JP2012163780A - Developer for electrostatic charge image development and production method of the same, and process cartridge and image forming apparatus using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a developer for electrostatic charge image development and a production method of the developer capable of suppressing toner adhesion to the surface of an electrostatic latent image holding body, while achieving both of good cleaning property and transfer property even in long-term use, and to provide a process cartridge and an image forming apparatus using the developer.SOLUTION: The developer for electrostatic charge image development comprises: a toner 100, which has an average circularity of 0.950 to 0.975 and which includes organic resin particles 104 fixed as partially embedded in surfaces of toner base particles 102, the organic resin particles produced by polymerizing a (meth)acrylic acid ester monomer and crosslinking the obtained polymer with a crosslinking component, and having a volume average particle diameter of 200 to 500 nm; and a carrier comprising a core material coated with a resin coating layer containing a copolymer of a monomer of a (meth)acrylic acid ester and/or of a (meth)acrylic acid having a cycloalkyl group in a side chain, and a monomer of a (meth)acrylic acid ester having a nitrogen atom in a side chain. A production method of the developer, and a process cartridge and an image forming apparatus using the developer are also provided.

Description

  The present invention relates to a developer for developing an electrostatic image, a method for producing the same, a process cartridge and an image forming apparatus using the developer.

  A method of visualizing (developing) image information through an electrostatic charge image such as electrophotography is currently used in various fields. In the electrophotographic method, for example, the surface of the electrostatic latent image holding member is charged by a charging unit, and an electrostatic latent image is formed on the surface of the electrostatic latent image holding member by an electrostatic latent image forming unit such as an exposure device. Toner is supplied to the surface of the electrostatic latent image holding member by a toner image forming unit such as a developing unit to develop the electrostatic latent image, and the toner image developed by the transfer unit is transferred to an intermediate transfer member or a recording medium. When the image is transferred to the intermediate transfer member, the image is subsequently transferred to the recording medium by the secondary transfer unit, and the transfer image transferred to the recording medium is fixed by the fixing unit to be visualized.

  On the other hand, the toner remaining on the surface of the electrostatic latent image holding member without being transferred by the transfer unit is then removed by a cleaning unit (cleaning unit) using a cleaning blade or the like, thereby cleaning the surface of the electrostatic latent image holding unit. Are subjected to the next image forming cycle.

  Various techniques have been proposed for the purpose of achieving both transferability by the transfer means (including secondary transfer means) and cleaning ability by the cleaning means in the image forming cycle described above.

  In Patent Document 1, aluminum oxide fine particles having a number average particle size of 5 to 50 nm, titanium oxide fine particles having a number average particle size of 5 to 50 nm, silica fine particles having a number average particle size of 30 to 100 nm, and resin fine particles having a number average particle size of 50 to 300 nm are disclosed. A technology is disclosed in which transfer efficiency is maintained even in a brush cleaning system and ghost is suppressed by a toner containing at least four types of external additives.

  Patent Document 2 discloses a toner that passes through a blade cleaner system by externally adding fine particles selected from silica, alumina, and titania and spherical resin fine particles having a particle size of 0.03 to 0.1 μm with irregularities on the surface. Discloses a technique for preventing the toner from adhering to a charging member or a photoreceptor.

  Patent Document 3 discloses a technique for improving transfer efficiency and suppressing transfer ghosting and transfer loss by externally adding 1 to 30 nm silica, alumina, titania fine particles and 70 to 900 nm spherical resin fine particles to the toner. It is disclosed.

  Patent Document 4 discloses a technique for increasing the transfer rate by attaching at least negatively charged resin fine particles and positively chargeable inorganic particles to the toner surface.

  Further, Patent Documents 5 to 9 described below suppress rapid burying of external additives by causing large-diameter particles to be unevenly distributed on the toner surface or by causing protrusions to be present on the toner surface. This technique reduces the adhesion force to the image carrier and improves the transfer efficiency.

  Patent Document 5 discloses a toner having a core-shell structure, in which the shell is 15% by mass or more and 120% by mass or less with respect to the core, and the shell has a hemispherical protrusion having a step of 0.3 μm or more. Yes.

  Patent Document 6 discloses a toner having a hydrophobic silica of 80 to 300 nm in a 0.04 layer from the toner surface.

  Patent Document 7 discloses a resin composition protrusion having a cross-linked structure on the toner surface, and an electrostatic charge that defines the relationship between the volume average particle diameter D50 and the outer diameter of the protrusion, and the solubility parameter of the resin composition protrusion and the toner base particle. A developing toner is disclosed.

  Patent Document 8 discloses a toner having protrusions made of organic resin fine particles having a composition different from that of the resin constituting the main component of the base particles on the surface of the base particles.

  In Patent Document 9, when a toner is manufactured, resin fine particles composed of styrene, an acrylate ester or a methacrylic acid ester monomer are added to an emulsified dispersion liquid before, during, or after emulsification to adhere and immobilize on the toner surface. In addition, a toner having a weight average particle diameter of 3 to 6 μm and a ratio of fine powder having a particle diameter of 3.17 μm or less of 1 to 30% is disclosed.

JP 2005-265988 A JP-A-8-268422 JP-A-9-288373 JP 2004-240158 A JP 2005-274964 A JP 2008-046416 A JP 2008-158319 A JP 2008-268872 A JP 2009-294533 A

  The present invention relates to a developer for developing an electrostatic image capable of suppressing toner fixation on the surface of an electrostatic latent image holding member while achieving both good cleaning properties and transferability even when used over time, and a method for producing the same, and It is an object to provide a process cartridge and an image forming apparatus using the same.

The above-mentioned subject is achieved by the present invention shown in the following <1> to <10>.
<1> The volume average particle size obtained by crosslinking a polymer obtained by polymerizing a (meth) acrylate monomer on the surface of toner base particles containing a binder resin is 200 to 500 nm. Organic resin particles in the range of a part of which is fixed in a state where the part is buried and the remaining part protrudes, a toner whose average circularity is in the range of 0.950 to 0.975,
Any monomer selected from (meth) acrylic acid ester and (meth) acrylic acid having a cycloalkyl group in the side chain on the surface of the core material, and (meth) acryl having a nitrogen atom in the side chain A carrier formed by coating a resin coating layer containing a copolymer with an acid ester monomer;
A developer for developing an electrostatic charge image, comprising:

    <2> Used for crosslinking the polymer with respect to 100 parts by mass of the polymer obtained by polymerizing a (meth) acrylate monomer in the organic resin particles fixed to the toner. The developer for developing an electrostatic charge image according to <1>, wherein a ratio of the obtained crosslinking component is in a range of 1 to 70 parts by mass.

    <3> A copolymer of at least one monomer selected from (meth) acrylic acid ester and (meth) acrylic acid having a cycloalkyl group in the side chain in the copolymer contained in the resin coating layer of the carrier. The developer for developing an electrostatic charge image according to <1> or <2>, wherein a polymerization ratio is in a range of 85 to 99.5% on a mass basis.

<4> An aggregating step of mixing the binder resin particle dispersion, the colorant dispersion, and the release agent dispersion, adding an aggregating agent thereto, and agglomerating to prepare an aggregated particle dispersion;
Next, organic resin particles having a particle diameter in the range of 200 to 500 nm obtained by crosslinking a polymer obtained by polymerizing a (meth) acrylic acid ester monomer with a crosslinking component, and a binder resin particle dispersion And adhering to the aggregated particle dispersion, and adhering to the aggregated particles to obtain adhered resin aggregated particles,
Next, a fusion step of heating the dispersion and fusing the adhered resin aggregated particles,
The method for producing a developer for developing an electrostatic charge image according to any one of <1> to <3>, wherein the toner is produced by a production method comprising:

    <5> The method for producing a developer for developing an electrostatic charge image according to <4>, wherein the binder resin particle dispersion is a polyester resin particle dispersion.

    <6> The acid value of the organic resin particles added and mixed in the attaching step is in the range of 10 to 20 mgKOH / g, and the acid value is higher than the acid value of the binder resin in the binder resin particle dispersion. The method for producing a developer for developing an electrostatic charge image according to <4> or <5>, wherein the developer is high.

    <7> An electrostatic latent image holding member that is detachable from an image forming apparatus and can hold an electrostatic latent image formed on a surface thereof, and the electrostatic charge according to any one of <1> to <3> Toner image forming means for containing a developer for image development and supplying toner in the developer for developing an electrostatic charge image to the electrostatic latent image formed on the surface of the electrostatic latent image holding member to form a toner image And a process cartridge.

    <8> An electrostatic latent image holding member capable of holding an electrostatic latent image formed on the surface, charging means for charging the surface of the electrostatic latent image holding member, and the surface of the charged electrostatic latent image holding member An electrostatic latent image forming means for forming an electrostatic latent image on the surface, and the electrostatic charge image developing developer according to any one of <1> to <3> are accommodated and formed on the surface of the electrostatic latent image holding member. A toner image forming means for supplying a toner in the developer for developing an electrostatic charge image to the electrostatic latent image formed thereon to form a toner image; a transfer means for transferring the toner image to a recording medium; An image forming apparatus comprising: a fixing unit that fixes a transferred image that has been transferred; and a cleaning unit that removes and cleans untransferred toner from an electrostatic latent image holding member remaining after transfer.

<9> An electrostatic latent image holding body capable of holding an electrostatic latent image formed on the surface, a charging means for charging the surface of the electrostatic latent image holding body, and the surface of the charged electrostatic latent image holding body An electrostatic latent image forming unit that forms an electrostatic latent image on the surface, a toner image forming unit that supplies toner to the electrostatic latent image formed on the surface of the electrostatic latent image holding member to form a toner image, and Transfer means for transferring the toner image to the recording medium, fixing means for fixing the transferred image transferred to the recording medium, and cleaning for removing the untransferred toner remaining on the electrostatic latent image holding member after the transfer. And means for
An image forming apparatus comprising the process cartridge according to <7>, wherein the electrostatic latent image holding member and the toner image forming unit are detachably mounted.

  According to the invention according to <1>, the toner adheres to the surface of the electrostatic latent image holding member while achieving both good cleaning properties and transferability even with use over time as compared with the case where the configuration of the present invention is not provided. It is possible to provide a developer for developing an electrostatic image capable of suppressing the above.

  According to the invention according to <2>, compared with the case where the configuration of the present invention is not provided, to the surface of the electrostatic latent image holding member while achieving both good cleaning properties and transferability even when used for a longer period of time. It is possible to provide a developer for developing an electrostatic image capable of suppressing toner adhesion.

  According to the invention according to <3>, the developer for developing an electrostatic charge image has a small difference in charge amount of the toner between the high temperature and high humidity environment and the low temperature and low humidity environment as compared with the case where the configuration of the present invention is not provided. Can be provided.

  According to the invention according to <4>, the toner adheres to the surface of the electrostatic latent image holding member while achieving both good cleaning properties and transferability even when used over time as compared with the case where the configuration of the present invention is not provided. It is possible to produce a developer for developing an electrostatic charge image capable of suppressing the above.

  According to the invention according to <5>, the toner adheres to the surface of the electrostatic latent image holding member while achieving both good cleaning properties and transferability even when used over time as compared with the case where the configuration of the present invention is not provided. It is possible to produce a developer for developing an electrostatic charge image capable of suppressing the above.

  According to the invention according to <6>, compared to the case where the configuration of the present invention is not provided, the surface of the electrostatic latent image holding member can be achieved while achieving both good cleaning properties and transferability even when used for a longer period of time. It is possible to produce a developer for developing an electrostatic image capable of suppressing toner adhesion.

  According to the invention according to <7>, the toner adheres to the surface of the electrostatic latent image holding member while achieving both good cleaning properties and transferability even with use over time as compared with the case where the configuration of the present invention is not provided. Therefore, it is possible to provide a process cartridge containing a developer for developing an electrostatic image capable of suppressing the above.

  According to the invention according to <8>, the toner adheres to the surface of the electrostatic latent image holding member while achieving both good cleaning properties and transferability even over time as compared with the case where the configuration of the present invention is not provided. It is possible to provide an image forming apparatus in which the above is suppressed.

  According to the invention according to <9>, the toner adheres to the surface of the electrostatic latent image holding member while achieving both good cleaning properties and transferability even when used over time as compared with the case where the configuration of the present invention is not provided. It is possible to provide an image forming apparatus in which the above is suppressed.

FIG. 2 is a schematic enlarged view schematically showing a surface state of a toner contained in a developer for electrostatic charge development according to the present invention. 1 is a schematic configuration diagram illustrating an image forming apparatus according to an exemplary embodiment that is an example of the present invention. 1 is a schematic cross-sectional view schematically showing a basic configuration of a preferred example of a process cartridge of the present invention.

<Developer for developing electrostatic image>
The developer for developing an electrostatic charge image of the present invention (hereinafter sometimes referred to as “developer”) is mainly composed of (meth) acrylic acid ester on the surface of toner base particles containing a binder resin. Organic resin particles having a volume average particle diameter in the range of 200 to 500 nm prepared from a material containing a cross-linking component are fixed in a state where a part thereof is buried and the remaining part protrudes, and the average circular shape thereof. A toner having a degree in the range of 0.950 to 0.975;
Any monomer selected from (meth) acrylic acid ester and (meth) acrylic acid having a cycloalkyl group in the side chain on the surface of the core material, and (meth) acryl having a nitrogen atom in the side chain A carrier formed by coating a resin coating layer containing a copolymer with an acid ester monomer;
It is characterized by containing.

  In the present invention, the toner base particles are the parts other than the organic resin particles that adhere to the surface of the central particles excluding the external additive constituting the toner, with a part of the center particles being buried and the remaining part protruding. The product with the organic resin particles added is referred to as “toner” or “toner particle”.

  FIG. 1 is a schematic enlarged view schematically showing the surface state of the toner contained in the developer for developing electrostatic charge of the present invention. As shown in FIG. 1, in the toner 100 of the present invention, the organic resin particles 104 are attached to the surface of the toner base particles 102 in a state in which a part thereof is buried and the remaining part protrudes. By having such a protruding portion, the toner in the present invention has excellent transferability and cleaning properties.

  In the present invention, the resin used for the organic resin particles (reference numeral 104 in FIG. 1) in the toner and the resin used in the resin coating layer in the carrier are both made of an acrylic resin, so that it is difficult to charge between them. On the other hand, after the toner is supplied to the electrostatic latent image holding member by development, the organic resin particle portion protrudes from the toner surface (see FIG. 1). Since the surface charge density between the two at the contact point is close, the electrostatic adhesion force at the contact portion with the electrostatic latent image holding member on the toner surface is reduced, and the structure of the present invention is provided. Transferability is improved as compared with the case where no.

  The organic resin particles are required to have a volume average particle diameter in the range of 200 to 500 nm, and preferably in the range of 250 to 350 nm. If the particle diameter of the organic resin particles is too small, the organic resin particles themselves are likely to be embedded in the surface of the toner base particles, the spacer effect cannot be obtained, and when an external additive described later is added, There is a concern that the effect of adding external additives will be diminished. On the other hand, if the organic resin particles have an excessively large particle size, it is difficult to fix the organic resin particles on the toner surface, the chargeability of the toner is lowered, and image quality defects such as fogging may occur.

  The volume average particle diameter of the organic resin particles can be measured by dispersing the particles in an aqueous medium and using, for example, Microtrac (trade name: LS13320, manufactured by Beckmann-Coulter).

  The degree of burying of the organic resin particles in the toner base particles is not particularly limited. However, if there are too few buried parts, there is a concern about detachment. As for the degree, it is desirable that approximately 40% or more of the entire organic resin particles are buried, more desirably 50% or more, and even more desirably 60% or more.

