, by charging the visible latent image using a transfer charger and charging the electrostatic latent image carrier, and can be performed by the transfer unit. The transfer unit preferably includes a primary transfer unit that forms a composite transfer image by transferring a visible image onto an intermediate transfer member, and a secondary transfer unit that transfers the composite transfer image onto a recording medium. .

[Intermediate transfer member]
There is no restriction | limiting in particular as said intermediate transfer body, According to the objective, it can select suitably from well-known transfer bodies, For example, a transfer belt etc. are mentioned suitably.
The intermediate transfer member preferably has a static friction coefficient of 0.1 to 0.6, and more preferably 0.3 to 0.5. The volume resistance of the intermediate transfer member is preferably from several Ωcm to 10 ³ Ωcm. Thus, by setting the volume resistance to several Ωcm or more and 10 ³ Ωcm or less, the intermediate transfer member itself is prevented from being charged, and the charge imparted by the charge imparting means hardly remains on the intermediate transfer member. Uneven transfer during the next transfer can be prevented. Further, it is possible to easily apply a transfer bias at the time of secondary transfer.

There is no restriction | limiting in particular as a material of the said intermediate transfer body, Although it can select suitably according to the objective from well-known materials, the following are suitable.
(1) A material having a high Young's modulus (tensile modulus) is used as a single-layer belt. For example, PC (polycarbonate), PVDF (polyvinylidene fluoride), PAT (polyalkylene terephthalate), PC (polycarbonate) Blend material with PAT (polyalkylene terephthalate), Blend material with ETFE (ethylene tetrafluoroethylene copolymer) and PC, Blend material with ETFE and PAT, Blend material with PC and PAT, Thermal curing of carbon black dispersion For example, a functional polyimide. These single-layer belts having a high Young's modulus have the advantage that the amount of deformation with respect to stress during image formation is small, and rib displacement is unlikely to occur particularly during color image formation.
(2) A belt having a two- to three-layer structure in which a belt having a high Young's modulus of (1) is used as a base layer and a surface layer or an intermediate layer is provided on the outer periphery thereof. It has a performance capable of preventing the line image from being lost due to the hardness of the belt.
(3) An elastic belt having a relatively low Young's modulus using resin, rubber, or elastomer, and such an elastic belt has an advantage that almost no void in a line image occurs due to its softness. In addition, the elastic belt is wider than the drive roll and tension roll, and the elasticity of the belt ears protruding from the roll can be used to prevent meandering, thus reducing costs without requiring ribs or meandering prevention devices. it can.
Among these, the elastic belt (3) is particularly preferable.

  The elastic belt is deformed corresponding to a toner layer and a recording medium having poor smoothness in the transfer portion. In other words, the elastic belt deforms following local irregularities, so that it is possible to obtain good adhesion without excessively increasing the transfer pressure with respect to the toner layer, and recording with poor flatness without missing characters. A transfer image with excellent uniformity can be obtained even on a medium.

  There is no restriction | limiting in particular as resin used for the said elastic belt, Although it can select suitably according to the objective, For example, a polycarbonate, a fluororesin (ETFE, PVDF), a polystyrene, chloropolystyrene, poly-alpha-methylstyrene Styrene-butadiene copolymer, styrene-vinyl chloride copolymer, styrene-vinyl acetate copolymer, styrene-maleic acid copolymer, styrene-acrylic acid ester copolymer (for example, styrene-methyl acrylate copolymer) Styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-phenyl acrylate copolymer, etc.), styrene-methacrylic acid ester copolymer (for example, Styrene-methyl methacrylate copolymer, styrene-methyl Styrenic resins (styrene or styrene substituted) such as ethyl crylate copolymer, styrene-phenyl methacrylate copolymer, styrene-α-methyl chloroacrylate copolymer, styrene-acrylonitrile-acrylic ester copolymer, etc. Homopolymer or copolymer), methyl methacrylate resin, butyl methacrylate resin, ethyl acrylate resin, butyl acrylate resin, modified acrylic resin (for example, silicone-modified acrylic resin, vinyl chloride resin-modified acrylic resin, Acrylic-urethane resin, etc.), vinyl chloride resin, styrene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, rosin-modified maleic acid resin, phenol resin, epoxy resin, polyester resin, polyester polyurethane resin, polyethylene, polypropylene , Poly Tajien, polyvinylidene chloride, ionomer resins, polyurethane resins, silicone resins, ketone resins, ethylene - ethyl acrylate copolymer, xylene resin, polyvinyl butyral resin, polyamide resin and modified polyphenylene oxide resins. These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as rubber | gum used for the said elastic belt, According to the objective, it can select suitably, For example, natural rubber, butyl rubber, fluororubber, acrylic rubber, EPDM, NBR, acrylonitrile butadiene styrene rubber, isoprene Rubber, styrene-butadiene rubber, butadiene rubber, ethylene-propylene rubber, ethylene-propylene terpolymer, chloroprene rubber, chlorosulfonated polyethylene, chlorinated polyethylene, urethane rubber, syndiotactic 1,2-polybutadiene, epichlorohydrin series Examples thereof include rubber, silicone rubber, fluorine rubber, polysulfide rubber, polynorbornene rubber, and hydrogenated nitrile rubber. These may be used individually by 1 type and may use 2 or more types together.

  The elastomer used for the elastic belt is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a polystyrene-based thermoplastic elastomer, a polyolefin-based thermoplastic elastomer, a polyvinyl chloride-based thermoplastic elastomer, a polyurethane-based heat Examples thereof include a plastic elastomer, a polyamide-based thermoplastic elastomer, a polyurea thermoplastic elastomer, a polyester-based thermoplastic elastomer, and a fluororesin-based thermoplastic elastomer. These may be used individually by 1 type and may use 2 or more types together.

  The conductive agent for adjusting the resistance value used in the elastic belt is not particularly limited and may be appropriately selected depending on the intended purpose. For example, metal powder such as carbon black, graphite, aluminum, nickel; tin oxide, titanium oxide And conductive metal oxides such as antimony oxide, indium oxide, potassium titanate, antimony oxide-tin oxide composite oxide (ATO), and indium oxide-tin oxide composite oxide (ITO). The conductive metal oxide may be coated with insulating fine particles such as barium sulfate, magnesium silicate, and calcium carbonate.

  Further, the surface layer of the elastic belt prevents contamination of the electrostatic latent image carrier by the elastic material, reduces the surface friction resistance to the transfer belt surface, and reduces the adhesion force of the toner, thereby cleaning and secondary transfer properties. What can be increased is required. For example, materials that can use one or more of polyurethane, polyester, epoxy resin, etc. to reduce surface energy and improve lubricity, such as fluororesin, fluorine compound, fluorocarbon, titanium dioxide, silicon car Powders such as bite and particles can be dispersed and used. Further, it is also possible to use a material having a surface energy reduced by forming a fluorine-rich layer on the surface by performing a heat treatment like the fluorine-based rubber material.

  The method for producing the elastic belt is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a centrifugal molding method in which a material is poured into a rotating cylindrical mold to form a belt, or a liquid paint is sprayed. Spray coating to form a film, dipping method in which a cylindrical mold is dipped in a solution of the material, casting method to inject into an inner mold and an outer mold, a compound is wrapped around a cylindrical mold and added For example, a method of performing sulfur polishing.

The method for preventing the elastic belt from stretching is not particularly limited and may be appropriately selected depending on the intended purpose. (1) A method for forming a rubber layer on a core layer having little elongation, (2 And a method of adding a material for preventing elongation to the core layer.
There is no restriction | limiting in particular as a material which comprises the core layer which prevents the said elongation, Although it can select suitably according to the objective, For example, natural fibers, such as cotton and silk; Polyester fiber, nylon fiber, acrylic fiber , Polyolefin fibers, polyvinyl alcohol fibers, polyvinyl chloride fibers, polyvinylidene chloride fibers, polyurethane fibers, polyacetal fibers, polyfluoroethylene fibers, phenol fibers, and other synthetic fibers; carbon fibers, glass fibers, boron fibers, and other inorganic fibers; iron Examples thereof include metal fibers such as fibers and copper fibers, and those made into a woven or yarn shape using these materials are preferably used.
The yarn may be twisted by one or a plurality of filaments, such as one twisted yarn, one-twisted yarn, various twisted yarns, or double yarn. The yarn can also be used after being subjected to an appropriate conductive treatment. Further, the woven fabric can be any woven fabric such as knitted weave, a cross-woven fabric can be used, and a conductive treatment may be used.