  On the other hand, if there are even a few protruding portions of the organic resin particles on the surface of the toner base particles, it can be expected that there will be a considerable effect of achieving both good transferability and cleaning properties. Moreover, since it is advantageous from a viewpoint of detachment | desorption suppression that a buried part is large, there is no upper limit in the grade of the burying of an organic resin particle.

  In the present invention, the average circularity of the toner is in the range of 0.95 to 0.975, and preferably in the range of 0.960 to 0.970. The toner having an average circularity within the range has a potato-like shape that is slightly more irregular than a spherical shape, like the toner 100 of the present invention shown in FIG.

  If the average circularity of the toner is too small, there will be many recesses on the toner surface, and the external additive will concentrate on the recesses, or the area of contact between the electrostatic latent image holding member and the toner will increase and transfer efficiency will decrease. On the other hand, when it is 0.975 or more, the toner becomes spherical, and the cleaning blade easily rolls, the blade part slips through, and filming occurs.

  Here, the average circularity of the toner is an index obtained by optically measuring about 4000 particle images using FPIA-3000 manufactured by Sysmex Corporation and analyzing the projected image of each particle. It is. In the present invention, an average value obtained by sampling 4000 toners is referred to as an average circularity.

  Specifically, first, the perimeter is calculated from the projection image of one particle (perimeter of the particle image). Next, the area of the projected image is calculated, a circle having the same area as the area is assumed, and the circumference of the circle is calculated (circumference length of the circle obtained from the equivalent circle diameter). The circularity is calculated as circularity = circumference of a circle obtained from the equivalent circle diameter / perimeter of the particle image. The closer the numerical value is to 1.0, the more spherical.

  Although there is an inter-apparatus error, 110 of the shape factor SF1 obtained by the following formula (I) is roughly equivalent to the circularity of 0.990 of FPIA-3000. The shape factor SF1 of 140 is substantially equivalent to the circularity of 0.945 of FPIA-3000.

・ Formula (I)
SF1 = (ML ² / A) × (π / 4) × 100
In the above formula (I), ML represents the absolute maximum length of the toner particles, and A represents the projected area of the toner particles.

  What is discussed in terms of the average circularity of the toner, the following volume average particle diameter, and other toner shapes, particle diameters and particle size characteristics is about toner particles (toner mother particles + organic resin particles) containing no external additive. However, since the presence of the external additive has only a negligible effect in these measurements, it may be an external toner to which the external additive is added or only toner particles in the actual measurement.

  In the present invention, the addition amount x (addition amount with respect to the toner base particles 100:%) of the organic resin particles immobilized on the toner surface is an amount such that the following formula (1) is larger than 5 and smaller than 60. Is preferred.

・ Formula (1)

In the above formula (1), TNd represents the volume average particle diameter (μm) of the toner, and RPd represents the volume average particle diameter (nm) of the organic resin particles.
When the above formula (1) is 5 or less, the effect of adhering the organic resin particles is large, and when it is 60 or more, there is a case where the toner image is melted at the time of fixing. Is unfavorable because of lowering.

  As described above, the resin used for the organic resin particles in the toner and the resin used for the resin coating layer in the carrier are both made of acrylic resin, so that both charged columns are close and the organic resin particles are on the surface. Since it is difficult to charge the existing portion, it is desired to appropriately charge the toner by securing an area of a portion where the organic resin particles do not exist on the surface of the toner so as to be in contact with the carrier. For the above reasons, the above formula (1) is described above in order to balance the volume average particle size (TNd) of the toner, the addition amount (x) of the organic resin particles, and the volume average particle size (RPd) in an appropriate relationship. It is desired to be within the range of the lower limit value, whereby the chargeability of the toner is stabilized, and it is possible to improve density reproducibility and suppress fogging.

  If the amount of organic resin particles added is too small, the number of organic resin particles present on the toner surface will decrease, and the effect of immobilizing the organic resin particles on the toner surface may be insufficient. The additive is buried, and transfer efficiency and cleaning properties are lowered. On the other hand, if the amount of the organic resin particles added is too large, charging may be reduced or melting may be inhibited during toner image fixing.

Hereinafter, the toner and the carrier will be described in detail.
[toner]
The toner of the present invention has a volume average particle diameter of 200 to 500 nm prepared from a material containing (meth) acrylic acid ester as a main component and a crosslinking component on the surface of toner base particles containing at least a binder resin. These organic resin particles are fixed in a state in which a part thereof is buried and the remaining part protrudes, and an external additive is further added as necessary. Further, as described above, the average circularity is in the range of 0.950 to 0.975.

<Toner base particles>
The toner base particles in the present invention include a binder, a colorant, a release agent, and other various internal additives as necessary.
Each component will be described below.

(Binder resin)
In the present invention, the binder resin used for the toner base particles is not particularly limited, and known materials can be used. Specifically, polyester resin, polyolefin resin, copolymer of styrene and acrylic acid or methacrylic acid, polyvinyl chloride, phenol resin, polyvinyl acetate, silicone resin, modified polyester resin, polyurethane, polyamide resin, furan resin, An epoxy resin, a xylene resin, a polyvinyl butyral, a terpene resin, a coumarone indene resin, a petroleum resin, a polyether polyol resin, or the like can be used alone or in combination. Among these, polyester resins and polyolefin resins are preferable, and polyester resins that are excellent in low-temperature fixability and excellent in image gloss and suitable for full-color images are most preferable.

  The polyester resin used for the binder resin may be either crystalline or amorphous, but by using the amorphous polyester resin and the crystalline polyester resin together, toner blocking prevention, image storability, And low temperature fixability are preferable.

As the polyester resin used for the toner base particles in the present invention, a known polyester resin can be used. Moreover, a commercial item may be used as a polyester resin, and what was synthesize | combined suitably may be used.
The polyester resin is synthesized from a polyvalent carboxylic acid component and a polyhydric alcohol component.

  Examples of the polyhydric alcohol component include ethylene glycol, propylene glycol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, bisphenol A, hydrogenated bisphenol A, bisphenol A alkylene oxide adduct, hydrogenated bisphenol A alkylene oxide adduct Etc. can be used.

  As the trivalent or higher alcohol component, glycerin, sorbitol, 1,4-sorbitan, trimethylolpropane, or the like can be used.

  Examples of the divalent carboxylic acid component to be condensed with the polyhydric alcohol component include maleic acid, maleic anhydride, fumaric acid, phthalic acid, terephthalic acid, isophthalic acid, malonic acid, succinic acid, glutaric acid, and acids thereof. The lower alkyl ester can be used.

  Examples of the polyvalent carboxylic acid component include oxalic acid, succinic acid, glutaric acid, adipic acid, peric acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,12 -Aliphatic dicarboxylic acids such as dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, malonic acid, mesaconic acid And aromatic dicarboxylic acids such as dibasic acids, and the like, and anhydrides and lower alkyl esters thereof.

  Examples of the trivalent or higher carboxylic acid include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, anhydrides thereof, and lower ones thereof. Examples thereof include alkyl esters.

  These may be used individually by 1 type and may use 2 or more types together. In addition, these enumerations are merely examples, and the present invention is not limited to these.

  The polyester resin preferably includes a resin having a mass average molecular weight of 30,000 to 80,000 as one of the constituent components. By including a resin having a mass average molecular weight of 30,000 to 80,000 as one of the constituent components, it becomes easy to control the average circularity described in detail later. A preferable range of the mass average molecular weight is 30,000 to 70,000, more preferably 30,000 to 60,000. If the mass average molecular weight is less than 30000, it is easily affected by the release agent, and if it exceeds 80000, the viscosity of the resin itself is high, and it is sometimes difficult to obtain a preferable average circularity.

  A polyester resin particle dispersion in which polyester resin particles are dispersed, used when producing toner particles by an emulsion aggregation method described later, is a polyester resin in a water-based medium such as a surfactant, a polymer acid, a polymer base, etc. After being dispersed together with the polymer electrolyte, it can be prepared by heating at a temperature equal to or higher than the glass transition temperature of the resin and processing using a homogenizer or pressure discharge type disperser capable of applying a strong shearing force. It can also be prepared by dissolving in a solvent, dispersing and emulsifying this in an ionic surfactant and water, and then removing the solvent. Furthermore, after dissolving in a solvent and neutralizing, it can also be prepared by phase inversion emulsification in which water is added to perform phase inversion with stirring, and then the solvent is removed. The polyester resin can be used by mixing a plurality of types of resins.

  The volume average particle size of the polyester resin particles is preferably 1 μm or less, more preferably 0.02 to 0.5 μm. When the volume average particle size of the polyester resin particles exceeds 1 μm, the particle size distribution and shape distribution of the finally obtained toner are broadened, and free particles are generated to cause uneven composition of the toner. May be affected. On the other hand, when the volume average particle diameter of the polyester resin particles is 1 μm or less, the above disadvantages are not obtained, uneven distribution among the toners is reduced, dispersion in the toners is improved, and variations in performance and reliability are reduced. Is advantageous. The volume average particle size of the polyester resin particles can be measured using, for example, Microtrac (trade name: LS13320, manufactured by Beckmann-Coulter).

(Coloring agent)
Various colorants can be added to the toner base particles of the toner of the present invention in order to impart a desired color. However, since there is a toner that does not require a colorant, such as a toner that forms a colorless and transparent image for imparting image gloss, the colorant is not an essential component of the toner in the present invention.

  There is no restriction | limiting in particular as a coloring agent which can be used by this invention, A well-known thing can be used. For example, Carbon Black, Chrome Yellow, Hansa Yellow, Benzidine Yellow, Slen Yellow, Quinoline Yellow, Permanent Yellow, Permanent Orange GTR, Pyrazolone Orange, Vulcan Orange, Watch Young Red, Permanent Red, Brilliantamine 3B, Prilianthamine 6B, Day Bon oil red, pyrazolone red, risor red, rhodamine B rake, lake red C, rose bengal, aniline blue, ultramarine blue, calco oil blue, melilen blue chloride, phthalocyanine blue, phthalocyanine green, malachite green oxalate, etc. Pigment, acridine, xanthene, azo, benzoquinone, azine, anthraquinone, dioxadi , Thiazine, azomethine, indico, lioindico, phthalocyanine, triphenylmethane, diphenylmethane, riadine, riazol, xanthene and other dyes used in combination of one or more be able to.

  The colorant content in the toner base particles is preferably in the range of 1 to 30 parts by mass with respect to 100 parts by mass of the binder resin. It is also effective to use a surface-treated colorant or a pigment dispersant as necessary. By appropriately selecting the type of the colorant, a toner of a desired color such as yellow toner, magenta toner, cyan toner, black toner can be obtained.

  The colorant particle dispersion used when the toner particles are produced by the emulsion aggregation method described later is obtained by dispersing the colorant in water together with a polymer electrolyte such as an ionic surfactant, a polymer acid or a polymer base. It is preferable to prepare. For the dispersion of the colorant, a known dispersion method can be used.For example, a general dispersion means such as a rotary shear type homogenizer, a ball mill having a medium, a sand mill, a dyno mill, or an optimizer can be adopted, and there is no limitation. It is not something.

  The volume average particle diameter of the colorant particles dispersed in the colorant particle dispersion is preferably 1 μm or less, and if in the range of 80 to 500 nm, the cohesiveness is good and the color in the toner base particles It is more preferable because the agent is well dispersed.

(Release agent)
The release agent in the toner is generally used for the purpose of improving the release property between the image and the fixing member at the time of fixing. Specific examples of the release agent usable for the toner base particles in the present invention include, for example, low molecular weight polyolefins such as polyethylene, polypropylene, and polybutene; silicones having a softening point that is softened by heating; oleic acid amide, erucic acid Fatty acid amides such as amide, ricinoleic acid amide, stearic acid amide; plant waxes such as carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil; animal waxes such as beeswax; montan wax, ozokerite, ceresin And mineral / petroleum waxes such as paraffin wax, microcrystalline wax and Fischer-Tropsch wax; and ester waxes such as fatty acid ester, montanic acid ester and carboxylic acid ester. In this invention, these mold release agents may be used individually by 1 type, and may use 2 or more types together.

  The addition amount of these release agents is preferably 1 to 20% by mass, more preferably 5 to 15% by mass, based on the total amount of toner base particles. Within the above range, the effect of the release agent is sufficient, and the reduction in the average circularity of the toner due to the change in the volume of the release agent accompanying the cooling of the toner base particles or the toner base particle preparation is controlled. Can do. If the addition amount of the release agent is too small, the effect of adding the release agent may not be exhibited. On the other hand, if it is too much, the fluidity may be extremely deteriorated and the charge distribution may be very wide.

(Other ingredients)
If necessary, inorganic or organic particles can be added to the toner base particles of the toner of the present invention.

  Examples of inorganic particles that can be added include silica, hydrophobized silica, alumina, titanium oxide, calcium carbonate, magnesium carbonate, tricalcium phosphate, colloidal silica, alumina-treated colloidal silica, cationic surface-treated colloidal silica, and anion surface-treated colloidal silica. These can be used alone or in combination, and it is desirable to use colloidal silica. The particle size is preferably 5 nm or more and 100 nm or less. It is also possible to use particles having different particle sizes in combination. The particles can be added directly at the time of toner production, but it is preferable to use particles dispersed in an aqueous medium such as water in advance using an ultrasonic disperser. In the dispersion, the dispersibility can be improved by using an ionic surfactant, a polymer acid, a polymer base, or the like.

  In addition, a known material such as a charge control agent may be added to the toner base particles. The number average particle diameter of the material added at that time is desirably 1 μm or less, and more preferably 0.01 μm or more and 1 μm or less. The number average particle diameter can be measured using, for example, a microtrack.

<Organic resin particles>
In the toner according to the present invention, the organic resin particles fixed in a state where a part of the toner base particles are buried in the toner base particles and the remaining part protrudes are (meth) acrylic acid ester (“acrylic acid ester and / or methacrylic acid ester”). It is a particle obtained by crosslinking a polymer of a monomer based on a crosslinking component, and its volume average particle diameter is in the range of 200 to 500 nm as described above. It is.

  Examples of the (meth) acrylic acid ester monomer constituting the organic resin particles include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, and methyl methacrylate. , Ethyl methacrylate, butyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, ethyl β-hydroxyacrylate, propyl γ-aminoacrylate, stearyl methacrylate, dimethylaminoethyl methacrylate, methacrylic acid And diethylaminoethyl. These monomers may be used alone or in combination of two or more. Among these, methyl methacrylate or cyclohexyl methacrylate is particularly preferable from the viewpoint of chargeability or the glass transition temperature of the polymer.

  For the polymerization of (meth) acrylic acid ester monomers, known polymerization techniques such as emulsion polymerization, miniemulsion, suspension polymerization and dispersion polymerization, initiators, emulsifiers and stabilizers can be used in combination. Yes, no limitation. Among these, the emulsion polymerization method is preferable in terms of producing resin particles.

  A chain transfer agent can be used during the polymerization of the (meth) acrylic acid ester monomer. Although there is no restriction | limiting in particular as a chain transfer agent, The compound which has a thiol component can be used. Specifically, alkyl mercaptans such as hexyl mercaptan, heptyl mercaptan, octyl mercaptan, nonyl mercaptan, decyl mercaptan, and dodecyl mercaptan are preferred, and in particular, the molecular weight distribution is narrow, so that the storage stability of toner at high temperatures is improved. preferable.

  Moreover, when manufacturing the polymer of a (meth) acrylic acid ester-type monomer by radical polymerization of a polymerizable monomer, it can superpose | polymerize using the initiator for radical polymerization.

  The initiator for radical polymerization that can be used is not particularly limited, and specific examples include hydrogen peroxide, acetyl peroxide, cumyl peroxide, tert-butyl peroxide, propionyl peroxide, benzoyl peroxide, and peroxide. Chlorobenzoyl, dichlorobenzoyl peroxide, bromomethylbenzoyl peroxide, lauroyl peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, diisopropyl peroxycarbonate, tetralin hydroperoxide, 1-phenyl-2-methylpropyl-1-hydroperoxide Tert-butyl hydroperoxide pertriphenyl acetate, tert-butyl performate, tert-butyl peracetate, tert-butyl perbenzoate, tert-butyl perphenyl acetate, tert-butyl permethoxyacetate, per-N- (3- Toluil) Peroxides such as tert-butyl vamate, 2,2′-azobispropane, 2,2′-dichloro-2,2′-azobispropane, 1,1′-azo (methylethyl) diacetate, 2,2′-azobis (2-amidinopropane) hydrochloride, 2,2′-azobis (2-amidinopropane) nitrate, 2,2′-azobisisobutane, 2,2′-azobisisobutyramide, 2, 2′-azobisisobutyronitrile, methyl 2,2′-azobis-2-methylpropionate, 2,2′-dichloro-2,2′-azobisbutane, 2,2′-azobis-2-methylbutyro Nitrile, dimethyl 2,2′-azobisisobutyrate, 1,1′-azobis (sodium 1-methylbutyronitrile-3-sulfonate), 2- (4-methylphenylazo) -2-methylmalono Nitrile, 4,4′-azobis-4-cyanovaleric acid, 3,5-dihydroxymethylphenylazo-2-methylmalonodinitrile, 2- (4-bromophenylazo) -2-allylmalonodinitrile, 2, 2'-azobis-2-methylvaleronitrile, 4,4'-azobis-4-cyanovaleric acid dimethyl, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobiscyclohexanenitrile, 2,2′-azobis-2-propylbutyronitrile, 1,1′-azobis-1-chlorophenylethane, 1,1′-azobis-1-cyclohexanecarbonitrile, 1,1′-azobis-1-cyclo Butanenitrile, 1,1′-azobis-1-phenylethane, 1,1′-azobiscumene, 4-nitrophenylazobenzylcyanoacetic acid Til, phenylazodiphenylmethane, phenylazotriphenylmethane, 4-nitrophenylazotriphenylmethane, 1,1'-azobis-1,2-diphenylethane, poly (bisphenol A-4,4'-azobis-4-cyano Azo compounds such as pentanoate) and poly (tetraethylene glycol-2,2′-azobisisobutyrate), 1,4-bis (pentaethylene) -2-tetrazene, 1,4-dimethoxycarbonyl-1 , 4-diphenyl-2-tetrazene and the like.

  The organic resin particles in the present invention are obtained by further crosslinking a polymer polymerized with the monomer and initiator using a crosslinking component. Examples of the crosslinking component that can be used in the present invention include the following. In addition, these crosslinking components can be used individually or in combination of 2 or more types.

  The crosslinkable monomer that can be used as the crosslinking component is a monomer having two or more polymerizable carbon-carbon unsaturated double bonds. Examples of such monomers include aromatic divinyl compounds such as divinylbenzene, divinylnaphthalene, and derivatives thereof; dimethacrylate compounds such as ethylene glycol dimethacrylate and diethylene glycol dimethacrylate, and intramolecular molecules such as divinyl ether. And a compound having two vinyl groups in the molecule, such as pentaerythritol triallyl ether and trimethylolpropane triacrylate.

  When the functional group of the polymer in the organic resin particle in the present invention has a carboxyl group, a compound having an epoxy group or an isocyanate group, a metal compound, or the like is preferably used as the crosslinking component.

  As the compound having an epoxy group, a compound having two or more epoxy groups, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether Glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, 1,3,4-diepoxybutane, allyl glycidyl ether, glycidyl acrylate, β-methyl glycidyl acrylate, glycidyl methacrylate, β-methacrylate And methyl glycidyl.

  Examples of the compound having an isocyanate group include polyisocyanate compounds such as tolylene diisocyanate, hydrogenated tolylene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, prepolymer having an isocyanate group (hydroxyl-containing polyester, hydroxyl-containing polyether). And a polymer having an isocyanate group at the terminal obtained by reacting the polyol with an excess amount of the above polyisocyanate).

  The metal compound is preferably a water-soluble metal compound having a valence of 2 or more, and halogens of metals such as boron, aluminum, iron, copper, zinc, tin, titanium, nickel, magnesium, vanadium, chromium and zirconium. Compound, salt (carbonate, nitrate, sulfate, etc.), oxide, or hydroxide can be exemplified. In particular, boric acid, borax, aluminum chloride, aluminum sulfate, ammonium zirconium carbonate, zirconium chloride, iron alum and the like are preferable.

  When the functional group of the polymer in the organic resin particle in the present invention has a hydroxyl group, the crosslinking component includes a compound having a carboxyl group or an acid anhydride group, a compound having an aldehyde group, a compound having an epoxy group, and nitrogen-containing Examples thereof include a compound, a compound having an acrylamide moiety, a compound having an isocyanate group, and a metal compound. Especially, the compound (especially polyhydric carboxylic acid or its acid anhydride) which has a carboxyl group or an acid anhydride group, and a metal compound are preferable.

  Examples of the polyvalent carboxylic acid having a carboxyl group or an acid anhydride group in this case include an aliphatic polycarboxylic acid, an alicyclic polycarboxylic acid, an aromatic polycarboxylic acid, an oxypolycarboxylic acid, and a heterocyclic polyvalent acid. Examples thereof include carboxylic acid.

  Examples of the aliphatic polycarboxylic acid include aliphatic saturated polycarboxylic acids having 2 to 10 carbon atoms (for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacine). Acid), or aliphatic unsaturated polycarboxylic acids having 4 to 6 carbon atoms (fumaric acid, maleic acid, maleic anhydride, citraconic acid, mesaconic acid, itaconic acid, etc.).

  Examples of the alicyclic polycarboxylic acid include alicyclic polycarboxylic acids having 8 to 10 carbon atoms (for example, 1,4-cyclohexanedicarboxylic acid, tetrahydrophthalic acid, hexahydrophthalic acid, etc.).

  Examples of the aromatic polycarboxylic acid include aromatic polycarboxylic acids having 8 to 12 carbon atoms or acid anhydrides thereof (for example, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc. ).

  Examples of the oxypolycarboxylic acid include oxypolycarboxylic acids having 3 to 6 carbon atoms (for example, tartronic acid, malic acid, tartaric acid, citric acid, etc.).

  The heterocyclic polyvalent carboxylic acid is a polyvalent carboxylic acid having at least one heteroatom selected from nitrogen, oxygen and sulfur atoms (for example, pyridinedicarboxylic acid, pyridinetricarboxylic acid, pyridinetetracarboxylic acid, tropic acid, etc.) ) And the like. As the polyvalent carboxylic acid in the heterocyclic polyvalent carboxylic acid, an aliphatic, alicyclic or aromatic polycarboxylic acid (particularly a polycarboxylic acid having 3 to 10 carbon atoms) is preferably used.

  A salt or partial salt of a polyvalent carboxylic acid is also preferably used. Examples of the polyvalent carboxylates include inorganic salts such as ammonium salts and alkali metal salts (potassium salts, sodium salts, etc.) and organic salts such as tertiary amines. As the polyvalent carboxylic acid, maleic acid or its acid anhydride (maleic anhydride) is particularly preferable.

  As the compound having an aldehyde group when the functional group of the binder resin in the organic resin particles in the present invention has a hydroxyl group, a compound having a plurality of aldehyde groups, such as glyoxal, malonaldehyde, glutaraldehyde, terephthalaldehyde, Examples include dialdehyde starch and acrolein copolymer acrylic resin.

  Examples of the nitrogen-containing compound when the functional group of the binder resin in the organic resin particles in the present invention has a hydroxyl group include, for example, alkoxy melamine having 1 to 4 carbon atoms such as methoxymethyl melamine, N-methylol melamine, N -Methylol group-containing compounds such as methylolurea, guanamines such as acetoguanamine and benzoguanamine, melamine-formalin resin, urea-formalin resin and the like.

  Examples of the compound having an acrylamide moiety when the functional group of the binder resin in the organic resin particles in the present invention has a hydroxyl group include methylene-bis (meth) acrylamide, N, N′-dimethylol-methylene-bisacrylamide, 1 , 1-bisacrylamide-ethane and the like.

  The compounds and metal compounds having an epoxy group or an isocyanate group when the functional group of the binder resin in the organic resin particles in the present invention has a hydroxyl group are the same as those described in the case of having a carboxyl group.

  In addition, when the functional group of the polymer in the organic resin particle in the present invention has a functional group other than a carboxyl group or a hydroxyl group, in consideration of the above explanation, a crosslink having a functional group capable of reacting with the functional group What is necessary is just to select an ingredient. For example, when the functional group is an amide group, a dihydroxy compound may be used.

  In the organic resin particles in the present invention, the ratio of the crosslinking component used for crosslinking the polymer with respect to 100 parts by mass of the polymer obtained by polymerizing the (meth) acrylic acid ester monomer is 1 to 70 parts by mass, more preferably 25 to 70 parts by mass, and even more preferably 30 to 60 parts by mass.

  By setting the ratio of the cross-linking component within the above range, for example, the organic resin particles can be used even when stressed by agitation in the developing device or stress received during primary transfer in a system having an intermediate transfer member. It is hard to be crushed and improves the sustainability of transfer maintenance and cleaning as compared with the case where it is out of the above range.

  If the ratio of the cross-linking component is too small, the organic resin particles are liable to be crushed by various stresses, and there is a concern that the transferability and the cleaning property are lowered. On the other hand, if the proportion of the cross-linking component is too large, the organic resin particles are not softened, so that the adhesion of the toner base particles to the binder resin tends to be lowered, and the organic resin particles are likely to be released from the toner surface. is there.

<Method for Producing Toner in the Present Invention>
The toner in the present invention is produced by adhering the organic resin particles on the surface of the toner base particles so that a part of the organic resin particles is buried and the remaining part protrudes. As a method of attaching the organic resin particles to the surface of the toner base particles, there are a dry method (dry manufacturing method) and a wet method (wet manufacturing method).

(Dry process)
In order to attach the organic resin particles to the surface of the toner base particles by a dry manufacturing method, when the toner base particles are manufactured by a dry manufacturing method, the toner base particles are left as they are, and the toner base particles are processed by a wet manufacturing method. In the case of a manufactured product, the organic resin particles are directly added to the toner base particles after drying, thereby applying a strong pressure (impact force) to both the particles. The particles may be attached later by pushing or driving the toner into the toner base particles. Here, there are no particular restrictions on the method for producing the toner base particles.

  As a method for applying a strong pressure to the organic resin particles and the toner base particles, for example, a hybridizer may be used. A hybridizer is a surface treatment device that repeatedly impinges particles on the disk by circulating air through a rotating disk and controls the state of adhesion to the particle surface. it can. As a result, the organic resin particles can be adhered by being pushed into the toner base particles.

  The operation of attaching the organic resin particles to the toner base particles and the application of a general toner external additive may be performed simultaneously. In this case, conditions for adhering organic resin particles to toner base particles are employed. By using organic resin particles having a particle size larger than that of a general toner external additive, the organic resin particles are selectively embedded in the toner base particles.

(Wet manufacturing method)
In order to attach the organic resin particles to the surface of the toner base particles by a wet process, the toner base particles are of a core-shell structure, and a core layer-forming resin is coated on the core to form a shell layer. At this time, the organic resin particles may be attached simultaneously. Here, there is no particular limitation on the manufacturing method for the core portion of the toner base particles. However, it is preferable to use an emulsion aggregation method that can easily produce toner base particles having a core-shell structure and is excellent in shape controllability of the toner base particles.

  In the case where the toner base particle manufacturing method is an emulsion aggregation method, it is of course possible to form a core once and then form a shell, but before fusing the aggregated particles, a binder resin particle dispersion is added to the toner base particles. The organic resin particles can be attached to the toner base particles by being added to and mixed with the aggregated particle dispersion, and then adhering to the aggregated particles and then fusing them after an operation of an adhesion step for obtaining the adhered resin aggregated particles.

  Hereinafter, a method for producing the toner according to the present invention by the emulsion aggregation method (a method for producing a toner in the method for producing a developer for developing an electrostatic charge image according to the present invention), an example in which the binder resin of the toner base particles is a polyester resin, This will be described in detail.

The production method suitable for the production of the toner in the present invention is:
An aggregating step of mixing the polyester resin particle dispersion, the colorant dispersion, and the release agent dispersion as the binder resin particle dispersion, adding an aggregating agent thereto, and agglomerating to prepare an aggregated particle dispersion; ,
Subsequently, the organic resin particles described above (specifically, organic particles having a particle diameter of 200 to 500 nm formed by crosslinking a polymer obtained by polymerizing a (meth) acrylic acid ester monomer with a crosslinking component). Resin particles) and polyester resin particle dispersion are added to and mixed with the aggregated particle dispersion, and attached to the aggregated particles to obtain attached resin aggregated particles;
Next, a fusion step of heating the dispersion and fusing the adhered resin aggregated particles,
including. Thereafter, the toner in the present invention can be obtained by performing operations of the cooling step and the washing / drying step.

(Preparation of mixed dispersion)
First, various dispersions used in the aggregation process are prepared. As the prepared dispersion, at least a polyester resin particle dispersion, a colorant dispersion, and a release agent dispersion are used, but other dispersions such as a charge control agent may be mixed as necessary.
These various dispersions are mixed at a predetermined ratio to prepare a mixed dispersion.

  When these several types of dispersions are mixed, the total solid content contained in the obtained mixed dispersion is preferably 40% by mass or less, and more preferably 2 to 20% by mass. The content of the colorant particles contained in the mixed dispersion is preferably 20% by mass or less, and more preferably 2 to 15% by mass. Further, the content of the release agent particles contained in the mixed dispersion is preferably 20% by mass or less, and more preferably 5 to 15% by mass.

  There is no restriction | limiting in particular about the preparation method of various dispersion liquids, The method selected suitably according to the objective is employable.

-Dispersing device-
There are no particular restrictions on the means of dispersion, but usable devices include, for example, Homomixer (Special Machine Industries Co., Ltd.), Thrasher (Mitsui Mining Co., Ltd.), Cavitron (Eurotech Co., Ltd.), Microfluidizer (Mizuho Kogyo Co., Ltd.), Menton Gaulin homogenizer (Gorin Inc.), Nanomizer (Nanomizer Inc.), Static mixer (Noritake Company) and other known dispersion devices. Further, as described above, solvent emulsification, phase inversion emulsification, and the like can be cited as long as they are resins.

-Dispersion medium-
Examples of the dispersion medium used for the preparation of various dispersions include an aqueous medium. Examples of the aqueous medium suitable as the dispersion medium include water such as distilled water and ion exchange water, and alcohols. These may be used individually by 1 type and may use 2 or more types together.

-Surfactant-
In the emulsion aggregation method, it is preferable to add and mix a surfactant in various dispersions. Suitable surfactants include, for example, anionic surfactants such as sulfate ester, sulfonate, phosphate, and soap; cationic surfactants such as amine salt type and quaternary ammonium salt type Suitable examples include nonionic surfactants such as polyethylene glycol, alkylphenol ethylene oxide adducts, and polyhydric alcohols. Among these, anionic surfactants and cationic surfactants are preferable. It is preferable that the nonionic surfactant is used in combination with the anionic surfactant or cationic surfactant. These surfactants may be used alone or in combination of two or more.

  Specific examples of the anionic surfactant include fatty acid soaps such as potassium laurate, sodium oleate and sodium castor oil; sulfate esters such as octyl sulfate, lauryl sulfate, lauryl ether sulfate and nonylphenyl ether sulfate; lauryl Sulfonate, dodecyl sulfonate, dodecyl benzene sulfonate, triisopropyl naphthalene sulfonate, sodium alkylnaphthalene sulfonate such as dibutyl naphthalene sulfonate; naphthalene sulfonate formalin condensate, monooctyl sulfosuccinate, dioctyl sulfosuccinate, lauric acid amide sulfonate, oleic acid amide Sulfonates such as sulfonates; lauryl phosphate, isopropyl phosphate , Phosphoric acid esters such as nonyl phenyl ether phosphate; dialkyl sodium sulfosuccinates, such as sodium dioctyl sulfosuccinate; sulfosuccinate lauryl disodium, sulfosuccinate salts such as polyoxyethylene sulfosuccinate Ling lauryl disodium; and the like.