There is no restriction | limiting in particular as a manufacturing method of the said core body layer, Although it can select suitably according to the objective, For example, (1) Covering the woven fabric woven in the cylinder shape on a metal mold | die etc. (2) A method of providing a covering layer on one or both sides of a core layer by immersing a woven fabric woven in a cylindrical shape into liquid rubber or the like, and (3) a thread on a mold or the like at an arbitrary pitch. For example, a method of winding in a spiral shape and providing a coating layer thereon may be used.
The thickness of the coating layer depends on the hardness of the coating layer, but if it is too thick, the surface expands and contracts and cracks are likely to occur on the surface layer. Also, it is not preferable that the thickness is too large (about 1 mm or more) because the expansion and contraction of the image is increased and the expansion and contraction of the image is increased.

The transfer unit (the primary transfer unit and the secondary transfer unit) has at least a transfer unit that peels and charges the visible image formed on the electrostatic latent image carrier to the recording medium side. Is preferred. There may be one transfer unit or two or more transfer units. 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 typically plain paper, but is not particularly limited as long as it can transfer an unfixed image after development, and can be appropriately selected according to the purpose. PET for OHP A base or the like can also be used.

The full color image forming apparatus will be described below.
[Tandem type image forming apparatus]
[Transfer means]
The tandem-type image forming apparatus has a plurality of image forming elements including at least an electrostatic latent image carrier (photoconductor), a charging unit, an exposure unit (image exposure unit), a developing unit, and a transfer unit. In this tandem type image forming apparatus, four image forming elements for yellow, magenta, cyan, and black are mounted, and each visible image is created in parallel with the four image forming elements, and is recorded on a recording medium or an intermediate transfer member. Therefore, a full color image can be formed at a higher speed.

  As the tandem type image forming apparatus, (1): as shown in FIG. 7, the surface passes through a transfer position that is a region facing each electrostatic latent image carrier 1 of a plurality of image forming elements. A direct transfer system in which a visible image formed on each electrostatic latent image carrier 1 is sequentially transferred to a moving recording medium S by a transfer means 2; (2): as shown in FIG. After the visible images on the respective electrostatic latent image carriers 1 of the image forming elements are sequentially transferred to the intermediate transfer member 4 by the primary transfer unit 2, the images on the intermediate transfer member 4 are recorded by the secondary transfer unit 5. There is an indirect transfer system that performs batch transfer to the medium S. In FIG. 8, the transfer device 5 serving as a transfer unit is a transfer conveyance belt, but may be a roller shape.

When the direct transfer method (1) shown in FIG. 7 is compared with the indirect transfer method (2) shown in FIG. 8, the direct transfer method (1) is a tandem type image in which the electrostatic latent image carriers 1 are arranged. The sheet feeding device 6 must be disposed upstream of the forming portion T, and the fixing device 7 serving as a fixing unit must be disposed downstream, which increases the size of the recording medium in the conveyance direction. On the other hand, in the indirect transfer method (2), the secondary transfer position can be set relatively freely, and the paper feeding device 6 and the fixing device 7 can be arranged so as to overlap the tandem type image forming unit T. There is an advantage that downsizing is possible.
In the direct transfer method (1), the fixing device 7 is disposed close to the tandem image forming unit T in order not to increase the size in the recording medium conveyance direction. Therefore, the fixing device 7 cannot be disposed with a sufficient margin that the recording medium S can bend, and an impact when the leading end of the recording medium S enters the fixing device 7 (particularly with a thick recording medium). In addition, the fixing device 7 tends to affect upstream image formation due to the speed difference between the recording medium conveyance speed when passing through the fixing device 7 and the recording medium conveyance speed by the transfer conveyance belt. On the other hand, in the indirect transfer method (2), the fixing device 7 can be disposed with a sufficient margin that the recording medium S can be bent, and therefore the fixing device 7 hardly affects image formation.

  For these reasons, indirect transfer systems have recently attracted attention. In this type of color image forming apparatus, as shown in FIG. 8, the transfer residual toner remaining on the electrostatic latent image carrier 1 after the primary transfer is removed by a cleaning device 8 as a cleaning unit, and the electrostatic latent image is thus removed. The surface of the carrier 1 is cleaned to prepare for the image formation again. Further, the transfer residual toner remaining on the intermediate transfer body 4 after the secondary transfer is removed by the intermediate transfer body cleaning device 9 to clean the surface of the intermediate transfer body 4 to prepare for image formation again.

[Fixing process and fixing means]
The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing unit. The fixing unit is not particularly limited and may be appropriately selected depending on the intended purpose. A fixing device having a fixing member and a heat source for heating the fixing member is preferably used.
The fixing member is not particularly limited as long as it can contact each other to form a nip portion, and can be appropriately selected according to the purpose. For example, a combination of an endless belt and a roller, a roller and a roller, The heating method from the surface of the fixing member by a combination of an endless belt and a roller or induction heating can be used in order to reduce the warm-up time and realize energy saving. It is preferable to use it.

  Examples of the fixing member include known heating and pressing means (combination of heating means and pressing means). In the case of a combination of the endless belt and the roller, for example, a combination of a heating roller, a pressure roller, and an endless belt may be used as the heating and pressing unit, and the combination of the roller and the roller may be used. In this case, for example, a combination of a heating roller and a pressure roller can be used.

  When the fixing member is an endless belt, the endless belt is preferably formed of a material having a small heat capacity. For example, an embodiment in which an offset prevention layer is provided on a substrate may be used. Examples of the material for forming the base include nickel and polyimide, and examples of the material for forming the offset prevention layer include silicone rubber and fluorine-based resin.

  When the fixing member is a roller, the cored bar of the roller is preferably formed of an inelastic member to prevent deformation (deflection) due to high pressure. There is no restriction | limiting in particular as this inelastic member, Although it can select suitably according to the objective, For example, high heat conductivity bodies, such as aluminum, iron, stainless steel, brass, are mentioned suitably. Moreover, it is preferable that the surface of the roller is covered with an offset prevention layer. The material for forming the offset prevention layer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include RTV silicone rubber, tetrafluoroethylene-perfluoroalkyl vinyl ether (PFA), and polytetrafluoroethylene. (PTFE).

  In the fixing step, the image by the toner may be transferred to the recording medium, and the recording medium on which the image has been transferred may be passed through the nip portion to fix the image to the recording medium. The image may be simultaneously transferred and fixed to the recording medium at the nip portion. The fixing step may be performed each time the toner of each color is transferred to the recording medium, or may be performed at the same time in a state where the toner of each color is stacked.

The nip portion is formed by bringing at least two fixing members into contact with each other.
The surface pressure of the nip portion is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 55N / cm ² or more, more preferably ^{70~500N / cm 2, 60~300N / cm} 2 Is more preferable. If the surface pressure of the nip portion is too high, the durability of the roller may decrease. On the other hand, when the surface pressure of the nip portion is less than 55 N / cm ² , the offset prevention property may be insufficient.

  The temperature at which the image is fixed to the recording medium by the toner (that is, the surface temperature of the fixing member by the heating means) is not particularly limited and may be appropriately selected depending on the intended purpose. ° C is preferred, and 150 to 220 ° C is more preferred. If the fixing temperature is less than 120 ° C, the fixability may be insufficient, and if it exceeds 240 ° C, it is not preferable in terms of realizing energy saving.

  As the fixing unit, (1) an aspect in which the fixing unit has at least one of a roller and a belt, is heated from a surface that is not in contact with the toner, and the transferred image transferred onto the recording medium is heated and pressed to fix the image. (Internal heating method) and (2) A mode in which the fixing unit has at least one of a roller and a belt, is heated from the surface in contact with the toner, and the transfer image transferred onto the recording medium is fixed by heating and pressing. (External heating method). It is also possible to use a combination of both.

As the internal heating type fixing means (1), for example, the fixing member itself has a heating means inside. Examples of such heating means include a heat source such as a heater and a halogen lamp.
As the (2) external heating type fixing means, for example, at least a part of the surface of at least one of the fixing members is preferably heated by the heating means. There is no restriction | limiting in particular as such a heating means, According to the objective, it can select suitably, For example, an electromagnetic induction heating means etc. are mentioned.

There is no restriction | limiting in particular as said electromagnetic induction heating means, Although it can select suitably according to the objective, What has a means to generate | occur | produce a magnetic field and a means to generate | occur | produce heat | fever by electromagnetic induction, etc. are suitable.
The electromagnetic induction heating means includes, for example, an induction coil disposed so as to be close to the fixing member (for example, a heating roller), a shielding layer provided with the induction coil, and an induction coil of the shielding layer. What consists of an insulating layer provided in the other side of the provided surface is preferable. In this case, it is preferable that the heating roller is formed of a magnetic material or a heat pipe.
The induction coil is arranged in a state of wrapping at least a semi-cylindrical portion on the opposite side of the contact portion between the heating roller and the fixing member (for example, a pressure roller, an endless belt, etc.) of the heating roller. Is preferred.

(Internal heating type fixing means)
FIG. 9 is a belt-type fixing device showing an example of an internal heating type fixing means. The belt-type fixing device 510 in FIG. 9 includes a heating roller 511, a fixing roller 512, a fixing belt 513, and a pressure roller 514.
The fixing belt 513 is stretched by a heating roller 511 and a fixing roller 512 that are rotatably arranged inside, and is heated to a predetermined temperature by the heating roller 511. The heating roller 511 has a built-in heating source 515 and is designed so that the temperature can be adjusted by a temperature sensor 517 attached in the vicinity of the heating roller 511. The fixing roller 512 is rotatably disposed inside the fixing belt 513 and in contact with the inner surface of the fixing belt 513. The pressure roller 514 is in contact with the outer side of the fixing belt 513 and the outer surface of the fixing belt 513 so as to press the fixing roller 512 and is rotatably arranged. The surface hardness of the fixing belt 513 is lower than the surface hardness of the pressure roller 514, and the nip portion N formed between the fixing roller 512 and the pressure roller 514 has an introduction side end and a discharge side of the recording medium S. An intermediate region located between the ends is located closer to the fixing roller 512 than the introduction side end and the discharge side end.

  In the belt-type fixing device 510 shown in FIG. 9, first, the recording medium S on which the toner image T to be fixed is formed is conveyed to the heating roller 511. The toner image T on the recording medium S is heated and melted by the heating roller 511 and the fixing belt 513 heated to a predetermined temperature by the action of the built-in heating source 515. In this state, the recording medium S is inserted into a nip portion N formed between the fixing roller 512 and the pressure roller 514. The recording medium S inserted into the nip N is brought into contact with the surface of the fixing belt 513 that rotates in conjunction with the rotation of the fixing roller 512 and the pressure roller 514 and is pressed when passing through the nip N. The toner image T is fixed on the recording medium S. Next, the recording medium S on which the toner image T is fixed passes between the fixing roller 512 and the pressure roller 514, is peeled off from the fixing belt 513, and is conveyed to a tray (not shown). At this time, the recording medium S is discharged toward the pressure roller 514, and the winding of the recording medium S around the fixing belt 513 is prevented. The fixing belt 513 is cleaned by the cleaning roller 516.

Further, the heat roll type fixing device 515 shown in FIG. 10 includes a heating roller 520 as the fixing member and a pressure roller 530 disposed in contact therewith.
The heating roller 520 has a hollow metal cylinder 521, the surface of which is covered with an offset prevention layer 522, and a heating lamp 523 is disposed therein. The pressure roller 530 includes a metal cylinder 531 and the surface thereof is covered with an offset prevention layer 532. In the pressure roller 530, the metal cylinder 531 may have a hollow shape, and a heating lamp 533 may be disposed therein.
The heating roller 520 and the pressure roller 530 are urged by a spring (not shown), and are rotatably provided in a pressure-contacted state to form a nip portion N. Further, the surface hardness of the offset prevention layer 522 in the heating roller 520 is lower than the surface hardness of the offset prevention layer 532 in the pressure roller 530, and in the nip portion N formed between the heating roller 520 and the pressure roller 530, An intermediate region located between the introduction side end and the discharge side end of the recording medium S is located closer to the heating roller 520 than the introduction side end and the discharge side end.

  In the heat roll type fixing device 515 shown in FIG. 10, first, the recording medium S on which the toner image T to be fixed is formed is conveyed to the nip portion N between the heating roller 520 and the pressure roller 530. The toner T on the recording medium S is heated and melted by the heating roller 520 heated to a predetermined temperature by the action of the built-in heating lamp 523, and at the same time, when passing through the nip portion N, the toner T is heated. The toner image T is fixed on the recording medium S by being pressed by the pressing force of the pressure roller 530. Next, the recording medium S on which the toner image T is fixed passes between the heating roller 520 and the pressure roller 530 and is conveyed to a tray (not shown). At this time, the recording medium S is discharged toward the pressure roller 530, and the recording medium S is prevented from being wound around the pressure roller 530. The heating roller 520 is cleaned by a cleaning roller (not shown).

[External heating type fixing means]
FIG. 11 shows an electromagnetic induction heating type fixing device 570 showing an example of an external heating type fixing unit. The electromagnetic induction heating type fixing device 570 of FIG. 11 includes a heating roller 566, a fixing roller 580, a fixing belt 567, a pressure roller 590, and an electromagnetic induction heating unit 560.
The fixing belt 567 is stretched by a heating roller 566 and a fixing roller 580 that are rotatably arranged inside, and is heated to a predetermined temperature by the heating roller 566.
The heating roller 566 has, for example, a hollow cylindrical magnetic metal member such as iron, cobalt, nickel, or an alloy of these metals. For example, the outer diameter is 20 to 40 mm and the wall thickness is 0.3 to 1.0 mm. It has a low heat capacity and quick temperature rise.

  The fixing roller 580 has, for example, a metal core 581 made of stainless steel or the like, and the surface thereof is formed by covering a heat-resistant silicone rubber with a solid or foamed elastic layer 582. It is disposed inside the fixing belt 567 and rotatably while being in contact with the inner surface of the fixing belt 567. The fixing roller 580 is provided with an outer diameter of about 20 to 40 mm in order to form a nip portion N having a predetermined width between the pressure roller 590 and the fixing roller 580 by the pressing force from the pressure roller 590, and is heated. It is larger than the roller 566. The elastic layer 582 has a thickness of about 4 to 6 mm, and is formed so that the heat capacity of the heating roller 566 is smaller than the heat capacity of the fixing roller 580, thereby shortening the warm-up time of the heating roller 566.

  The pressure roller 590 has a metal core 591 made of a metal cylindrical member having high thermal conductivity such as copper or aluminum, and the surface thereof is covered with an elastic layer 592 having high heat resistance and toner releasability. The fixing roller 580 is in contact with the outer surface of the fixing belt 567 and the outer surface of the fixing belt 567 so as to be in pressure contact with the fixing belt 567, and is rotatably disposed. In addition to the above metal, SUS may be used for the metal core 591.

  The electromagnetic induction heating unit 560 is disposed in the vicinity of the heating roller 566 and in the axial direction of the heating roller 566. The electromagnetic induction heating unit 560 includes an excitation coil 561 that is a magnetic field generation unit, and a coil guide plate 562 around which the excitation coil 561 is wound. The coil guide plate 562 has a semi-cylindrical shape disposed close to the outer peripheral surface of the heating roller 566, and the exciting coil 561 is formed by passing a long exciting coil wire along the coil guide plate 562 in the axial direction of the heating roller 566. It is one that is wound around alternately. The exciting coil 561 is connected to a driving power source (not shown) whose frequency is variable. On the outside of the excitation coil 561, a semi-cylindrical excitation coil core 563 made of a ferromagnetic material such as ferrite is fixed to the excitation coil core support member 564 and is disposed close to the excitation coil 561.

  In the electromagnetic induction heating type fixing device 570 shown in FIG. 11, when the excitation coil 561 of the electromagnetic induction heating unit 560 is energized, an alternating magnetic field is formed around the electromagnetic induction heating unit 560, close to the excitation coil 561, and The heating roller 566 surrounded by the excitation coil 561 is preheated uniformly and efficiently by excitation of overcurrent. The recording medium S on which the toner image T to be fixed is formed is conveyed to the nip N between the fixing roller 580 and the pressure roller 590. The toner image T on the recording medium S is then heated by the fixing belt 567 heated at the contact portion W1 with the heating roller 566 by the heating roller 566 heated to a predetermined temperature by the action of the electromagnetic induction heating unit 560. It is heated and becomes a molten state. In this state, the recording medium S is inserted into a nip portion N formed between the fixing roller 580 and the pressure roller 590. The recording medium S inserted into the nip N is brought into contact with the surface of the fixing belt 567 that rotates in conjunction with the rotation of the fixing roller 580 and the pressure roller 590, and is pressed when passing through the nip N. The toner image T is fixed on the recording medium S.

  Next, the recording medium S on which the toner image T is fixed passes between the fixing roller 580 and the pressure roller 590, is peeled off from the fixing belt 567, and is conveyed to a tray (not shown). At this time, the recording medium S is discharged toward the pressure roller 590 and the winding of the recording medium S around the fixing belt 567 is prevented. The fixing belt 567 is cleaned by a cleaning roller (not shown).

An electromagnetic induction type roll fixing device 525 shown in FIG. 12 includes a fixing roller 520 as the fixing member, a pressure roller 530 arranged in contact with the fixing roller 520, a fixing roller 520 and a pressure roller. The fixing unit includes an electromagnetic induction heating source 540 that heats from the outside.
The fixing roller 520 has a metal core 521, and the surface thereof is formed by covering a heat insulating elastic layer 522, a heat generating layer 523, and a release layer 524 in this order. Further, the pressure roller 530 has a core metal 531, and the surface thereof is formed by covering a heat insulating elastic layer 532, a heat generating layer 533, and a release layer 534 in this order. Note that the release layer 524 and the release layer 534 are formed of tetrafluoroethylene-perfluoroalkyl vinyl ether (PFA).