  Specific examples of the cationic surfactant include amine salts such as laurylamine hydrochloride, stearylamine hydrochloride, oleylamine acetate, stearylamine acetate, stearylaminopropylamine acetate; lauryltrimethylammonium chloride, dilauryldimethyl. Ammonium chloride, distearyl ammonium chloride, distearyl dimethyl ammonium chloride, lauryl dihydroxyethyl methyl ammonium chloride, oleyl bispolyoxyethylene methyl ammonium chloride, lauroyl aminopropyl dimethyl ethyl ammonium etosulphate, lauroyl aminopropyl dimethyl hydroxyethyl ammonium perchlorate, alkylbenzene Dimethylammonium chloride, alkyl Quaternary ammonium salts such as trimethyl ammonium chloride; and the like.

  Specific examples of the nonionic surfactant include polyoxyethylene octyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether and other alkyl ethers; Alkylphenyl ethers such as oxyethylene nonyl ether; alkyl esters such as polyoxyethylene laurate, polyoxyethylene stearate, polyoxyethylene oleate; polyoxyethylene lauryl amino ether, polyoxyethylene stearyl amino ether, poly Alkylamines such as oxyethylene oleyl amino ether, polyoxyethylene soybean amino ether, polyoxyethylene beef tallow amino ether; Alkyl amides such as xylethylene lauric acid amide, polyoxyethylene stearic acid amide, polyoxyethylene oleic acid amide; vegetable oil ethers such as polyoxyethylene castor oil ether, polyoxyethylene rapeseed oil ether; lauric acid diethanolamide, stearin Alkanolamides such as acid diethanolamide and oleic acid diethanolamide; sorbitan ester ethers such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate Etc.

  In addition, each preparation method of the polyester resin particle dispersion and the colorant dispersion is as described in each section.

(Aggregation process)
In the agglomeration step, first, a polyester resin particle dispersion, a colorant dispersion, a release agent dispersion, and other components are mixed, and an aggregating agent is added to the obtained mixed dispersion to obtain a binder resin. By heating to a temperature in the vicinity of the glass transition temperature, aggregated particles are formed by aggregating particles composed of the respective components.

  Aggregated particles are formed by adding an aggregating agent at room temperature while stirring with a rotary shearing homogenizer.

  As the aggregating agent used in the aggregating step, it is preferable to use a divalent or higher-valent inorganic metal salt or a divalent or higher-valent metal complex in addition to a surfactant having a reverse polarity to the surfactant used as a dispersant for various dispersions. it can. In particular, when an inorganic metal salt or a metal complex is used, it is preferable because the amount of the surfactant used can be reduced and the charging characteristics of the toner can be improved.

  Examples of the inorganic metal salt include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate, and inorganic such as polyaluminum chloride, polyaluminum hydroxide, and calcium polysulfide. Examples thereof include metal salt polymers. Among these, an aluminum salt and a polymer thereof are particularly preferable. In order to obtain a sharper particle size distribution, aggregated particles having a narrow particle size distribution can be prepared when the valence of the inorganic metal salt is large. Is more suitable.

  The amount of the flocculant added varies depending on the ion concentration at the time of aggregation, but is generally preferably 0.05 to 1.00% by mass with respect to the solid content of the mixed dispersion (each material component that becomes a toner component). 10-0.70 mass% is more preferable. If the amount is less than 0.05% by mass, the effect of the flocculant hardly appears, and if it exceeds 1.00% by mass, there is a concern that overaggregation may occur, and a toner having a large particle size is likely to be generated. Image defects may occur. Further, strong aggregation occurs in the toner preparation apparatus, which is not preferable for production.

(Adhesion process)
When producing toner base particles having a core-shell structure, the coating layer is formed by attaching the resin particles containing the organic resin particles and the polyester resin described above to the surface of the aggregated particles formed through the above-described aggregation process as the adhesion process. (In the present invention, agglomerated particles in which a coating layer is further provided on the surface of the agglomerated particles are referred to as “adhesive resin agglomerated particles”). Here, the coating layer corresponds to a shell layer of toner base particles formed through a fusion process described later.

  The coating layer can be formed by adding and mixing the aforementioned organic resin particles and polyester resin in the aggregated particle dispersion in which the aggregated particles are formed in the aggregation process, and attaching them to the aggregated particles. Accordingly, other components such as a flocculant (eg, pH adjusting agent, dispersing agent, etc.) may be added.

  The polyester resin particles used in the adhered resin particle dispersion may be the same as or different from the polyester resin particles used in the core. When changing, those having a glass transition temperature higher (+0 to 20 ° C.) than the polyester resin used in the core are preferably used from the viewpoint of thermal storage characteristics.

  After the adhered resin particles are uniformly adhered to the surface of the aggregated particles to form a coating layer to obtain the adhered resin aggregated particles, the coating layer on the surface of the adhered resin aggregated particles is obtained by heating and fusing in a fusion step described later. The resin particles made of the polyester resin contained in the resin melt to form a shell layer. At this time, the organic resin particles contained in the coating layer are melted and taken into the shell layer without being melted, and are fixed in a state where a part thereof is buried and the remaining part is projected. It is possible to effectively prevent the release agent and the colorant contained in the core located inside the shell layer from being exposed to the surface of the toner base particles.

  By adjusting the thickness of the shell layer formed on the surface of the toner base particles to be smaller than the particle size of the organic resin particles to be adhered, a state where a part thereof is buried and the remaining part protrudes is obtained. Thus, the organic resin particles can be adhered. In particular, it is desirable to control the thickness of the shell layer so that the organic resin particles have a desired degree of exposure. A plurality of shell layers can also be formed by changing the resin.

  However, as described above, the shell layer also has a desirable thickness, and if it is not possible to secure a sufficient shell layer thickness when the organic resin particles are to be exposed to a desired degree of exposure, the operation of the attaching step is performed a plurality of times. The thickness of the target shell layer is ensured, and the organic resin particles may be added first or simultaneously during the final operation. In the final operation, the thickness of the outermost layer of the shell layer may be controlled so that the organic resin particles have a desired degree of exposure.

  There is no restriction | limiting in particular as an addition mixing method of the adhesion resin particle dispersion in an adhesion process, For example, you may carry out gradually and may be performed in steps divided | segmented into multiple times. Thus, by adding and mixing the adhering resin particle dispersion, the generation of fine particles can be suppressed, and the amount of the release agent on the toner surface can be controlled. The distribution can be narrowed.

  Conditions for adhering the adhering resin particles made of the binder resin for the shell layer to the aggregated particles are as follows.

  First, the heating temperature in the adhesion step is preferably in the temperature range near the glass transition temperature of the polyester resin for the core contained in the aggregated particles to the glass transition temperature of the binder resin for the shell layer, but the aggregation temperature is Since it fluctuates depending on the amount of the flocculant etc., it is not decided unconditionally. As a rough guide, the range of −25 ° C. to + 10 ° C. is preferable based on the glass transition temperature of the polyester resin for the core.

  The heating time in the attaching step depends on the heating temperature and cannot be defined generally, but is usually about 5 minutes to 2 hours.

  In the adhering step, the dispersion obtained by additionally adding the adhering resin particle dispersion to the mixed dispersion in which the aggregated particles are formed may be allowed to stand or may be gently stirred by a mixer or the like. The latter case is advantageous in that uniform adhered resin aggregated particles are easily formed.

  In the attaching step, the amount of the attached resin particle dispersion depends on the particle size of the polyester resin particles contained therein, but the thickness of the finally formed shell layer is about 20 to 500 nm. Preferably it is selected. If the thickness of the shell layer is less than 20 nm, a large amount of release agent may be present on the toner surface. If the thickness of the shell layer exceeds 500 nm, the adhered resin particles are likely to be included in the shell layer. It is not preferable.

(Fusion process)
In the fusion step, the attached resin aggregated particles obtained in the attachment step are fused by heating. A fusion process can be implemented above glass transition temperature, such as a polyester resin contained. As the fusion time, a short time is sufficient if the heating temperature is high, and a long time is necessary if the heating temperature is low. That is, the fusion time depends on the temperature of heating and cannot be generally defined, but is generally 10 minutes to 20 hours.

  In the fusing step, a cross-linking reaction may be performed simultaneously with heating, or a separate cross-linking reaction may be performed after the fusion is completed.

(Washing / drying process)
The fused particles obtained through the fusion process and the cooling process are subjected to solid-liquid separation such as filtration, washing, and drying. As a result, toner base particles in a state where no external additive is added are obtained.

  In the production method of the toner according to the present invention described above by the emulsion aggregation method, the acid value (mg number of KOH necessary for neutralizing 1 g of resin) of the organic resin particles added and mixed in the adhering step is 10 to 20 mg KOH. / G, preferably in the range of 14-18 mg KOH / g, and the acid value is more than the acid value of the binder resin mixed in the aggregation process or added in the adhesion process Is preferably high, and more preferably 2 mgKOH / g or more.

  The acid value was measured according to JIS K0070 using a neutralization titration method. That is, an appropriate amount of a sample is taken, 100 ml of a solvent (diethyl ether / ethanol mixed solution) and a few drops of an indicator (phenolphthalein solution) are added, and shaken sufficiently until the sample is completely dissolved in a water bath. This was titrated with a 0.1 mol / l potassium hydroxide ethanol solution, and the end point was when the indicator was light red for 30 seconds. When the acid value is A, the sample amount is S (g), the 0.1 mol / l potassium hydroxide ethanol solution used for the titration is B (ml), and f is the factor of the 0.1 mol / l potassium hydroxide ethanol solution. , A = (B × f × 5.611) / S.

  By making the acid value of the organic resin particles higher than the acid value of the binder resin that constitutes the toner base particles, the organic resin particles are added to the toner due to an increase in the amount of electrostatic repulsion of carboxyl groups during the fusion process. It becomes easy to orient on the surface of the mother particle.

  When the acid value of the organic resin particles is lower than the acid value of the binder resin constituting the toner base particles, or when the acid value of the organic resin particles is too low, the organic resin particles are used during the fusing step. May be included in the toner base particles, and the spacer effect due to the protruding organic resin particles may be insufficient. On the other hand, if the acid value is too high, the electrostatic repulsion amount of the carboxyl group is high. Therefore, there is a concern that the toner may be detached from the toner surface during the fusing process, and thus it is desirable to set the appropriate range.

<External toner>
The toner in the present invention can be used as an externally added toner by externally mixing inorganic particles and organic particles as fluidity aids, cleaning aids, abrasives and the like as external additives.

  Examples of inorganic particles that can be externally added include all particles usually used as external additives on the toner surface, such as silica, alumina, titanium oxide, calcium carbonate, magnesium carbonate, tricalcium phosphate, and cerium oxide. . These inorganic particles preferably have a hydrophobic surface.

  Examples of the organic particles that can be externally added include, for example, vinyl resins such as styrene polymers, (meth) acrylic polymers, and ethylene polymers, polyester resins, silicone resins, fluorine resins, and the like on the outside of normal toner surfaces. All the particles used as an additive are mentioned.

  These external additives preferably have a primary particle size of 0.01 μm or more and 0.5 μm or less. Further, a lubricant can be added. Examples of the lubricant include fatty alcohol amides such as ethylene bisstearyl amide and oleic amide, and higher alcohols such as fatty acid metal salt unilin such as zinc stearate and calcium stearate. The primary particle size is preferably 0.5 μm or more and 8.0 μm or less.

  In addition, two or more types of inorganic particles may be used from the inorganic particles, and one of the inorganic particles may have an average primary particle size of 30 nm to 200 nm, more preferably 30 nm to 180 nm. preferable.

  Specifically, silica, alumina, and titanium oxide are preferable, and it is particularly preferable to add hydrophobized silica as an essential component. In particular, it is preferable to use silica and titanium oxide in combination, or to use silica having different particle diameters in combination. It is also preferable to use organic particles having a particle size of 80 nm or more and 500 nm or less in combination. Examples of the hydrophobizing agent for hydrophobizing the external additive include known materials, such as silane coupling agents, titanate coupling agents, aluminate coupling agents, and zirconium coupling agents. Examples include silicone oil and polymer coating treatment.

  The external additive is adhered or fixed to the toner surface by applying a mechanical impact force with a V-type blender, a sample mill or a Henschel mixer.

<Average Particle Size of Toner in the Present Invention>
The toner in the present invention preferably has a volume average particle size (TNd) in the range of 2 μm to 9 μm, more preferably in the range of 3 μm to 7 μm. If the particle size is too large, it will be difficult to reproduce a high-definition image. Conversely, if the particle size is too small, reverse polarity toner may be produced, which may affect the image quality such as background stains and color loss. .

  Of course, when each demerit can be overcome, or when these demerits do not become a problem, the thing of the particle size out of the said range may be sufficient.

  The volume average particle size can be measured using Multisizer II (manufactured by Beckman Coulter, Inc.) with an aperture diameter of 100 μm. In this case, the measurement is carried out after dispersing the toner in an electrolytic aqueous solution (isoton aqueous solution) (concentration: 1% by mass), adding a surfactant (trade name: Contaminone), and dispersing it for 300 seconds or more with an ultrasonic disperser. went.

[Career]
The carrier in the present invention has at least one monomer selected from (meth) acrylic acid ester and (meth) acrylic acid having a cycloalkyl group in the side chain on the surface of the core material, and a nitrogen atom in the side chain. A carrier in which a resin coating layer containing a copolymer with a (meth) acrylic acid ester-based monomer is coated, and the carrier in which the resin coating layer is formed on the core material as described above is generally “ It is referred to as “coat carrier”, “resin coating carrier” or the like.

<Core>
The core material (carrier core material) used for the carrier in the present invention is not particularly limited, and examples thereof include magnetic metals such as iron, steel, nickel and cobalt, magnetic oxides such as ferrite and magnetite, and glass beads. In particular, when a magnetic brush method is used, a magnetic metal is desirable. The number average particle diameter of the carrier core material is generally preferably 10 μm or more and 40 μm or less, and more preferably 15 μm or more and 35 μm or less.

<Resin coating layer>
In the carrier in the present invention, the resin coating layer formed on the surface of the core material is
(A-1) (meth) acrylic acid ester, and
(A-2) (meth) acrylic acid having a cycloalkyl group in the side chain,
At least one monomer selected from
(B) a (meth) acrylic acid ester monomer having a nitrogen atom in the side chain;
Of the copolymer.

(A-1) (Meth) acrylic acid ester Specific examples of the (meth) acrylic acid ester used for the carrier in the present invention include methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. Cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, and the like. The same material as the stearyl methacrylate monomer in the organic resin particles used in the toner of the present invention may be used, or another material may be used.

(A-2) (Meth) acrylic acid having a cycloalkyl group in the side chain As the cycloalkyl group in (meth) acrylic acid having a cycloalkyl group used for a carrier in the present invention, a 3- to 10-membered ring can be adopted. The thing of the range of carbon number 3-6 membered ring is preferable. Specific examples include cyclohexyl group, adamantyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, isobornyl group, norbornyl group, boronyl group and the like. From the viewpoint of availability of monomers, a cyclohexyl group and an adamantyl group are particularly preferable.

  The cycloalkyl group is a hydrogen bonded to the carbon of the C—C double bond of acrylic acid and methacrylic acid, or a hydrogen bonded to the carbon of the methyl group corresponding to the carbon side chain of the C—C double bond of methacrylic acid. Instead, it is bonded as a side chain of acrylic acid or methacrylic acid. Bonding may be performed by a conventional method of organic chemistry.