The fixing roller 520 and the pressure roller 530 are urged by a spring (not shown) so as to be rotatable while being in pressure contact with each other, and form a nip portion N.
The electromagnetic induction heating source 540 is disposed in the vicinity of the fixing roller 520 and the pressure roller 530, respectively, and heats the heat generation layer 523 and the heat generation layer 533 by electromagnetic induction. In the fixing device shown in FIG. 12, the electromagnetic induction heating source 540 preheats the fixing roller 520 and the pressure roller 530 uniformly and efficiently. In addition, since the combination of the roller and the roller, a high surface pressure of the nip portion N can be easily realized.

[Cleaning process and cleaning means]
The cleaning step is a step of removing toner remaining on the electrostatic latent image carrier, and can be suitably performed by a cleaning unit. Further, the developing means has a developer carrier that abuts on the surface of the electrostatic latent image carrier, and develops the electrostatic latent image formed on the electrostatic latent image carrier and By collecting the residual toner on the latent image carrier, cleaning can be performed without providing a cleaning means (cleaning-less method).

  The cleaning means 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, Examples thereof include an electrostatic brush cleaner, a magnetic roller cleaner, a cleaning blade, a brush cleaner, and a web cleaner. Among these, a cleaning blade having a high toner removing ability, a small size and an inexpensive price is particularly preferable. Examples of the material of the rubber blade used for the cleaning blade include urethane rubber, silicone rubber, fluorine rubber, chloroprene rubber, butadiene rubber, and the like. Among these, urethane rubber is particularly preferable.

  FIG. 13 is an explanatory diagram showing an enlarged view of the vicinity of the contact portion 615 with the electrostatic latent image carrier in the cleaning blade 613. The cleaning blade 613 is provided with a toner blocking surface 617 that forms a space S that expands from the contact portion 615 toward the upstream side in the rotation direction of the electrostatic latent image carrier with the surface of the photosensitive drum 1. Yes. In the present embodiment, the toner blocking surface 617 extends from the contact portion 615 to the upstream side in the rotation direction of the photosensitive drum 1 so that the space S has an acute angle.

As shown in FIG. 13, the toner blocking surface 617 is provided with a coating portion 618 as a high friction portion having a higher friction coefficient than the cleaning blade 613. The coating portion 618 is formed of a material (high friction material) having a higher friction coefficient than the material forming the cleaning blade 613. Examples of such a high friction material include DLC (diamond-like carbon). The high friction material is not limited to DLC. The coating unit 618 is provided in a range where the toner blocking surface 617 does not contact the surface of the photosensitive drum 1.
Although not shown, the cleaning unit includes a toner collection blade that collects the residual toner scraped by the cleaning blade, a toner collection coil that conveys the residual toner collected by the toner collection blade to the collection unit, and the like. ing.

[Cleaning-less image forming apparatus]
FIG. 14 is a schematic diagram illustrating an example of a cleaningless image forming apparatus in which the developing unit also serves as the cleaning unit.
In FIG. 14, 1 is a photosensitive drum as an electrostatic latent image carrier, 620 is a brush charging device as contact charging means, 603 is an exposure device as exposure means, 604 is a developing device as development means, and 640 is a supply. A paper cassette, 650 is a roller transfer means, and P is a recording medium.

  In this cleaningless image forming apparatus, the untransferred toner on the surface of the photosensitive drum 1 reaches the position of the contact charging device 620 that is in contact with the photosensitive drum 1 by the subsequent rotation of the photosensitive drum 1, and reaches the photosensitive drum 1. The toner is temporarily collected by a magnetic brush portion (not shown) of the brush charging member 621 that is in contact with the toner, and the collected toner is discharged again to the surface of the photosensitive drum 1, and finally the developer in the developing device 604. At the same time, the toner is collected by the developer carrier 631 and the photosensitive drum 1 is repeatedly used for image formation.

  Here, the developing means 604 also serves as a cleaning means that the toner slightly remaining on the photosensitive drum 1 after the transfer is developed bias (between the DC voltage applied to the developer carrier 631 and the surface potential of the photosensitive drum 1). It means a method of collecting by (potential difference). In such a cleaningless image forming apparatus in which the developing unit also serves as a cleaning unit, the transfer residual toner is collected by the developing unit 604 and is used after the next step, so that waste toner is eliminated, maintenance is free, and a cleanerless system is used. Therefore, the advantage in terms of space is remarkably large, and the image forming apparatus can be greatly downsized.

[Other processes and other 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.

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

  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.

[Image Forming Apparatus and Image Forming Method]
Next, one mode for carrying out the image forming method by the image forming apparatus of the present invention will be described with reference to FIG. An image forming apparatus 100 shown in FIG. 15 includes a photosensitive drum 10 as an electrostatic latent image carrier, a charging roller 20 as a charging unit, exposure 30 by an exposure device as an exposure unit, and a developing device as a developing unit. 40, an intermediate transfer member 50, a cleaning blade 60 as a cleaning means, and a static elimination lamp 70 as a static elimination means.

  The intermediate transfer member 50 is an endless belt, and is designed so as to be movable in the direction of the arrow in the figure by three rollers 51 that are arranged on the inner side and stretch the belt. Part of the three rollers 51 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. The intermediate transfer member 50 is provided with a cleaning blade 90 in the vicinity thereof, and the transfer capable of applying a transfer bias for transferring (secondary transfer) a visible image (toner image) to the recording medium 95. A transfer roller 80 serving as a means is arranged to face. Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the toner image on the intermediate transfer member 50 is connected to the electrostatic latent image carrier 10 and the intermediate transfer member in the rotation direction of the intermediate transfer member 50. It is disposed between the contact portion with the body 50 and the contact portion between the intermediate transfer member 50 and the recording medium 95.

  The developing device 40 includes a developing belt 41 as a developer carrying member, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C provided around the developing belt 41. The black developing unit 45K includes a developer accommodating portion 42K, a developer supplying roller 43K, and a developing roller 44K. The yellow developing unit 45Y includes a developer accommodating portion 42Y, a developer supplying roller 43Y, and a developing roller 44Y. The magenta developing unit 45M includes a developer accommodating portion 42M, a developer supplying roller 43M, and a developing roller 44M, and the cyan developing unit 45C includes a developer accommodating portion 42C and a developer supplying roller 43C. And a developing roller 44C. Further, the developing belt 41 is an endless belt, is rotatably stretched by a plurality of belt rollers, and a part thereof is in contact with the electrostatic latent image carrier 10.

  In the image forming apparatus 100 shown in FIG. 15, for example, the charging roller 20 charges the photosensitive drum 10 uniformly. The exposure device performs imagewise exposure 30 on the photosensitive drum 10 to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum 10 is developed by supplying toner from the developing device 40 to form a toner image. The toner image is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied from the roller 51 and further transferred (secondary transfer) onto the recording medium 95. As a result, a transfer image is formed on the recording medium 95. The residual toner on the electrostatic latent image carrier 10 is removed by the cleaning blade 60, and the charge on the electrostatic latent image carrier 10 is once removed by the static elimination lamp 70.

  Another mode for carrying out the image forming method by the image forming apparatus of the present invention will be described with reference to FIG. The image forming apparatus 100 shown in FIG. 16 does not include the developing belt 41 as the developer carrying member in the image forming apparatus 100 shown in FIG. 15, and the black developing unit 45 </ b> K is disposed around the electrostatic latent image carrying member 10. The yellow developing unit 45Y, the magenta developing unit 45M, and the cyan developing unit 45C are configured in the same manner as the image forming apparatus 100 shown in FIG. Show. In FIG. 16, the same components as those in FIG. 15 are denoted by the same reference numerals.

  A schematic view of FIG. 20 shows another example of the full-color image forming apparatus of the present invention. FIG. 21 is a schematic diagram showing still another example of the full-color image forming apparatus of the present invention. In FIG. 20, reference numeral 321 is a photosensitive member, 323 is an exposure unit, 325 is a transfer unit, 326 is a recording medium, 327 is a fixing unit, and 341 to 344 are image forming elements for each color (black, yellow, magenta, cyan). Show. In FIG. 21, reference numeral 311 denotes a charging means, 321 denotes a photosensitive member, 323 denotes an exposure means, 324 denotes a developing means, 325 denotes a transfer means, 326 denotes a recording medium, 327 denotes a fixing means, 330 denotes a cleaning means, and 351 to 354 denote reference numerals. Each color (black, yellow, magenta, cyan) image forming element, 355 is an intermediate transfer member, and 356 is a roller.

[Tandem type image forming apparatus and image forming method]
Another mode for carrying out the image forming method by the image forming apparatus of the present invention will be described with reference to FIG. The image forming apparatus shown in FIG. 17 is a tandem type color image forming apparatus. The tandem image forming apparatus 100 includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.

The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16, and can be rotated clockwise in FIG. In the vicinity of the support roller 15, an intermediate transfer member cleaning unit 17 for removing residual toner on the intermediate transfer member 50 is disposed. A tandem in which four image forming units 18 of yellow, cyan, magenta, and black are arranged to face each other on the intermediate transfer member 50 stretched between the support roller 14 and the support roller 15 along the conveyance direction. A mold developing device 120 is disposed. An exposure unit 21 is disposed in the vicinity of the tandem developing device 120. On the opposite side of the intermediate transfer member 50 from the side where the tandem developing device 120 is arranged, the secondary transfer unit 22 is arranged. In the secondary transfer unit 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the recording medium conveyed on the secondary transfer belt 24 and the intermediate transfer member 50 are in contact with each other. Is possible. A fixing unit 25 is disposed in the vicinity of the secondary transfer unit 22.
In the tandem image forming apparatus 100, a reversing device 28 for reversing the recording medium in order to form an image on both sides of the recording medium is disposed in the vicinity of the secondary transfer unit 22 and the fixing unit 25. .

Next, formation of a full-color image (color copy) using the tandem developing device 120 will be described. That is, first, a document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and the document is set on the contact glass 32 of the scanner 300. 400 is closed.
When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the contact glass 32. Immediately after that, the scanner 300 is driven, and the first traveling body 33 and the second traveling body 34 travel. At this time, light from the light source is emitted from the first traveling body 33 and reflected light from the document surface is reflected by the mirror in the second traveling body 34 and is received by the reading sensor 36 through the imaging lens 35 to be color. An original (color image) is read and used as black, yellow, magenta, and cyan image information.

Each image information of black, yellow, magenta, and cyan is stored in each image forming unit 18 (black image forming unit, yellow image forming unit, magenta image forming unit, and cyan image forming unit) in the tandem developing device 120. Each image forming unit forms black, yellow, magenta, and cyan toner images.
That is, each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem developing device 120 is respectively static, as shown in FIG. An electrostatic latent image carrier 10 (an electrostatic latent image carrier 10K for black, an electrostatic latent image carrier 10Y for yellow, an electrostatic latent image carrier 10M for magenta, and an electrostatic latent image carrier 10C for cyan); A charger 60 that uniformly charges the electrostatic latent image carrier, and the electrostatic latent image carrier is exposed like an image corresponding to each color image based on each color image information (L in FIG. 18). An exposure unit that forms an electrostatic latent image corresponding to each color image on the electrostatic latent image carrier, and each color toner (black toner, yellow toner, magenta toner, and cyan toner) for the electrostatic latent image. Using current A developing device 61 for forming a toner image with each color toner, a transfer charger 62 for transferring the toner image onto the intermediate transfer member 50, a cleaning means 63, and a static eliminator 64. Each monochrome image (black image, yellow image, magenta image, and cyan image) can be formed based on the image information of each color. The black image, the yellow image, the magenta image, and the cyan image formed in this way are respectively transferred to the black electrostatic latent image carrier 10K on the intermediate transfer member 50 that is rotationally moved by the support rollers 14, 15 and 16. Black image formed on top, yellow image formed on electrostatic latent image carrier 10Y for yellow, magenta image formed on electrostatic latent image carrier 10M for magenta, and electrostatic latent image carrier for cyan The cyan image formed on 10C is sequentially transferred (primary transfer). Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

  On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed the recording medium from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143, and one sheet at a time by the separation roller 145. The paper is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 to stop. Alternatively, the recording roller 142 is rotated to feed out the recording medium on the manual feed tray 54, separated one by one by the separation roller 52, put into the manual feed path 53, and abutted against the registration roller 49 and stopped. The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the recording medium. Then, the registration roller 49 is rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 50, and the recording medium is sent between the intermediate transfer member 50 and the secondary transfer unit 22. Then, by transferring (secondary transfer) the composite color image (color transfer image) onto the recording medium by the secondary transfer means 22, a color image is transferred and formed on the recording medium. The residual toner on the intermediate transfer member 50 after image transfer is cleaned by the intermediate transfer member cleaning means 17.

  The recording medium on which the color image has been transferred is conveyed by the secondary transfer means 22 and sent to the fixing means 25, where the combined color image (color transfer image) is generated by heat and pressure. Is fixed on the recording medium. After that, the recording medium is switched by the switching claw 55 and discharged by the discharge roller 56 and stacked on the paper discharge tray 57. Alternatively, the recording medium is switched by the switching claw 55 and reversed by the reversing device 28 and led again to the transfer position. After the image is also recorded on the back surface, the image is discharged by the discharge roller 56 and stacked on the discharge tray 57.

[Process cartridge]
The process cartridge for a full-color image forming apparatus of the present invention forms at least a photosensitive member, a charging unit that uniformly charges the surface of the photosensitive member, and image exposure on the uniformly charged surface of the photosensitive member to form an electrostatic latent image. An exposure means (image exposure means), a developing means for developing the formed electrostatic latent image using the toner of the present invention (easily stored and transported and excellent in handleability), developed Other means such as a transfer means for transferring the toner image to the recording medium and one means selected from a cleaning means for removing the toner remaining on the surface of the photoconductor after the transfer are further integrated. The image forming apparatus main body having the above-described means is configured to be detachable and can be suitably used for toner replenishment.
The developing means includes at least a developer container that contains the developer of the present invention, and an electrostatic latent image carrier that carries and conveys the developer contained in the developer container. Furthermore, a layer thickness regulating member for regulating the thickness of the toner layer to be carried may be provided.
The process cartridge of the present invention can be detachably provided in various electrophotographic apparatuses, facsimiles, and printers, and is preferably provided detachably in the above-described image forming apparatus.

Here, for example, as shown in FIG. 19, the process cartridge includes a photosensitive member 101, and further includes a charging unit 102, a developing unit 104, and a cleaning unit 107, and further includes other members as necessary. Do it. The process cartridge example of FIG. 19 has a transfer means 108 for transferring a developed toner image on the photoreceptor 101 to a recording medium (image receiving paper) 105.
As the photoreceptor 101, the above-described one can be used. A light source capable of writing with high resolution is used for the exposure means 103. An arbitrary charging member is used for the charging unit 102.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. In the following, “part” means mass part, and “%” means mass%.

A carrier (ferrite carrier) used for a two-component developer was produced as follows.
(Carrier production)
A coating material having the following composition was dispersed with a stirrer for 10 minutes to prepare a coating solution. The coating solution and 5000 parts of a core material (Mn ferrite particles, mass average particle size = 35 μm) were placed in a fluidized bed and The coating liquid was applied to the core material by applying the coating liquid while forming a swirl flow provided with stirring blades. The obtained coated product was baked in an electric furnace at 250 ° C. for 2 hours to produce a carrier.
[Composition of coating material]
Toluene 450 parts Silicone resin (SR2400, manufactured by Toray Dow Corning Silicone,
Nonvolatile content 50% by mass) 450 parts Aminosilane (SH6020, manufactured by Toray Dow Corning Silicone) 10 parts Carbon black 10 parts

  Also, “preparation of aqueous phase”, “synthesis of low molecular weight polyester”, “synthesis of polyester prepolymer”, “synthesis of ketimine”, and “masterbatch (MB)” for the preparation of toner by polymer elongation method Was done. Furthermore, a release agent dispersion (wax dispersion) for use in Examples and Comparative Examples was prepared as follows.

(Preparation of aqueous phase)
In a reaction vessel equipped with a stirrer and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 83 parts of styrene, 83 parts of methacrylic acid, When 110 parts of butyl acrylate and 1 part of ammonium persulfate were charged and stirred at 400 rpm for 15 minutes, a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and an aqueous vinyl resin (a copolymer of sodium salt of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate). A dispersion [fine particle dispersion 1] was obtained. The volume average particle diameter of [fine particle dispersion 1] measured by LA-920 was 105 nm. A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component. The Tg of the resin was 59 ° C., and the mass average molecular weight was 150,000.
Subsequently, 990 parts of water, 83 parts of [fine particle dispersion 1], 37 parts of a 48.5% aqueous solution of sodium dodecyldiphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries) and 90 parts of ethyl acetate are mixed and stirred. A milky white liquid was obtained. This is called [Aqueous Phase 1].

(Synthesis of low molecular weight polyester)
In a reaction vessel equipped with a condenser, stirrer and nitrogen inlet tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 2-mole adduct, 208 parts terephthalic acid, 46 parts adipic acid, and Add 2 parts of dibutyltin oxide, react for 8 hours at 230 ° C under normal pressure, and then react for 5 hours under reduced pressure of 10-15mmHg, then put 44 parts of trimellitic anhydride into the reaction vessel, 180 ° C at normal pressure For 2 hours to obtain [Low molecular polyester 1]. [Low molecular polyester 1] had a number average molecular weight of 2500, a weight average molecular weight of 6700, a Tg of 43 ° C., and an acid value of 255 mgKOH / g.