  (A-1) (meth) acrylic acid ester and (A-2) (meth) acrylic acid having a cycloalkyl group in the side chain may be used either alone or both. I do not care.

(B) (meth) acrylic acid ester monomer having nitrogen atom in side chain The nitrogen of “(meth) acrylic acid ester monomer having nitrogen atom in side chain” used for carrier in the present invention Examples of the supply source include amino group, methylamino group, carbamoyl group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, A 2-pyridylamino group, a sulfonamide group, a sulfamoyl group, a carbamoyl group amide group and the like can be mentioned. A group in which these groups (hereinafter sometimes simply referred to as “nitrogen-containing groups”) are bonded to the side chain of the (meth) acrylate monomer is used. Further, the (meth) acrylic acid ester monomer referred to here is the same as the stearyl methacrylate monomer in the organic resin particles used in the toner of the present invention, and suitable examples thereof are also present in the side chain. The same applies except for those having a nitrogen atom.

  The nitrogen-containing group is hydrogen bonded to carbon of the C—C double bond of acrylic acid and methacrylic acid, or hydrogen bonded to carbon of the methyl group corresponding to the side chain of the carbon of C—C double bond of methacrylic acid. Instead of bonding as a side chain of acrylic acid or methacrylic acid, hydrogen may be bonded instead of hydrogen bonded to carbon constituting the ester.

  Specific examples of such (meth) acrylic acid ester monomers having a nitrogen atom in the side chain include ester compounds (polyamide, polyimide, etc.), dimethylaminomethyl methacrylate, dimethylaminoethyl methacrylate, N, N-dimethyl. Aminomethyl acrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate, N, N-dimethylaminomethyl methacrylate, N, N-dimethylaminoethyl methacrylate, N, N-dimethylaminopropyl methacrylate, N , N-diethylaminomethyl acrylate, N, N-diethylaminoethyl acrylate, N, N-diethylaminopropyl acrylate, N, N-diethylaminomethyl methacrylate, N, N-diethylaminoethyl methacrylate Relate, N, N-diethylaminopropyl methacrylate, N, N-dipropylaminomethyl acrylate, N, N-dipropylaminoethyl acrylate, N, N-dipropylaminopropyl acrylate, N, N-dipropylaminomethyl methacrylate, N, N-dipropylaminoethyl methacrylate, N, N-dipropylaminopropyl methacrylate, N, N-methylethylaminomethyl acrylate, N, N-methylethylaminoethyl acrylate, N, N-methylethylaminopropyl acrylate, N, N-methylethylaminomethyl methacrylate, N, N-methylethylaminoethyl methacrylate, N, N-methylethylaminopropyl methacrylate, N, N-methylpropylaminomethyl acrylate, , N-methylpropylaminoethyl acrylate, N, N-methylpropylaminopropyl acrylate, N, N-methylpropylaminomethyl methacrylate, N, N-methylpropylaminoethyl methacrylate, N, N-methylpropylaminopropyl methacrylate, N , N-ethylpropylaminomethyl acrylate, N, N-ethylpropylaminoethyl acrylate, N, N-ethylpropylaminopropyl acrylate, N, N-ethylpropylaminomethyl methacrylate, N, N-ethylpropylaminoethyl methacrylate, N , N-ethylpropylaminopropyl methacrylate and the like. Of these, dimethylaminoethyl methacrylate is preferred from the viewpoint of charge imparting ability.

  The resin coating layer of the carrier in the present invention is at least one selected from (A-1) (meth) acrylic acid ester described above and (A-2) (meth) acrylic acid having a cycloalkyl group in the side chain. A copolymer of such a monomer and (B) a (meth) acrylic acid ester monomer having a nitrogen atom in the side chain, the former monomer copolymerization ratio [{(A -1) + (A-2)} / {(A-1) + (A-2) + (B)}] is within a range of 85.0 to 99.5% on a mass basis. Preferably, it is in the range of 95.0 to 98.0%. By setting the copolymerization ratio within the above range, the hydrophobicity of the resin coating layer is increased, and the difference in charge between a high temperature and high humidity environment and a low temperature and low humidity environment can be reduced.

  Examples of the method for forming the resin coating layer on the surface of the carrier core material include an immersion method in which a powder of the carrier core material is immersed in the solution for forming the coating layer, and a solution for forming the coating layer on the surface of the carrier core material. Spray method for spraying, fluidized bed method for spraying the solution for forming the coating layer in a state where the carrier core material is floated by flowing air, and mixing the carrier core material and the solution for forming the coating layer in a kneader coater to remove the solvent. Examples of the kneader coater method include a powder coat method in which the coating resin is granulated and mixed in the carrier core material and the kneader coater at a temperature equal to or higher than the melting temperature of the coating resin, and then coated. The kneader coater method and the powder coat method are particularly preferable. .

  For the production of the carrier, a heating kneader, a heating Henschel mixer, a UM mixer or the like may be used. Depending on the amount of the coating resin, a heating fluidized rolling bed, a heating kiln, or the like may be used.

  The average film thickness of the resin coating layer formed by the above method is usually in the range of 0.1 μm to 10 μm, and more preferably 0.2 μm to 5 μm.

In general, the carrier is required to have an appropriate electric resistance value in terms of function, and specifically, it is desirable that the electric resistance value is 10 ⁹ Ωcm or more and 10 ¹⁴ Ωcm or less. For example, when the electrical resistance value is as low as 10 ⁶ Ωcm as in an iron powder carrier, an insulating (volume resistivity is 10 ¹⁴ Ωcm or more) resin is coated, and the conductive powder is dispersed in the resin coating layer. It is desirable.

  Specific examples of the conductive powder include metals such as gold, silver and copper; carbon black; semiconductive oxides such as titanium oxide and zinc oxide; titanium oxide, zinc oxide, barium sulfate, aluminum borate and potassium titanate. And the like, such as powder coated with tin oxide, carbon black, or metal. Among these, carbon black is preferable.

  The volume average particle diameter (CAd) of the carrier in the present invention is preferably in the range of 10 to 50 μm, more preferably 10 to 40 μm, still more preferably 15 to 35 μm. By setting the volume average particle size of the carrier to an appropriate size as described above, scumming and density unevenness resulting from the rise of charge, deterioration of charge distribution, and reduction of charge amount due to toner particle size reduction are improved. be able to.

  The mixing ratio of the toner and the carrier in the developer for developing an electrostatic charge image of the present invention is not particularly limited and may be appropriately selected depending on the intended purpose. The range of about 15: 100 is preferable, and the range of about 4: 100 to 12: 100 is more preferable.

[Image forming apparatus, toner container, process cartridge]
First, the image forming apparatus of the present invention using the developer for developing an electrostatic image of the present invention will be described, and then the process cartridge will be described. Note that the following image forming apparatus and process cartridge are examples, and the present invention is not limited to these examples.

<Image forming apparatus>
The image forming apparatus of the present invention includes an electrostatic latent image holding body capable of holding an electrostatic latent image formed on a surface, charging means for charging the surface of the electrostatic latent image holding body, and the charged electrostatic electrostatic image. An electrostatic latent image forming means for forming an electrostatic latent image on the surface of the latent image holding member, and the electrostatic latent image developing developer of the present invention, and an electrostatic latent image formed on the surface of the electrostatic latent image holding member. A toner image forming means for supplying a toner in the developer for developing an electrostatic charge image to the image to form a toner image; a transfer means for transferring the toner image to a recording medium; and a transfer transferred to the recording medium. The image forming apparatus includes: a fixing unit that fixes the image; and a cleaning unit that removes and cleans the untransferred toner of the electrostatic latent image holding member remaining after the transfer.

  In this embodiment, the transfer means is exemplified by an intermediate transfer type that transfers via an intermediate transfer member. A primary transfer means that primarily transfers a developed toner image to the intermediate transfer member, and an intermediate transfer member. Secondary transfer means for secondary transfer of the transferred toner image to a recording material. Furthermore, the image forming apparatus according to this embodiment includes a cleaning unit that removes toner remaining on the surface of the electrostatic latent image holding member after being transferred by the primary transfer unit.

  FIG. 2 is a schematic configuration diagram illustrating an example of the image forming apparatus according to the present embodiment. The image forming apparatus 200 includes an electrostatic latent image holding member 201 that is a so-called photoconductor, a charger 202 that is a charging unit, an image writing unit 203 that is an electrostatic latent image forming unit, and a rotary developing device that is a toner image forming unit. 204, a primary transfer roll 205 as a primary transfer means (transfer means), a cleaning device 206 as a cleaning means by a cleaning blade, and a recording paper (recording medium) P are laminated with a plurality of color toner images and collectively. Intermediate transfer member 207 that is an intermediate transfer member to be transferred, three support rolls 208, 209, and 210 that stretch and support intermediate transfer member 207 together with primary transfer roll 205, and secondary transfer roll that is a secondary transfer unit (transfer unit) 211, a conveyance belt 212 that conveys the recording paper P after the secondary transfer, and the recording paper P that has been conveyed by the conveyance belt 212 is heated two times Sandwiched between Lumpur 213 and the pressure roll 214 is configured to include a fixing device (fixing unit) 215 and for fixing the toner image by heat and pressure.

  The electrostatic latent image holding member 201 is formed in a drum shape as a whole, and has a photosensitive layer on its outer peripheral surface (drum surface). The electrostatic latent image holding member 201 is provided to be rotatable in the direction of arrow C in FIG. The charger 202 uniformly charges the surface of the electrostatic latent image holding member 201. The image writing device 203 forms an electrostatic latent image by irradiating the electrostatic latent image holding member 201 uniformly charged by the charger 202 with image-like light X.

  The rotary developing device 204 includes four developing devices 204Y, 204M, 204C, and 204K that store developers including toners for yellow, magenta, cyan, and black, respectively. In this apparatus, the developer 204Y contains yellow toner, the developer 204M contains magenta toner, the developer 204C contains cyan toner, and the developer 204K contains developer containing black toner. By using the developer for developing an electrostatic charge image of the present invention described above as the developer contained in at least one of these four developing devices, the requirements of the image forming apparatus of the present invention are satisfied. In this embodiment, the developer for all the developing devices is a developer for developing an electrostatic image that satisfies the requirements of the present invention.

  The rotary developing device 204 is driven to rotate so that the four developing devices 204Y, 204M, 204C, and 204K sequentially approach and face the electrostatic latent image holding member 201, thereby electrostatic latent images corresponding to the respective colors. The toner is transferred to the image to form a toner image.

  Here, the developing device in the rotary developing device 204 may be partially removed according to the required image. For example, a rotary developing device including three developing devices such as the developing device 204Y, the developing device 204M, and the developing device 204C may be used. In addition, these developing units may be used by converting them into developing units containing a developer of a desired color such as blue, green, red, etc., and a new developing unit is added and five or more developing units are added. It is good also as a rotary developing device.

  The primary transfer roll 205 sandwiches the intermediate transfer member 207 with the electrostatic latent image holding member 201 and transfers the toner image formed on the surface of the electrostatic latent image holding member 201 to the endless belt-like intermediate transfer member 207. Transfer (primary transfer) to the outer peripheral surface. The cleaning device 206 cleans (removes) toner or the like remaining on the surface of the electrostatic latent image holding member 201 after transfer. The inner peripheral surface of the intermediate transfer member 207 is stretched by a plurality of support rolls 208, 209, 210 and a primary transfer roll 205, and is supported so as to be able to go around in the arrow D direction and in the opposite direction. The secondary transfer roll 211 performs intermediate transfer while sandwiching a recording sheet (recording medium) P conveyed in the direction of arrow E by a sheet conveying unit (not shown) with the intermediate transfer member 207 wound around the support roll 210. The toner image transferred to the outer peripheral surface of the body 207 is transferred (secondary transfer) to the recording paper P.

  The image forming apparatus 200 sequentially forms a toner image on the surface of the electrostatic latent image holding member 201 and transfers it onto the outer peripheral surface of the intermediate transfer member 207, and operates as follows. That is, first, the electrostatic latent image holding member 201 is driven to rotate, and the surface of the electrostatic latent image holding member 201 is uniformly charged by the charger 202 (charging process), and then the electrostatic latent image holding member 201 is charged. Are irradiated with image light from the image writing device 203 to form an electrostatic latent image (latent image forming step).

  The electrostatic latent image is developed by, for example, a yellow developing device 204Y (development process), and then the toner image is transferred to the outer peripheral surface of the intermediate transfer member 207 by the primary transfer roll 205 (primary transfer process). At this time, the toner remaining on the surface of the electrostatic latent image holding member 201 without being transferred to the intermediate transfer member 207 is cleaned by the cleaning device 206.

  Further, the intermediate transfer member 207 on which the yellow toner image is formed on the outer peripheral surface is rotated once in the direction of the arrow D while holding the yellow toner image on the outer peripheral surface (at this time, the electrostatic latent image holding member 201). And the intermediate transfer body 207 and the cleaning device 206 are separated from each other.), For example, at a position where the next magenta toner image is transferred onto the yellow toner image. It is done.

  Thereafter, for magenta, cyan, and black toners, charging by the charger 202, image light irradiation by the image writing device 203, formation of toner images by the developing devices 204M, 204C, and 204K, and an intermediate transfer member, as described above. The transfer of the toner image to the outer peripheral surface 207 is sequentially repeated.

  In the present embodiment, for example, when a red image is formed, the developing unit 204M applies the yellow toner image formed on the intermediate transfer body 207 through the development process and the primary transfer process onto the electrostatic latent image holding body 201. The magenta toner image formed in the above is transferred so as to be arranged in the primary transfer process.

  When the transfer of the four color toner images to the outer peripheral surface of the intermediate transfer member 207 is thus completed, the toner images are collectively transferred to the recording paper P by the secondary transfer roll 211 (secondary transfer step). As a result, a recording image in which a black toner image, a cyan toner image, a magenta toner image, and a yellow toner image are appropriately stacked in order from the image forming surface is obtained on the image forming surface of the recording paper P. After the toner image is transferred onto the surface of the recording paper P by the secondary transfer roll 211, the toner image transferred by the fixing device 215 is heated and fixed (fixing step).

  Hereinafter, a charging unit, an electrostatic latent image holder, an electrostatic latent image forming unit, a toner image forming unit, a transfer unit, an intermediate transfer member, a cleaning unit, a fixing unit, and a recording medium in the image forming apparatus 200 of FIG. 1 will be described. .

(Charging means)
For example, a charging device such as a corotron is used as the charging device 202 as the charging means, but a conductive or semiconductive charging roll may be used. A contact charger using a conductive or semiconductive charging roll may apply a direct current or an alternating current applied to the electrostatic latent image holding member 201. For example, the charger 202 charges the surface of the electrostatic latent image holding member 201 by generating a discharge in a minute space near the contact portion with the electrostatic latent image holding member 201.

  The surface of the electrostatic latent image holding member 201 is usually charged to −300 V or more and −1000 V or less by the charging unit. The conductive or semiconductive charging roll may have a single layer structure or a multiple structure. Further, a mechanism for cleaning the surface of the charging roll may be provided.

(Electrostatic latent image carrier)
The electrostatic latent image holding member 201 has a function of forming a latent image (electrostatic charge image). As the electrostatic latent image holding member, an electrophotographic photosensitive member is preferable. The electrostatic latent image holding member 201 is formed by forming a photosensitive layer including an organic photosensitive layer on the outer peripheral surface of a cylindrical conductive substrate. In general, the photosensitive layer has an undercoat layer formed on the surface of the substrate as necessary, and further includes a charge generation layer containing a charge generation material and a charge transport layer containing a charge transport material in this order. It is. The order of stacking the charge generation layer and the charge transport layer may be reversed.