(Synthesis of polyester prepolymer)
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction pipe, 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, reacted at 230 ° C. at normal pressure for 8 hours, and further reacted at reduced pressure of 10 to 15 mmHg for 5 hours to obtain [Intermediate Polyester 1]. [Intermediate Polyester 1] had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, Tg of 55 ° C., an acid value of 0.55 mgKOH / g, and a hydroxyl value of 515 mgKOH / g.
Next, 410 parts of [Intermediate polyester 1], 89 parts of isophorone diisocyanate and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Polymer 1] was obtained. [Prepolymer 1] had a free isocyanate mass% of 1.53%.

(Synthesis of ketimine)
In a reaction vessel equipped with a stirrer 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 obtain [ketimine compound]. The amine value of the [ketimine compound] was 418 mgKOH / g.

(Production of master batch (MB))
1200 parts of water, carbon black (Printex 35 [DBP oil absorption = 42 ml / 100 mg, pH = 9.5], manufactured by Dexa) 540 parts, polyester resin 1200 parts are added, and mixed with a Henschel mixer (manufactured by Mitsui Mining). The mixture was kneaded at 150 ° C. for 30 minutes using two rolls, rolled and cooled, and pulverized with a pulverizer to obtain a [masterbatch].

(Preparation of release agent dispersant 1)
9 parts of paraffin wax having a melting point of 75 ° C., 21 parts of [low molecular weight polyester 1], 64 parts of ethyl acetate, vinyl polymer (acrylic acid methyl ester-acrylic acid polyester oligomer copolymer (SP value: 13.0, weight average) (Molecular weight: 2.9 × 10 ⁴ ) A crystallization liquid obtained by heating a mixture consisting of 6 parts to 78 ° C. and then cooling was put into a bead mill disperser and dispersed for 2 hours to obtain a release agent dispersion liquid 1. .

(Preparation of release agent dispersion 2)
Same as the preparation of the release agent dispersion liquid 1 except that the vinyl polymer is a methacrylic acid methyl ester-methacrylic acid polyester oligomer copolymer (SP value: 10.3, weight average molecular weight: 0.6 × 10 ⁴ ). Thus, a release agent dispersion 2 was prepared.

(Preparation of release agent dispersion 3)
Same as the preparation of the release agent dispersion 1 except that the vinyl polymer was a methacrylic acid methyl ester-methacrylic acid polyester oligomer copolymer (SP value: 12.1, weight average molecular weight: 1.7 × 10 ⁴ ). Thus, a release agent dispersion 3 was prepared.

(Preparation of release agent dispersion 4)
Preparation of release agent dispersion 1 except that instead of vinyl polymer, methacrylic acid methyl ester-butyl acrylate copolymer (SP value: 11.2, weight average molecular weight: 2.0 × 10 ⁴ ) was used. In the same manner as described above, a release agent dispersion 4 was prepared.

(Preparation of release agent dispersion 5)
Release agent dispersion 1 except that instead of the vinyl polymer, polyethylene, polystyrene, polyacrylonitrile, butyl acrylate graft copolymer (SP value: 11.2, weight average molecular weight: 1.3 × 10 ⁴ ) was used. In the same manner as in the above, release agent dispersion 5 was prepared.

(Preparation of release agent dispersion 6)
A release agent dispersion 6 was prepared in the same manner as the release agent dispersion 1 except that the release agent was carnauba wax having a melting point of 85 ° C.

[Example 1]
(Create oil phase)
In a container equipped with a stirring blade, 260 parts of the release agent dispersion 1 and 100 parts of ethyl acetate were charged. Next, while stirring the contents of the container, 56 parts of [Master batch 1] and 184 parts of [Low molecular weight polyester 1] were added to the container and mixed for 1 hour to obtain [Raw material solution 1].
600 parts of [Raw Material Solution 1] was transferred to another container and mixed with a TK homomixer at a rotation speed of 8000 rpm for 1 hour to obtain [Pigment / WAX Dispersion 1]. The solid content concentration of [Pigment / WAX Dispersion 1] was 55%.

(Emulsification / dispersion / dissolution / washing / drying)
600 parts of [Pigment / WAX Dispersion 1], 60 parts of [Prepolymer 1], and 4.6 parts of [Ketimine Compound 1] are put in a container, and 1 at 5000 rpm with a TK homomixer (manufactured by Koki Co., Ltd.). After mixing for 1 minute, 1200 parts of [Aqueous Phase 1] was added to the container and mixed with a TK homomixer at 13,000 rpm for 1 minute to obtain [Emulsion Slurry 1]. [Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 40 ° C. for 4 hours to obtain [Dispersion slurry 1]. [Dispersion Slurry 1] had a volume average particle size of 5.16 μm and a number average particle size of 4.56 μm (measured with Multisizer II).

Subsequently, 100 parts of [Dispersion Slurry 1] were filtered under reduced pressure, 100 parts of ion-exchanged water was added to the filter cake, and the mixture was mixed for 10 minutes at 12000 rpm using a TK homomixer, followed by filtration. To the obtained filter cake, 300 parts of ion-exchanged water was added, mixed for 10 minutes at 12000 rpm using a TK homomixer, and then filtered twice. 20 parts of a 10 wt% aqueous sodium hydroxide solution was added to the obtained filter cake, mixed at 12000 rpm for 30 minutes using a TK homomixer, and then filtered under reduced pressure. To the obtained filter cake, 300 parts of ion-exchanged water was added, mixed at 12000 rpm for 10 minutes using a TK homomixer, and then filtered. To the obtained filter cake, 300 parts of ion-exchanged water was added, mixed for 10 minutes at 12000 rpm using a TK homomixer, and then filtered twice. Further, 20 parts of 10 wt% hydrochloric acid was added to the obtained filter cake, and the mixture was mixed for 10 minutes at 12000 rpm using a TK homomixer, and then filtered. To the obtained filter cake, 300 parts of ion-exchanged water was added, mixed for 10 minutes at 12000 rpm using a TK homomixer, and then filtered twice to obtain a filter cake.
The obtained 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 particles.

(Production of toner)
To 100 parts of the obtained toner base particles, 0.8 part of silica having a hydrophobized average particle diameter of 12 nm (product name “RX200” manufactured by Nippon Aerosil Co., Ltd.) is added, and surface treatment is performed using a Henschel mixer. Toner 1 was prepared by a conventional method.

[Example 2]
A toner 2 was obtained in the same manner as in Example 1 except that the release agent dispersion 2 was used instead of the release agent dispersion 1 in Example 1.
Example 3
A toner 3 was obtained in the same manner as in Example 1 except that the release agent dispersion 3 was used instead of the release agent dispersion 1 in Example 1.
Example 4
In Example 1, 160 parts of [low molecular polyester 1], vinyl polymer (acrylic acid methyl ester-acrylic acid polyester oligomer copolymer (SP value: 13.0, weight average molecular weight: 2.9 × 10 ⁴ )) Toner 4 was obtained in the same manner as in Example 1 except that the amount was 24 parts.
Example 5
In Example 1, 130 parts of [low molecular weight polyester 1], vinyl polymer (acrylic acid methyl ester-acrylic acid polyester oligomer copolymer (SP value: 13.0, weight average molecular weight: 2.9 × 10 ⁴ )) Toner 5 was obtained in the same manner as in Example 1 except that the amount was 54 parts.
Example 6
A toner 6 was obtained in the same manner as in Example 1 except that the release agent dispersion 6 was used instead of the release agent dispersion 1 in Example 1.

[Comparative Example 1]
In Example 1, a toner 7 was obtained in the same manner as in Example 1 except that the release agent dispersion 4 was used instead of the release agent dispersion 1.

[Comparative Example 2]
A toner 8 was obtained in the same manner as in Example 1 except that the release agent dispersion 5 was used instead of the release agent dispersion 1 in Example 1.

  The toners of Examples 1 to 6 and Comparative Examples 1 and 2 thus obtained were measured for toner physical properties and image density and evaluated for fusing as follows. The results are shown in Tables 1 and 2.

(Toner particle size)
The average particle size and the particle size distribution of the toner are determined by the car Coulter counter method. Examples of the measuring device for the particle size distribution of toner particles include Coulter Counter TA-II and Coulter Multisizer II (both manufactured by Coulter). In the present invention, measurement was performed using a Coulter Counter TA-II type connected to an interface (manufactured by Nikka Giken Co., Ltd.) for outputting number distribution and volume distribution and a PC 9801 personal computer (manufactured by NEC).