  These are laminated photoreceptors in which a charge generation material and a charge transport material are contained in separate layers (charge generation layer, charge transport layer), but both the charge generation material and the charge transport material are the same. A single layer type photoreceptor included in the layer may be used, and a laminated type photoreceptor is preferable. Further, an intermediate layer may be provided between the undercoat layer and the photosensitive layer. In addition, other types of photosensitive layers such as an amorphous silicon photosensitive film may be used in addition to the organic photosensitive layer.

(Electrostatic latent image forming means)
The image writing device 203 which is an electrostatic latent image forming unit is not particularly limited. For example, a light source such as semiconductor laser light, LED light, liquid crystal shutter light, or the like is provided on the surface of the electrostatic latent image holder. Examples of the optical system apparatus that exposes the light in the same manner.

(Toner image forming means)
The toner image forming unit has a function of developing a latent image formed on the electrostatic latent image holding member with a developer containing toner to form a toner image. Such a toner image forming unit is not particularly limited as long as it has the above-described function, and may be appropriately selected according to the purpose. For example, a toner for developing an electrostatic charge image may be a brush, a roller, or the like. For example, a known developing device having a function of attaching to the electrostatic latent image holding member 201 may be used. At the time of development, a DC voltage is normally used for the electrostatic latent image holding member 201, but an AC voltage may be further superimposed and used.

(Transfer means)
As the transfer means (in this embodiment, both the primary transfer means and the secondary transfer means), for example, a charge having a polarity opposite to that of the toner of the toner image is applied from the back side of the recording medium, and the toner is generated by electrostatic force. What is necessary is just to use the transfer roll and the transfer roll press apparatus using the electroconductive or semiconductive roll etc. which transfer an image to the recording medium surface, or the direct contact with the back surface of a recording medium.

  A direct current may be applied to the transfer roll as a transfer current applied to the electrostatic latent image holding member, or an alternating current may be applied in a superimposed manner. For the transfer roll, various conditions or specifications may be appropriately set according to the image area width to be charged, the shape of the transfer charger, the opening width, the process speed (peripheral speed), and the like. Further, a single layer foam roll or the like is suitably used as a transfer roll for cost reduction.

(Intermediate transfer member)
A known intermediate transfer member may be used as the intermediate transfer member. Materials used for the intermediate transfer member include polycarbonate resin (PC), polyvinylidene fluoride (PVDF), polyalkylene phthalate, PC / polyalkylene terephthalate (PAT) blend material, ethylene tetrafluoroethylene copolymer (ETFE) / PC, ETFE / PAT, PC / PAT blend materials, and the like can be mentioned. From the viewpoint of mechanical strength, an intermediate transfer belt using a thermosetting polyimide resin is preferable.

(Cleaning means)
The cleaning means may be selected as appropriate as long as it cleans the residual toner on the electrostatic latent image carrier, such as a blade cleaning system, a brush cleaning system, or a roll cleaning system. In the invention, it is preferable to use a cleaning blade having a high cleaning property. As described above, in the present invention, a somewhat irregular so-called potato-shaped toner is used, so that the toner sinks under the cleaning blade as compared with a so-called spherical toner having a high sphericity. Therefore, high cleaning performance can be expected.

  Examples of the material for the cleaning blade include urethane rubber, neoprene rubber, and silicone rubber. Among them, it is particularly preferable to use a polyurethane elastic body because of its excellent wear resistance.

  In addition, when using toner with high transfer efficiency, the aspect which does not use a cleaning means may be sufficient.

(Fixing means)
The fixing unit (fixing device) fixes the toner image transferred to the recording medium by heating, pressurizing, or heating / pressing. In addition to the two-roll system as in the present embodiment, a belt-roll nip system in which the heating side or the pressure side is in the form of a belt and the other in the form of a roll, and a two-belt system in which both the heating side and the pressure side are in the form of a belt are exemplified. As for the belt, in addition to a system in which the belt is stretched by a plurality of rolls, a free belt system in which the belt is not stretched can be used. In the present invention, any type of fixing device may be used.

(recoding media)
Examples of a recording medium (recording paper) on which a toner image is transferred to form a final recording image include plain paper, an OHP sheet, and the like used for electrophotographic copying machines and printers. In order to further improve the smoothness of the image surface after fixing, it is preferable that the surface of the recording medium is as smooth as possible. For example, coated paper in which the surface of plain paper is coated with a resin, art paper for printing, etc. Preferably used.

In this embodiment, for example, the plain paper has a smoothness measured by JIS-P-8119 in the range of 15 to 80 seconds, and a basis weight measured by JIS-P-8124 is 80 g / m. ² or less. Examples of the coated paper include those having a coating layer on one side of a paper substrate and having a smoothness in the range of 150 seconds to 1000 seconds.

  The image forming apparatus according to the present embodiment described above contains a developer for developing an electrostatic charge image that exhibits excellent functions and effects based on the present invention, so that excellent cleaning and transferability can be obtained even when used over time. The toner sticking to the surface of the electrostatic latent image holding member can be suppressed while satisfying both of the above.

  While the image forming apparatus of the present invention has been described in detail with reference to the preferred embodiment, the present invention is not limited to the above embodiment. For example, in the above-described embodiment, each color latent image is formed on one electrostatic latent image holding member 201 by the rotary developing device 204 having developing units for the number of colors, and transferred to the intermediate transfer member 207 each time. Although the apparatus is illustrated, each color unit having an electrostatic latent image holding member, a charging unit, a toner image forming unit, a cleaning unit, and the like corresponding to the number of colors is arranged in parallel facing the intermediate transfer member (physically linear The toner images of the respective colors formed by the respective units are primarily transferred to an intermediate transfer medium, sequentially stacked, and then collectively transferred to a recording medium. An image forming apparatus called a tandem method may be used.

  Further, the image forming apparatus of the present invention can add various conventionally known or non-known various configurations in addition to the components described in the above-described embodiment, and the image of the present invention is still added by the addition. As long as the configuration of the forming apparatus is provided, it is, of course, included in the scope of the present invention. For example, a charge removal means can be provided as a subsequent process of the cleaning means. The static elimination means will be outlined in the process cartridge section.

  In addition, those skilled in the art can appropriately modify the image forming apparatus of the present invention in accordance with conventionally known knowledge. Of course, such modifications are included in the scope of the present invention as long as the configuration of the image forming apparatus of the present invention is provided.

<Process cartridge>
In the present invention, the “process cartridge” is integrally provided with two or more of the components in the image forming apparatus, and is removable from the image forming apparatus main body for the purpose of maintenance, repair, periodic replacement of consumables, and the like. Means a collection of components. In the present invention, among the components in the image forming apparatus, the electrostatic latent image holding member and the toner image forming means are included, and other components are optional.

  FIG. 3 is a schematic cross-sectional view schematically showing a basic configuration of a preferred example of the process cartridge of the present invention. A process cartridge 300 shown in FIG. 3 includes an electrostatic latent image holding member 307, a charger (charging means) 308, a developing device (toner image forming means) 311 and a cleaning device (cleaning means) 313. Are provided with an opening 318 for exposure and an opening 317 for static elimination exposure, and a mounting rail 316 is further attached, and these are integrated. The developing device 311 contains the developer for developing an electrostatic image of the present invention described above.

  The process cartridge 300 is detachable from an image forming apparatus main body including a transfer device 312, a fixing device 315, and other components not shown, and constitutes an image forming apparatus together with the image forming apparatus main body. .

  Since the electrostatic latent image holding member 307, the charger (charging means) 308, and the cleaning device (cleaning means) 313 have already been described in the section of the embodiment of the image forming apparatus, details of the process cartridge are omitted. The same thing can be used in 300.

  Regarding the transfer device 312 for transferring the toner image developed on the surface of the electrostatic latent image holding member 307 to the recording paper 500, both the primary transfer unit and the secondary transfer unit are collectively described in the section of the embodiment of the image forming apparatus. Since the content described as “transfer means” also applies to the process cartridge 300 as it is, detailed description thereof is omitted.

  Examples of the static eliminator (light static eliminator) (not shown) include tungsten lamps and LEDs. Examples of the light quality used in the photostatic process include white light such as tungsten lamps and red light such as LED light. Is mentioned. The intensity of irradiation light in the light neutralization process is usually set to output several times to about 30 times the amount of light indicating the half exposure sensitivity of the electrostatic latent image carrier.

  In the process cartridge 300 of this example, light from such a light neutralizing device is taken in through the opening 317, and the surface of the electrostatic latent image holding member 307 is neutralized.

  On the other hand, image-like exposure light from an exposure apparatus (exposure means) (not shown) is taken in from the opening 318 in the process cartridge 300 of this example, and is irradiated onto the surface of the electrostatic latent image holding member 307 to be electrostatic latent. An image is formed.

  The process cartridge 300 shown in FIG. 3 includes a charger 308, a cleaning device 313, an opening 318 for exposure, and an opening 317 for static elimination exposure, in addition to the electrostatic latent image holding member 307 and the developing device 311. However, in the present invention, these devices and the like can be selectively combined. In the process cartridge of the present invention, the electrostatic latent image holding member and the development image forming means such as the developing device 311 are essential components, and the other components are optional elements.

  Such a process cartridge of the present invention is mounted on the above-described image forming apparatus (preferably, a so-called tandem image forming apparatus), and exhibits a superior effect and effect based on the present invention. By accommodating the toner, it is possible to suppress adhesion of the toner to the surface of the electrostatic latent image holding member while achieving both good cleaning properties and transferability even when used over time.

  Hereinafter, although an example and a comparative example are given and the present invention is explained more concretely in detail, the present invention is not limited to the following examples. Unless otherwise specified, all “parts” and “%” are based on mass.

<Synthesis of polyester as binder resin>
-Preparation of polyester resin (1)-
Bisphenol A ethylene oxide 2-mole adduct: 114 parts Bisphenol A propylene oxide 2-mole adduct: 84 parts Terephthalic acid dimethyl ester: 77.5 parts Dodecenyl succinic acid: 15.0 parts Trimellitic acid: 7.5 Part

  The above components were put into a flask equipped with a stirrer, a nitrogen introduction tube, a temperature sensor, and a rectifying tower, and the temperature was raised to 190 ° C. over 1 hour. After stirring the reaction system, dibutyltin oxide 3. 0 parts were added. Further, 6 hours were required while distilling off the generated water, the temperature was raised from 190 ° C. to 240 ° C., and the dehydration condensation reaction was continued at 240 ° C. for another 2 hours to synthesize polyester resin (1).

  The obtained polyester resin (1) had a glass transition temperature of 57.5 ° C., an acid value of 12.3 mg KOH / g, a mass average molecular weight of 52,000, and a number average molecular weight of 5,100.

<Measurement of resin molecular weight>
In the present invention, the molecular weight of the resin to be used is measured by using a THF (THF) soluble material, measured with a THF solvent using a Tosoh GPC / HLC-8120, a Tosoh column / TSKgel SuperHM-M (15 cm), and monodispersed. This is a molecular weight calculated using a molecular weight calibration curve prepared with a polystyrene standard sample.

<Measuring method of glass transition temperature>
The glass transition temperature of the synthesized resin refers to a value measured by a method (DSC method) defined in ASTM D3418-82.

-Preparation of polyester resin dispersion (1)-
Polyester resin (1) (Mw: 52,000): 200 parts by mass Ethyl acetate: 120 parts by mass Sodium hydroxide aqueous solution (0.3N): 0.1 parts by mass

  The above components were put into a separable flask, heated at 70 ° C., and stirred by a three-one motor (manufactured by Shinto Kagaku Co., Ltd.) to prepare a resin mixture. While further stirring this resin mixture, 500 parts by mass of ion-exchanged water was gradually added, phase inversion emulsification was carried out, and the solvent was removed to obtain a polyester resin dispersion (1) (solid content concentration: 35% by mass). It was adjusted.). The volume average particle size of the resin particles in the dispersion was 220 nm.

-Preparation of colorant dispersion-
Carbon black (Cabot Corp .: Regal 330): 100 parts by mass Ionic surfactant (Daiichi Kogyo Seiyaku: Neogen R): 10 parts by mass Ion-exchanged water: 490 parts by mass

  The above components were mixed and dissolved, and dispersed for 30 minutes using a homogenizer (manufactured by IKA: Ultra Turrax T50) to prepare a colorant dispersion liquid in which a colorant (carbon black) was dispersed (solid content concentration) : Adjusted to 20% by mass).

-Preparation of release agent dispersion-
Paraffin wax (Nippon Seiwa Co., Ltd .: HNP0190, melting point 85 ° C .: 100 parts by mass Cationic surfactant (Kao Co., Ltd .: Sanizol B50): 10 parts by mass ion exchanged water: 390 parts by mass

  The above components were mixed, heated to 95 ° C., dispersed using a homogenizer (IKA: Ultra Tarrax T50), then dispersed with a pressure discharge homogenizer, and a release agent having an average particle size of 550 nm was obtained. A release agent dispersion liquid was prepared by dispersion (the solid content concentration was adjusted to 20% by mass).

A dispersion for adhering resin particles was prepared as follows.
-Preparation of resin particle dispersion (1) for adhesion-
Trimethylolpropane trimethacrylate: 400 parts by mass Methyl methacrylate: 570 parts by mass Acrylic acid: 30 parts by mass

  On the other hand, 2 parts by weight of the anionic surfactant Dowfax (manufactured by Dow Chemical Co., Ltd.) dissolved in 550 parts by weight of ion-exchanged water was placed in a flask, and the above mixed solution was added. The mixture was added, dispersed and emulsified, and 50 parts by mass of an ion exchange aqueous solution in which 6 parts by mass of ammonium persulfate was dissolved was added while slowly stirring and mixing for 10 minutes.

Next, after sufficiently replacing the inside of the system with nitrogen, the flask was heated with an oil bath while stirring until the inside of the system reached 70 ° C. to carry out emulsion polymerization.
As a result, a resin particle dispersion (1) for adhesion having a central particle size (volume average particle size) of 320 nm and a resin acid value of 14.5 mg-KOH / g was obtained (the solid content was adjusted to 35%).

-Preparation of resin particle dispersion (2) for adhesion-
-Ethylene glycol dimethacrylate: 400 parts by mass-Methyl methacrylate: 570 parts by mass-Acrylic acid: 30 parts by mass

  On the other hand, 2 parts by weight of the anionic surfactant Dowfax (manufactured by Dow Chemical Co., Ltd.) dissolved in 550 parts by weight of ion-exchanged water was placed in a flask, and the above mixed solution was added. The mixture was added, dispersed and emulsified, and 50 parts by mass of an ion exchange aqueous solution in which 6 parts by mass of ammonium persulfate was dissolved was added while slowly stirring and mixing for 10 minutes.

Next, after sufficiently replacing the inside of the system with nitrogen, the flask was heated with an oil bath while stirring until the inside of the system reached 70 ° C. to carry out emulsion polymerization.
As a result, a resin particle dispersion liquid (2) for adhesion having a central particle diameter (volume average particle diameter) of 340 nm and a resin acid value of 15.2 mg-KOH / g was obtained (adjusted solid content to 35%).

-Preparation of resin particle dispersion (3) for adhesion-
・ Divinylbenzene: 400 mass parts ・ Methyl methacrylate: 570 mass parts ・ Acrylic acid: 30 mass parts

  On the other hand, 2 parts by weight of the anionic surfactant Dowfax (manufactured by Dow Chemical Co., Ltd.) dissolved in 550 parts by weight of ion-exchanged water was placed in a flask, and the above mixed solution was added. The mixture was added, dispersed and emulsified, and 50 parts by mass of an ion exchange aqueous solution in which 6 parts by mass of ammonium persulfate was dissolved was added while slowly stirring and mixing for 10 minutes.