The measurement method is described below.
First, 0.1 to 5 ml of a surfactant (preferably alkyl benzene sulfonate) is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution. Here, the electrolytic solution is a solution prepared by preparing a 1% NaCl aqueous solution using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the measurement device is used to measure the volume and number of toner particles or toner using a 100 μm aperture as an aperture. Volume distribution and number distribution are calculated.
As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 Less than 35 to 8.00 μm; less than 8.00 to less than 10.08 μm; less than 10.08 to less than 12.70 μm; less than 12.70 to less than 16.00 μm; less than 16.00 to less than 20.20 μm; Uses 13 channels of less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm, and targets particles having a particle size of 2.00 μm to less than 40.30 μm. The volume-based volume average particle diameter (Dv) obtained from the volume distribution according to the present invention and the number average particle diameter (Dn) obtained from the number distribution and the ratio Dv / Dn were obtained.

(Molecular weight measurement)
The molecular weight according to the present invention is measured by GPC (gel permeation chromatography) as follows. Resin prepared by stabilizing the column in a heat chamber at 40 ° C., and flowing THF (tetrahydrofuran) as a solvent at a flow rate of 1 ml / min to the column at this temperature to prepare a sample concentration of 0.05 to 0.06% by weight. Measurement is performed by injecting 50 to 200 μl of a THF sample solution. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of the prepared calibration curve and the number of counts using several types of monodisperse polystyrene standard samples. As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical Co. Or molecular weight made by Toyo Soda Industry Co., Ltd. is 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9. It is suitable to use x10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ , and use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.

(Glass transition point Tg (℃))
The glass transition point is measured with a Rigaku THRMOFLEX TG8110 manufactured by Rigaku Corporation at a temperature increase rate of 10 ° C./min.
A method for measuring Tg will be outlined. As an apparatus for measuring Tg, a TG-DSC system TAS-100 manufactured by Rigaku Corporation was used.
First, about 10 mg of a sample is placed in an aluminum sample container, which is placed on a holder unit and set in an electric furnace. First, after heating from room temperature to 150 ° C. at a temperature rising rate of 10 ° C./min, the sample was allowed to stand at 150 ° C. for 10 minutes, the sample was cooled to room temperature and allowed to stand for 10 minutes, and the temperature rising rate was again increased to 150 ° C. under a nitrogen atmosphere. DSC measurement was carried out by heating at / min. Tg was calculated from the contact point between the tangent line of the endothermic curve near the Tg and the base line using the analysis system in the TAS-100 system.

(Electric charge evaluation)
(1) 15 seconds stirring charge amount Each toner 10g and ferrite carrier 100g obtained are placed in a stainless steel pot up to 30% of the internal volume in an environment with a temperature of 28 ° C and a humidity of 80%, and the stirring speed of 100 rpm is 15 seconds. The mixture was stirred, and the charge amount (μC / g) of the toner was measured by a blow-off method [manufactured by Toshiba Chemical Corporation: using TB-200].
(2) Charge amount for 10 minutes stirring Charge amount was measured in the same manner as in the above (1) except that the stirring time of 15 seconds in (1) was changed to 10 minutes.

(Fixability evaluation)
Using a device in which the fixing unit of a Ricoh copier (MF2200) using a Teflon (registered trademark) roller as a fixing roller was modified, type 6200 paper manufactured by Ricoh was set in this and a copying test was performed. The cold offset temperature (fixing lower limit temperature) and the hot offset temperature (hot offset resistant temperature) were determined by changing the fixing temperature. The minimum fixing temperature of the conventional low-temperature fixing toner is about 140 to 150 ° C. The evaluation conditions for low-temperature fixing are as follows: the paper feed linear velocity is 120 to 150 mm / sec, the surface pressure is 1.2 kgf / cm ² , the nip width is 3 mm, and the high temperature offset is the paper feed linear velocity of 50 mm / sec. The surface pressure was set to 2.0 kgf / cm ² and the nip width was 4.5 mm.

(Heat resistant storage stability)
After the toner was stored at 55 ° C. for 8 hours, it was sieved with a 42 mesh sieve for 2 minutes, and the residual ratio on the wire mesh was regarded as heat resistant storage stability. A toner having better heat-resistant storage stability has a lower residual ratio. The following four levels were evaluated.
×: 30% or more △: 20-30%
○: 10 to 20%
A: Less than 10%

<Image density>
About each obtained developer, the adhesion amount of each developer is 1.00 ± on copy paper (TYPE6000 <70W>, manufactured by Ricoh) using a tandem type color electrophotographic apparatus (image Neo 450, manufactured by Ricoh). A solid image of 0.05 mg / cm ² was formed. The solid image was repeatedly formed on 8000 copy sheets. The image density of the obtained solid image was visually observed at the initial stage and after endurance of 8000 sheets, and evaluated based on the following criteria. The higher the image density obtained, the higher the density image can be formed. This evaluation corresponds to an embodiment of the toner container, the process cartridge, the image forming apparatus, and the image forming method of the present invention.

[Evaluation criteria]
(Double-circle): The image density did not change and the high image quality was obtained at the initial stage and after the endurance of 8000 sheets.
A: After 8000 sheets were used, the image density was slightly lowered and the image quality was lowered.
X: After the endurance of 8000 sheets, the image density was remarkably lowered and the image quality was greatly lowered.

<Fusion>
Further, after the image formation, the fusion of the toner to the OPC photoreceptor was visually observed and evaluated based on the following criteria.
[Evaluation criteria]
○: No fusion of toner to the photoreceptor was observed.
X: Fusion of toner to photoreceptor was observed.

(Evaluation results)
From the above evaluation results, the toner of the present invention has good heat-resistant storage stability, a stable charge amount, and hardly causes toner fusion, so that a high-quality image can be obtained over a long period of time.

(Reference in FIG. 1)
310 Charging roller 311 Core metal 312 Resistance adjustment layer 313 Protective layer (reference numerals in FIGS. 2 and 3)
310 Charging roller 314 Corona charger 321 Photosensitive drum 323 Exposure means 324 Development means 325 Transfer means 326 Recording medium 327 Fixing means 330 Cleaning means 331 Static elimination device (reference numeral in FIG. 4)
302 Spacer 303 Spring 304 Power supply 310 Charging roller 311 Charging roller shaft 321 Photosensitive drum H Minute gap (reference numeral in FIG. 5)
1 Photosensitive drum 401 Casing 401
402 Developing roller 411 Agitator 411
412 Supply roller 412
413 Regulating blade (reference numeral in FIG. 6)
1 Photosensitive drum 424 Two-component developing device 441 Screw 441
442 Development sleeve 443 Doctor blade (reference numerals in FIGS. 7 and 8)
1 Electrostatic latent image carrier (photosensitive drum)
2 Transfer means (FIG. 7), primary transfer means (FIG. 8)
3 Conveying belt 4 Intermediate transfer member 5 Secondary transfer unit 6 Paper feeding device 7 Fixing unit 8 Cleaning unit 9 Intermediate transfer unit cleaning unit S Recording medium S
T Toner image (reference numeral in FIG. 9)
510 Belt-type fixing device 511 Heating roller 512 Fixing roller 513 Fixing belt 514 Pressure roller 515 Heating source 516 Cleaning roller 517 Temperature sensor S Recording medium T Toner image (reference numeral in FIG. 10)
515 Heat roll type fixing device 520 Heating roller 530 Pressure roller 521 Metal cylinder 522 Offset prevention layer 523 Heating lamp 531 Metal cylinder 532 Offset prevention layer 533 Heating lamp (reference numeral in FIG. 11)
560 Electromagnetic induction heating means 561 Excitation coil 562 Coil guide plate 563 Excitation coil core 564 Excitation coil core support member 566 Heating roller 567 Fixing belt 570 Electromagnetic induction heating type fixing device 580 Fixing roller 581 Core metal 582 Elastic layer 590 Pressure roller 591 Core metal 592 Elastic layer S Recording medium T Toner image (reference numeral in FIG. 12)
520 Fixing roller 521 Core metal 522 Heat insulation elastic layer 523 Heat generation layer 524 Release layer 525 Roll fixing device 530 Pressure roller 540 Electromagnetic induction heating source 531 Core metal 532 Heat insulation elastic layer 533 Heat generation layer 534 Release layer N Nip (see FIG. 13 sign)
1 Photosensitive drum 613 Cleaning blade 613
615 Contact portion 617 Toner blocking surface 618 Coating portion S Space (reference numeral in FIG. 14)
1 Photosensitive drum 603 Exposure device 604 Development device 620 Brush charging device 621 Brush charging member 631 Developer carrier 640 Paper feed cassette 650 Roller transfer means P Recording medium (reference numerals in FIGS. 15 and 16)
10 Photosensitive drum 10K Electrostatic latent image carrier for black 10Y Electrostatic latent image carrier for yellow 10M Electrostatic latent image carrier for magenta 10C Electrostatic latent image carrier for cyan 14 Support roller 15 Support roller 16 Support roller 17 Intermediate transfer cleaning means 18 Image forming means 20 Charging roller 21 Exposure means 22 Secondary transfer means 23 Roller 24 Secondary transfer belt 25 Fixing means 26 Fixing belt 27 Pressure roller 28 Reversing device 30 Exposure 32 Contact glass 33 First traveling body 34 Second traveling body 35 Imaging lens 36 Reading sensor 40 Developing device 41 Developing belt 42K Developer container 42Y Developer container 42M Developer container 42C Developer container 43K Developer supply roller 43Y Developer supply roller 43M Developer Supply roller 43C Developer supply roller 44K Development roller 44Y Development roller Roller 44M Development roller 44C Development roller 45K Black development unit 45Y Yellow development unit 45M Magenta development unit 45C Cyan development unit 49 Registration roller 50 Intermediate transfer member 51 Roller 52 Separation roller 53 Manual feed path 54 Manual feed tray 55 Switching Claw 56 Discharge roller 57 Discharge tray 58 Corona charger 60 Cleaning means 61 Developer 62 Transfer charger 63 Cleaning means 64 Charger 70 Charger lamp 80 Transfer roller 90 Cleaning means 95 Recording medium 100 Image forming apparatus (FIGS. 17 and 18) Sign)
10 electrostatic latent image carrier 10K black electrostatic latent image carrier 10Y yellow electrostatic latent image carrier 10M magenta electrostatic latent image carrier 10C cyan electrostatic latent image carrier 14 support roller 15 support roller 16 Support roller 50 Intermediate transfer member 60 Charger 61 Developer 62 Transfer charger 63 Cleaning means 64 Charger L Exposure 100 Tandem type image forming apparatus 101 Electrostatic latent image carrier 102 Charging means 103 Exposure means 104 Development means 105 Recording medium 107 Cleaning means 108 Transfer means 120 Tandem type developing device 130 Document table 142 Paper feed roller 143 Paper bank 144 Paper feed cassette 145 Separation roller 146 Paper feed path 147 Transport roller 148 Paper feed path 150 Copier main body 200 Paper feed table 220 Heating roller 230 Pressure roller 300 Scanner 302 Fill 303 Spring 311 Core metal 312 Resistance adjustment layer 313 Protective layer 310 Charging roller 321 Electrostatic latent image carrier 323 Exposure unit 324 Development unit 325 Transfer unit 326 Recording medium 327 Fixing unit 330 Cleaning unit 331 Static elimination device 400 Automatic document feeder (ADF) )
401 casing 402 developing roller 411 agitator 412 supply roller 413 regulating blade 510 belt type fixing device 511 heating roller 512 fixing roller 513 fixing belt 514 pressure roller 515 heat roll type fixing device 525 roll type fixing device 570 electromagnetic induction heating type fixing device 613 Cleaning blade S Recording medium P Recording medium (reference numeral in FIG. 19)
Reference Signs List 101 photoconductor 102 charging means 103 exposure means 104 developing means 105 recording medium (image receiving paper)
107 Cleaning means 108 Transfer means (reference numeral in FIG. 20)
321 Photosensitive member 323 Exposure unit 325 Transfer unit 326 Recording medium 327 Fixing units 341 to 344 Image forming elements for respective colors (black, yellow, magenta, cyan) (reference numerals in FIG. 21)
311 Charging means 321 Photoconductor 323 Exposure means 324 Development means 325 Transfer means 326 Recording medium 327 Fixing means 330 Cleaning means 351 to 354 Image forming element 355 for each color (black, yellow, magenta, cyan) Intermediate transfer body 356 Roller

Japanese Patent No. 2537503 JP 09-34167 A JP-A-11-149180 JP 2001-249485 A JP 2001-249492 A JP 2007-264621 A Japanese Patent Publication No.52-3304 Japanese Patent Publication No. 7-82255

Claims (23)

It contains at least a binder resin, a release agent, and a colorant,
The binder resin contains at least a polyester resin and a vinyl polymer containing, as a monomer unit, one or more selected from an acrylic ester and a methacrylic ester, and the acrylic acid of the vinyl polymer A toner characterized in that at least a part of the ester or methacrylic acid ester is a monomer unit obtained by condensing a polyester oligomer having a hydroxyl group at the terminal to acrylic acid and methacrylic acid.   The toner according to claim 1, wherein the vinyl polymer has a weight average molecular weight of 3,000 to 30,000.   The toner according to claim 1, wherein the vinyl polymer has an SP value of 10.0 to 13.0.   The toner according to claim 1, wherein the polyester resin has a glass transition temperature Tg of 30 ° C. or more and 70 ° C. or less.   The mass ratio [(B) / (A)] of the polyester resin (A) and the vinyl polymer (B) is 1/99 to 20/80. The toner described.   The toner according to any one of claims 1 to 5, wherein an addition amount of the vinyl polymer is 5 to 100 parts by mass with respect to 100 parts by mass of the release agent.   7. The toner according to claim 1, wherein a mass ratio of the release agent to the binder resin [(release agent / binder resin) × 100] is 0.1 to 20% by mass.   The toner according to claim 1, wherein the toner is formed in a liquid medium.   The toner according to claim 8, wherein the toner particles formed in the liquid medium are obtained by suspending a polymer solution in an aqueous medium.   Toner particles formed in the liquid medium dissolve or disperse a polymer having a site capable of reacting with a compound having an active hydrogen group, a binder resin, a colorant, and a release agent in at least an organic solvent, The organic solvent consisting of the solution or dispersion is dispersed in an aqueous medium containing resin fine particles, and the organic solvent is reacted with or while reacting the polymer having a site capable of reacting with the compound having active hydrogen groups. The toner according to claim 9, which is obtained by removing the toner.   The toner according to claim 8, wherein the toner particles formed in the liquid medium are obtained by aggregating resin fine particles in the liquid medium.   The toner according to claim 8, wherein the toner particles have a weight average particle diameter of 3 to 15 μm.   13. The ratio (Dv / Dn) between the weight average particle diameter (Dv) and the number average particle diameter (Dn) of the toner particles is 1.25 or less. 13. toner.   A developer comprising the toner according to claim 1.   A toner-filled container filled with the toner according to claim 1. An electrostatic latent image carrier, a charging unit for charging the surface of the electrostatic latent image carrier, an exposure unit for exposing the charged electrostatic latent image carrier surface to form an electrostatic latent image, and the static Developing means for developing an electrostatic latent image with toner to form a visible image; Transfer means for transferring the visible image to a recording medium; Fixing means for fixing the transferred image transferred to the recording medium; An image forming apparatus having at least
The image forming apparatus according to claim 1, wherein the toner is the toner according to claim 1.   The developing means has a magnetic field generating means fixed inside, and has a developer carrying member that can rotate by carrying a two-component developer comprising a magnetic carrier and a toner on the surface. The image forming apparatus described.   The image forming apparatus according to claim 16, wherein the developing unit includes a developer carrier to which toner is supplied, and a layer thickness regulating member that forms a thin layer of toner on the surface of the developer carrier.   19. The fixing unit according to claim 16, wherein the fixing unit includes at least one of a roller and a belt, and the fixing unit heats and presses the transfer image transferred onto the recording medium by heating from a surface not in contact with the toner. The image forming apparatus according to any one of the above.   19. The fixing unit according to claim 16, wherein the fixing unit has at least one of a roller and a belt, and is a fixing unit that heats and presses a transfer image transferred onto a recording medium by heating from a surface in contact with the toner. An image forming apparatus according to claim 1.   A fixing unit includes a heating roller made of magnetic metal and heated by electromagnetic induction on a recording medium on which an unfixed image is formed, a fixing roller arranged in parallel with the heating roller, the heating roller, and the fixing An endless belt-like toner heating medium that is stretched between rollers and heated by the heating roller and rotated by the rollers, and is pressed against the fixing roller via the toner heating medium, and the toner heating medium A fixing unit having a pressure roller that rotates in a forward direction to form a fixing nip portion, and heat-fixes the unfixed image by passing between the toner heating medium and the pressure roller. The image forming apparatus according to any one of 16 to 18. A charging process for charging the surface of the electrostatic latent image carrier, an exposure process for exposing the charged electrostatic latent image carrier surface to form an electrostatic latent image, and developing the electrostatic latent image using toner. An image forming method including at least a developing step for forming a visible image, a transferring step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium. ,
An image forming method, wherein the toner is the toner according to claim 1. The image forming apparatus main body includes at least an electrostatic latent image carrier and developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier using toner to form a visible image. A removable process cartridge,
The process cartridge according to claim 1, wherein the toner is the toner according to claim 1.

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