Next, after sufficiently replacing the inside of the system with nitrogen, the flask was heated with an oil bath while stirring until the inside of the system reached 70 ° C. to carry out emulsion polymerization.
As a result, a resin particle dispersion (3) for adhesion having a center particle size (volume average particle size) of 350 nm and a resin acid value of 16.2 mg-KOH / g was obtained (adjusted solid content to 35%).

-Preparation of resin particle dispersion (4) for adhesion-
Trimethylolpropane trimethacrylate: 400 parts by mass Methyl methacrylate: 570 parts by mass Acrylic acid: 30 parts by mass

  On the other hand, 6 parts by mass of the anionic surfactant Dowfax (manufactured by Dow Chemical Co., Ltd.) dissolved in 550 parts by mass of ion-exchanged water was placed in a flask, and the above mixed solution was added. The mixture was added, dispersed and emulsified, and 50 parts by mass of an ion exchange aqueous solution in which 6 parts by mass of ammonium persulfate was dissolved was added while slowly stirring and mixing for 10 minutes.

Next, after sufficiently replacing the inside of the system with nitrogen, the flask was heated with an oil bath while stirring until the inside of the system reached 70 ° C. to carry out emulsion polymerization.
As a result, a resin particle dispersion liquid (4) for adhesion having a central particle size (volume average particle size) of 220 nm and a resin acid value of 17.5 mg-KOH / g was obtained (the solid content was adjusted to 35%).

-Preparation of resin particle dispersion (5) for adhesion-
Trimethylolpropane trimethacrylate: 400 parts by mass Methyl methacrylate: 570 parts by mass Acrylic acid: 30 parts by mass

  On the other hand, 1 part by mass of the anionic surfactant Dowfax (manufactured by Dow Chemical Co., Ltd.) dissolved in 550 parts by mass of ion-exchanged water was placed in a flask, and the above mixed solution was added. The mixture was added, dispersed and emulsified, and 50 parts by mass of an ion exchange aqueous solution in which 6 parts by mass of ammonium persulfate was dissolved was added while slowly stirring and mixing for 10 minutes.

Next, after sufficiently replacing the inside of the system with nitrogen, the flask was heated with an oil bath while stirring until the inside of the system reached 70 ° C. to carry out emulsion polymerization.
As a result, a resin particle dispersion (5) for adhesion having a central particle diameter (volume average particle diameter) of 480 nm and a resin acid value of 13.8 mg-KOH / g was obtained (the solid content was adjusted to 35%).

-Preparation of resin particle dispersion (6) for adhesion-
Trimethylolpropane trimethacrylate: 650 parts by mass Methyl methacrylate: 320 parts by mass Acrylic acid: 30 parts by mass

  On the other hand, 3 parts by mass of the anionic surfactant Dowfax (manufactured by Dow Chemical Co., Ltd.) dissolved in 550 parts by mass of ion-exchanged water was placed in a flask, and the above mixed solution was added. The mixture was added, dispersed and emulsified, and 50 parts by mass of an ion exchange aqueous solution in which 6 parts by mass of ammonium persulfate was dissolved was added while slowly stirring and mixing for 10 minutes.

Next, after sufficiently replacing the inside of the system with nitrogen, the flask was heated with an oil bath while stirring until the inside of the system reached 70 ° C. to carry out emulsion polymerization.
As a result, a resin particle dispersion liquid (6) for adhesion having a center particle diameter (volume average particle diameter) of 340 nm and a resin acid value of 15.2 mg-KOH / g was obtained (the solid content was adjusted to 35%).

-Preparation of resin particle dispersion (7) for adhesion-
Trimethylolpropane trimethacrylate: 50 parts by mass Methyl methacrylate: 920 parts by mass Acrylic acid: 30 parts by mass

  On the other hand, 3 parts by mass of the anionic surfactant Dowfax (manufactured by Dow Chemical Co., Ltd.) dissolved in 550 parts by mass of ion-exchanged water was placed in a flask, and the above mixed solution was added. The mixture was added, dispersed and emulsified, and 50 parts by mass of an ion exchange aqueous solution in which 6 parts by mass of ammonium persulfate was dissolved was added while slowly stirring and mixing for 10 minutes.

Next, after sufficiently replacing the inside of the system with nitrogen, the flask was heated with an oil bath while stirring until the inside of the system reached 70 ° C. to carry out emulsion polymerization.
As a result, a resin particle dispersion (7) for adhesion having a center particle diameter (volume average particle diameter) of 350 nm and a resin acid value of 15.6 mg-KOH / g was obtained (adjusted solid content to 35%).

-Preparation of resin particle dispersion (8) for adhesion-
Trimethylolpropane trimethacrylate: 400 parts by weight Methyl methacrylate: 590 parts by weight Acrylic acid: 10 parts by weight

  On the other hand, 3 parts by mass of the anionic surfactant Dowfax (manufactured by Dow Chemical Co., Ltd.) dissolved in 550 parts by mass of ion-exchanged water was placed in a flask, and the above mixed solution was added. The mixture was added, dispersed and emulsified, and 50 parts by mass of an ion exchange aqueous solution in which 6 parts by mass of ammonium persulfate was dissolved was added while slowly stirring and mixing for 10 minutes.

Next, after sufficiently replacing the inside of the system with nitrogen, the flask was heated with an oil bath while stirring until the inside of the system reached 70 ° C. to carry out emulsion polymerization.
Thereby, a resin particle dispersion (8) for adhesion having a central particle diameter (volume average particle diameter) of 360 nm and a resin acid value of 13.0 mg-KOH / g was obtained (adjusted solid content to 35%).

-Preparation of resin particle dispersion (9) for adhesion-
Trimethylolpropane trimethacrylate: 400 parts by weight Methyl methacrylate: 540 parts by weight Acrylic acid: 60 parts by weight

  On the other hand, 3 parts by mass of the anionic surfactant Dowfax (manufactured by Dow Chemical Co., Ltd.) dissolved in 550 parts by mass of ion-exchanged water was placed in a flask, and the above mixed solution was added. The mixture was added, dispersed and emulsified, and 50 parts by mass of an ion exchange aqueous solution in which 6 parts by mass of ammonium persulfate was dissolved was added while slowly stirring and mixing for 10 minutes.

Next, after sufficiently replacing the inside of the system with nitrogen, the flask was heated with an oil bath while stirring until the inside of the system reached 70 ° C. to carry out emulsion polymerization.
As a result, a resin particle dispersion (9) for adhesion having a central particle diameter (volume average particle diameter) of 340 nm and a resin acid value of 19.5 mg-KOH / g was obtained (the solid content was adjusted to 35%).

-Preparation of resin particle dispersion (10) for adhesion-
Trimethylolpropane trimethacrylate: 400 parts by mass Styrene: 570 parts by mass Acrylic acid: 30 parts by mass

  On the other hand, 3 parts by mass of the anionic surfactant Dowfax (manufactured by Dow Chemical Co., Ltd.) dissolved in 550 parts by mass of ion-exchanged water was placed in a flask, and the above mixed solution was added. The mixture was added, dispersed and emulsified, and 50 parts by mass of an ion exchange aqueous solution in which 6 parts by mass of ammonium persulfate was dissolved was added while slowly stirring and mixing for 10 minutes.

Next, after sufficiently replacing the inside of the system with nitrogen, the flask was heated with an oil bath while stirring until the inside of the system reached 70 ° C. to carry out emulsion polymerization.
As a result, a resin particle dispersion (10) for adhesion having a central particle diameter (volume average particle diameter) of 340 nm and a resin acid value of 15.5 mg-KOH / g was obtained (the solid content was adjusted to 35%).

-Preparation of resin particle dispersion (11) for adhesion-
Trimethylolpropane trimethacrylate: 400 parts by mass Methyl methacrylate: 570 parts by mass Acrylic acid: 30 parts by mass

  On the other hand, 10 parts by mass of the anionic surfactant Dowfax (manufactured by Dow Chemical Co., Ltd.) dissolved in 550 parts by mass of ion-exchanged water was placed in a flask, and the above mixed solution was added. The mixture was added, dispersed and emulsified, and 50 parts by mass of an ion exchange aqueous solution in which 6 parts by mass of ammonium persulfate was dissolved was added while slowly stirring and mixing for 10 minutes.

Next, after sufficiently replacing the inside of the system with nitrogen, the flask was heated with an oil bath while stirring until the inside of the system reached 70 ° C. to carry out emulsion polymerization.
As a result, a resin particle dispersion (11) for adhesion having a central particle diameter (volume average particle diameter) of 150 nm and a resin acid value of 15.0 mg-KOH / g was obtained (the solid content was adjusted to 35%).

-Preparation of resin particle dispersion (12) for adhesion-
Trimethylolpropane trimethacrylate: 400 parts by mass Methyl methacrylate: 570 parts by mass Acrylic acid: 30 parts by mass

  On the other hand, 1.5 parts by weight of the anionic surfactant Dowfax (manufactured by Dow Chemical Co., Ltd.) dissolved in 550 parts by weight of ion-exchanged water was placed in a flask and mixed as described above. The solution was added, dispersed and emulsified, and 50 parts by mass of an ion exchange aqueous solution in which 6 parts by mass of ammonium persulfate was dissolved was added while slowly stirring and mixing for 10 minutes.

Next, after sufficiently replacing the inside of the system with nitrogen, the flask was heated with an oil bath while stirring until the inside of the system reached 70 ° C. to carry out emulsion polymerization.
Thereby, a resin particle dispersion (12) for adhesion having a center particle diameter (volume average particle diameter) of 650 nm and a resin acid value of 15.2 mg-KOH / g was obtained (the solid content was adjusted to 35%).

-Preparation of resin particle dispersion (13) for adhesion-
-Methyl methacrylate: 970 parts by mass-Acrylic acid: 30 parts by mass

  On the other hand, 10 parts by mass of the anionic surfactant Dowfax (manufactured by Dow Chemical Co., Ltd.) dissolved in 550 parts by mass of ion-exchanged water was placed in a flask, and the above mixed solution was added. The mixture was added, dispersed and emulsified, and 50 parts by mass of an ion exchange aqueous solution in which 6 parts by mass of ammonium persulfate was dissolved was added while slowly stirring and mixing for 10 minutes.

Next, after sufficiently replacing the inside of the system with nitrogen, the flask was heated with an oil bath while stirring until the inside of the system reached 70 ° C. to carry out emulsion polymerization.
As a result, a resin particle dispersion (13) for adhesion having a central particle size (volume average particle size) of 300 nm and a resin acid value of 16.0 mg-KOH / g was obtained (adjusted solid content to 35%).

<Toner production method>
-Production of Toner (1)-
A toner (1) was produced by an agglomeration method using a core composition that forms the following aggregate, a shell composition for adhering particles, and a resin particle composition for adhering.

(Core composition for forming aggregates)
-Ion exchange water: 650 parts by mass-Polyester resin dispersion (1) (solid content: 35% by mass): 180 parts by mass-Colorant (carbon) dispersion (solid content: 25% by mass): 25 parts by mass Mold dispersion (solid content: 20% by mass): 35 parts by mass Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK, solid content 20% by mass): 10 parts by mass

(Shell composition for particle adhesion)
Polyester resin dispersion (1) (solid content: 35% by mass): 71.4 parts by mass Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK, solid content 20% by mass): 10 parts by mass

(Adhesive resin particle composition)
-Adhesive resin particle dispersion (1) (solid content: 35% by mass): 12.9 parts

  The above core composition was put into a 3 liter reaction vessel equipped with a thermometer, pH meter, and stirrer, and the temperature was controlled from the outside with a mantle heater, at a temperature of 30 ° C. and at a stirring rotation speed of 150 rpm for 30 minutes. Retained.

  PAC in which 1.0 part of PAC (polyaluminum chloride: Oji Paper Co., Ltd .: 30% powder product) 1.0 part was dissolved in 10 parts of ion-exchanged water while being dispersed with a homogenizer (manufactured by IKA Japan: Ultra Tarax T50). An aqueous solution was added. Then, 0.3 mol / l (0.3N) nitric acid aqueous solution was added to adjust the pH in the aggregation process to 3.5. The temperature was raised to 50 ° C., and the particle size was measured with Coulter Multisizer II (aperture diameter: 50 μm, manufactured by Coulter, Inc.) to obtain an aggregate having a volume average particle size of 5.0 μm.

  Subsequently, a mixed liquid of the particle adhesion shell composition and the adhesion resin particle composition was added, and the shell resin and the resin particles were adhered to the surface of the aggregate (shell structure).

  Subsequently, 40 parts of 10% by mass of an aqueous NTA (nitrilotriacetic acid) metal salt solution (Cyrest 70: manufactured by Kyrest Co., Ltd.) was added, and then the pH was adjusted to 9. using a 1 mol / l (1N) aqueous sodium hydroxide solution. 0. Thereafter, the temperature was raised to 90 ° C. at a rate of temperature rise of 0.05 ° C./min, and held at 90 ° C. for 3 hours, the shell composition was united, cooled, and filtered to obtain coarse toner particles. This was further re-dispersed with ion-exchanged water and filtered, and washed until the electrical conductivity of the filtrate was 20 μS / cm or less, and then vacuum-dried in an oven at 40 ° C. for 5 hours. Thus, toner particles were obtained.

  1.5 parts by weight of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50) and 1.0 part by weight of hydrophobic titanium oxide (manufactured by Nippon Aerosil Co., Ltd., T805) with respect to 100 parts by weight of the obtained toner particles Were mixed and blended at 10,000 rpm for 30 seconds using a sample mill. Thereafter, the toner (1) was prepared by sieving with a vibration sieve having an opening of 45 μm. The obtained toner (1) had a volume average particle diameter of 6.0 μm. Other characteristic values relating to the toner (1) are shown in Table 1 below.

-Production of Toner (2)-
Toner as in Example 1 except that 12.9 parts by mass of the resin particle dispersion liquid (2) for adhesion was used instead of the resin particle dispersion liquid (1) used as the resin particle composition for adhesion. (2) was produced. The obtained toner had a volume average particle diameter of 6.0 μm. Other characteristic values relating to the toner (2) are shown in Table 1 below.

-Production of Toner (3)-
Toner as in Example 1 except that 12.9 parts by mass of the resin particle dispersion (3) for adhesion was used instead of the resin particle dispersion (1) for adhesion used as the resin particle composition for adhesion. (3) was produced. The obtained toner had a volume average particle diameter of 6.0 μm. Other characteristic values relating to the toner (3) are shown in Table 1 below.

-Production of Toner (4)-
Toner as in Example 1 except that 12.9 parts by weight of the resin particle dispersion liquid (4) for adhesion was used instead of the resin particle dispersion liquid (1) used as the resin particle composition for adhesion. (4) was produced. The obtained toner had a volume average particle size of 5.9 μm. Other characteristic values relating to the toner (4) are shown in Table 1 below.

-Production of Toner (5)-
Toner as in Example 1, except that 12.9 parts by mass of the resin particle dispersion (5) for adhesion was used instead of the resin particle dispersion (1) for adhesion used as the resin particle composition for adhesion. (5) was produced. The obtained toner had a volume average particle diameter of 5.8 μm. Other characteristic values relating to the toner (5) are shown in Table 1 below.

-Production of Toner (6)-
Except that the coalescence time was changed to 90 minutes, granulation was performed in the same manner as in Example 1 to produce Toner (6). The obtained toner had a volume average particle size of 5.9 μm. Other characteristic values relating to the toner (6) are shown in Table 1 below.

-Production of Toner (7)-
Granulation was carried out in the same manner as in Example 1 except that the coalescence time was changed to 240 minutes, whereby Toner (7) was produced. The obtained toner had a volume average particle diameter of 6.2 μm. Other characteristic values relating to the toner (7) are shown in Table 1 below.

-Production of Toner (8)-
A toner (8) was produced in the same manner as in Example 1, except that the amount of the resin particle dispersion for adhesion (1) used as the resin particle composition for adhesion was 2.9 parts by mass. The obtained toner had a volume average particle diameter of 5.8 μm. Other characteristic values relating to the toner (8) are shown in Table 1 below.

-Production of Toner (9)-
Toner as in Example 1 except that 28.6 parts by mass of the resin particle dispersion (9) for adhesion was used instead of the resin particle dispersion (1) for adhesion used as the resin particle composition for adhesion. (9) was produced. The obtained toner had a volume average particle diameter of 6.1 μm. Other characteristic values relating to the toner (9) are shown in Table 1 below.

-Production of Toner (10)-
Toner in the same manner as in Example 1 except that 12.9 parts by mass of the resin particle dispersion liquid (6) for adhesion was used instead of the resin particle dispersion liquid (1) used as the resin particle composition for adhesion. (10) was produced. The obtained toner had a volume average particle diameter of 6.1 μm. Other characteristic values relating to the toner (10) are shown in Table 1 below.

-Production of Toner (11)-
Toner in the same manner as in Example 1 except that 12.9 parts by mass of the resin particle dispersion (7) for adhesion was used instead of the resin particle dispersion (1) for adhesion used as the resin particle composition for adhesion. (11) was produced. The obtained toner had a volume average particle diameter of 6.0 μm. Other characteristic values relating to the toner (11) are shown in Table 1 below.

-Production of Toner (12)-
Toner as in Example 1 except that 12.9 parts by weight of the resin particle dispersion (8) for adhesion was used instead of the resin particle dispersion (1) for adhesion used as the resin particle composition for adhesion. (12) was produced. The obtained toner had a volume average particle diameter of 6.0 μm. Other characteristic values relating to the toner (12) are shown in Table 1 below.

-Production of Toner (13)-
Toner as in Example 1 except that 12.9 parts by weight of the resin particle dispersion (9) for adhesion was used instead of the resin particle dispersion (1) for adhesion used as the resin particle composition for adhesion. (13) was produced. The obtained toner had a volume average particle diameter of 5.8 μm. Other characteristic values relating to the toner (13) are shown in Table 1 below.

-Production of Toner (14)-
Toner as in Example 1 except that 12.9 parts by weight of the resin particle dispersion (10) for adhesion was used instead of the resin particle dispersion (1) for adhesion used as the resin particle composition for adhesion. (14) was produced. The obtained toner had a volume average particle size of 6.3 μm. Other characteristic values relating to the toner (14) are shown in Table 1 below.

-Production of Toner (15)-
Toner in the same manner as in Example 1 except that 12.9 parts by mass of the resin particle dispersion (11) for adhesion was used instead of the resin particle dispersion (1) for adhesion used as the resin particle composition for adhesion. (15) was produced. The obtained toner had a volume average particle size of 5.4 μm. Other characteristic values relating to the toner (15) are shown in Table 1 below.

-Production of Toner (16)-
Toner as in Example 1 except that 12.9 parts by weight of the resin particle dispersion liquid (12) for adhesion was used instead of the resin particle dispersion liquid (1) used as the resin particle composition for adhesion. (16) was produced. The obtained toner had a volume average particle size of 5.5 μm. Other characteristic values relating to the toner (16) are shown in Table 1 below.

-Production of Toner (17)-
Granulation was carried out in the same manner as in Example 1 except that the coalescence time was changed to 30 minutes, and a toner (17) was produced. The obtained toner had a volume average particle size of 5.6 μm. Other characteristic values relating to the toner (17) are shown in Table 1 below.

-Production of Toner (18)-
Granulation was carried out in the same manner as in Example 1 except that the coalescence time was changed to 300 minutes, whereby a toner (18) was produced. The obtained toner had a volume average particle diameter of 5.8 μm. Other characteristic values relating to the toner (18) are shown in Table 1 below.

-Production of Toner (19)-
A toner (19) was produced in the same manner as in Example 1 except that the adhesion resin particle dispersion (1) was not added. The obtained toner had a volume average particle size of 5.9 μm. Other characteristic values relating to the toner (19) are shown in Table 1 below.

-Production of Toner (20)-
A toner (20) was produced in the same manner as in Example 1, except that the amount of the adhering resin particle dispersion (1) added was changed to 42.9 parts by mass. The obtained toner had a volume average particle diameter of 6.2 μm. Other characteristic values relating to the toner (20) are shown in Table 1 below.

-Production of Toner (21)-
A toner (21) was produced in the same manner as in Example 1 except that the aggregate particle size during toner granulation was 6.5 μm. The obtained toner had a volume average particle diameter of 7.2 μm. Other characteristic values relating to the toner (21) are shown in Table 1 below.

-Production of Toner (22)-
Toner as in Example 1 except that 12.9 parts by mass of the resin particle dispersion (14) for adhesion was used instead of the resin particle dispersion (1) for adhesion used as the resin particle composition for adhesion. (22) was produced. The obtained toner had a volume average particle diameter of 6.4 μm. Other characteristic values relating to the toner (22) are shown in Table 1 below.

<Toner volume average particle diameter measuring method>
The volume average particle diameter of the toner was measured using Multisizer II (manufactured by Beckman-Coulter) with an aperture diameter of 100 μm. In this case, the measurement is carried out after dispersing the toner in an electrolytic aqueous solution (isoton aqueous solution) (concentration: 1% by mass), adding a surfactant (trade name: Contaminone), and dispersing it for 300 seconds or more with an ultrasonic disperser. went.

<Method of preparing magnetic particles for carrier>
-Magnetic particles A for carrier-
The carrier magnetic particles A were prepared as follows.
Fe ₂ O ₃ : 70 parts by mass, MnO ₂ : 22.5 parts by mass, Mg (OH) ₂ : 6.5 parts by mass are mixed and pulverized in a wet ball mill for 30 hours, and granulated and dried by a spray dryer. After that, first calcining was performed at 850 ° C. for 7 hours using a rotary kiln. The first calcined product thus obtained was pulverized with a wet ball mill for 2 hours to give a volume average particle size of 2.1 μm, then granulated and dried with a spray dryer, and then at 910 ° C. for 6 hours using a rotary kiln. Second calcination was performed. The second calcined product thus obtained was pulverized with a wet ball mill for 4.8 hours to a volume average particle size of 5.5 μm, further granulated and dried with a spray dryer, and then heated at a temperature of 950 using an electric furnace. The main calcination was performed at a temperature of 16 hours. The carrier magnetic particles A having a volume average particle diameter of 34.0 μm were prepared through the crushing step and the classification step.

-Magnetic particles B for carriers-
The carrier magnetic particles B were prepared as follows.
Fe ₂ O ₃ : 68 parts by mass, MnO ₂ : 23.5 parts by mass, Mg (OH) ₂ : 7.5 parts by mass are mixed and pulverized in a wet ball mill for 35 hours, and granulated and dried by a spray dryer. After that, first calcining was performed at 810 ° C. for 7 hours using a rotary kiln. The first calcined product thus obtained was pulverized with a wet ball mill for 3 hours to give a volume average particle size of 1.8 μm, then granulated and dried with a spray dryer, and then at 910 ° C. for 6 hours using a rotary kiln. Second calcination was performed. The second calcined product thus obtained was pulverized with a wet ball mill for 4.8 hours to a volume average particle size of 4.5 μm, further granulated and dried with a spray dryer, and then heated at a temperature of 950 using an electric furnace. The main calcination was performed at a temperature of 16 hours. The carrier magnetic particles B having a volume average particle size of 25.0 μm were prepared through the crushing step and the classification step.

-Magnetic particles C for carriers-
The carrier magnetic particles C were prepared as follows.
Fe ₂ O ₃ : 70 parts by mass, MnO ₂ : 22.5 parts by mass, Mg (OH) ₂ : 6.5 parts by mass are mixed and pulverized in a wet ball mill for 25 hours, and granulated and dried by a spray dryer. After that, first calcining was performed at 870 ° C. for 7 hours using a rotary kiln. The first calcined product thus obtained was pulverized for 1.5 hours with a wet ball mill to a volume average particle size of 2.2 μm, then granulated and dried with a spray dryer, and then at 910 ° C. using a rotary kiln. Second pre-baking for 6 hours was performed. The second calcined product thus obtained was pulverized for 4.8 hours with a wet ball mill to a volume average particle size of 6.2 μm, further granulated and dried with a spray dryer, and then heated to 980 ° C. using an electric furnace. The main baking was performed for 16 hours. The carrier magnetic particles C having a volume average particle diameter of 48.0 μm were prepared through the crushing step and the classification step.

<Method for preparing carrier coat resin>
-Carrier coat resin A-
The carrier coat resin A was prepared as follows.
960 parts by mass of cyclohexyl methacrylate (cyclohexyl methacrylate), 20 parts by mass of dimethylaminoethyl methacrylate (dimethylaminoethyl methacrylate), 30 parts by mass of methyl methacrylate, 1000 parts by mass of benzene, and 20 parts by mass of azobisisobutyronitrile were mixed. The mixture was heated to 60 ° C. and shaken for 8 hours for polymerization. The reaction product was dissolved in methyl ethyl ketone and precipitated with 7 times the amount of hexane to obtain a resin A for carrier coating. The obtained carrier coat resin A had an acid value of 25.0 mg · KOH / g and a mass average molecular weight of 99,000.

-Carrier coat resin B-
The carrier coat resin B was prepared as follows.
920 parts by mass of cyclohexyl methacrylate (cyclohexyl methacrylate), 50 parts by mass of dimethylaminoethyl methacrylate (dimethylaminoethyl methacrylate), 30 parts by mass of methyl methacrylate, 1000 parts by mass of benzene, and 20 parts by mass of azobisisobutyronitrile were mixed. The mixture was heated to 60 ° C. and shaken for 8 hours for polymerization. The reaction product was dissolved in methyl ethyl ketone and precipitated with 7 times the amount of hexane to obtain a resin B for carrier coating. The obtained carrier coat resin B had an acid value of 24.2 mg · KOH / g and a mass average molecular weight of 86,000.

-Carrier coat resin C-
The carrier coat resin C was prepared as follows.
50 parts by mass of dimethylaminoethyl methacrylate (dimethylaminoethyl methacrylate), 950 parts by mass of methyl methacrylate, 1000 parts by mass of benzene, and 20 parts by mass of azobisisobutyronitrile are mixed, heated to 60 ° C. and shaken for 8 hours. And polymerized. The reaction product was dissolved in methyl ethyl ketone and precipitated with 7 times the amount of hexane to obtain a carrier coat resin C. The obtained carrier coat resin C had an acid value of 24.2 mg · KOH / g and a mass average molecular weight of 86,000.

-Carrier coat resin D-
The carrier coat resin D was prepared as follows.
845 parts by weight of cyclohexyl methacrylate (cyclohexyl methacrylate), 125 parts by weight of dimethylaminoethyl methacrylate (dimethylaminoethyl methacrylate), 30 parts by weight of methyl methacrylate, 1000 parts by weight of benzene, and 20 parts by weight of azobisisobutyronitrile were mixed. The mixture was heated to 60 ° C. and shaken for 8 hours for polymerization. The reaction product was dissolved in methyl ethyl ketone and precipitated with 7 times the amount of hexane to obtain a resin D for carrier coating. The obtained carrier coat resin D had an acid value of 20.5 mg · KOH / g and a mass average molecular weight of 92,000.

-Carrier coat resin E-
The carrier coat resin E was prepared as follows.
965 parts by weight of cyclohexyl methacrylate (cyclohexyl methacrylate), 10 parts by weight of dimethylaminoethyl methacrylate (dimethylaminoethyl methacrylate), 30 parts by weight of methyl methacrylate, 1000 parts by weight of benzene, and 20 parts by weight of azobisisobutyronitrile were mixed. The mixture was heated to 60 ° C. and shaken for 8 hours for polymerization. The reaction product was dissolved in methyl ethyl ketone and precipitated with 7 times the amount of hexane to obtain a carrier coating resin E. The obtained carrier coat resin E had an acid value of 18.0 mg · KOH / g and a mass average molecular weight of 92,000.

-Carrier coat resin F-
The carrier coat resin F was prepared as follows.
1000 parts by mass of cyclohexyl methacrylate (cyclohexyl methacrylate), 1000 parts by mass of benzene, and 20 parts by mass of azobisisobutyronitrile were mixed, heated to 60 ° C., shaken for 8 hours, and polymerized. The reaction product was dissolved in methyl ethyl ketone and precipitated with 7 times the amount of hexane to obtain a resin F for carrier coating. The obtained carrier coat resin F had an acid value of 16.0 mg · KOH / g and a mass average molecular weight of 120,000.

-Carrier coat resin G-
The carrier coat resin G was prepared as follows.
980 parts by mass of styrene, 1000 parts by mass of benzene, and 20 parts by mass of azobisisobutyronitrile were mixed, heated to 60 ° C., shaken for 8 hours, and polymerized. The reaction product was dissolved in methyl ethyl ketone and precipitated with 7 times the amount of hexane to obtain a resin G for carrier coating. The obtained carrier coat resin G had an acid value of 18.0 mg · KOH / g and a mass average molecular weight of 115,000.

<Manufacture of carriers>
-Carrier 1
Carrier magnetic particles A: 1000 parts by mass Toluene: 100 parts by mass Carrier carrier resin A: 25 parts by mass Carbon black (VXC 72; manufactured by Cabot Corporation): 2.6 parts by mass

  Of the above materials, the carrier coat resin A was diluted with toluene, carbon black was added, and the mixture was stirred with a homogenizer for 5 minutes to prepare a resin solution. The resin solution and carrier magnetic particles A are placed in a vacuum degassing kneader and stirred at 90 ° C. for 20 minutes, and then the pressure is reduced to remove toluene, and cooling and stirring are performed until the product temperature reaches 60 ° C. The coated carrier was taken out and sieved with a 75 μm sieving mesh to obtain carrier 1.

-Carrier 2-
Carrier 2 was obtained in the same manner as carrier 1, except that the carrier coat resin A used in the production of carrier 1 was replaced with the carrier coat resin B.

-Career 3-
A carrier 3 was obtained in the same manner as the carrier 1 except that the carrier coat resin A used in the production of the carrier 1 was replaced with the carrier coat resin C.

-Carrier 4-
A carrier 4 was obtained in the same manner as the carrier 1 except that the carrier coat resin A used in the production of the carrier 1 was replaced with the carrier coat resin D.

-Carrier 5-
A carrier 5 was obtained in the same manner as the carrier 1 except that the carrier coat resin A used in the production of the carrier 1 was replaced with the carrier coat resin E.

-Carrier 6
A carrier 6 was obtained in the same manner as the carrier 1 except that the carrier magnetic particles A used in the production of the carrier 1 were replaced with the carrier magnetic particles B.

-Carrier 7-
A carrier 7 was obtained in the same manner as the carrier 1 except that the carrier coat resin A used in the production of the carrier 1 was replaced with the carrier coat resin F.

-Carrier 8-
A carrier 8 was obtained in the same manner as the carrier 1 except that the carrier coat resin A used in the production of the carrier 1 was replaced with the carrier coat resin G.

-Carrier 9-
A carrier 9 was obtained in the same manner as the carrier 1 except that the carrier magnetic particles A used in the production of the carrier 1 were replaced with the carrier magnetic particles C.

<Method for producing externally added toner>
By adding externally 1 part of colloidal silica (manufactured by Nippon Aerosil Co., Ltd., R972) to 100 parts of each of the obtained toners 1 to 22, the mixture is mixed using a Henschel mixer. Toners 1 to 25 were obtained.

<Manufacture of developers of Examples 1 to 18 and Comparative Examples 1 to 13>
The externally added toners 1 to 22 and the carriers 1 to 9 obtained as described above were mixed in the combinations shown in Table 2 below so that the toner concentration was 7% by mass. Two-component electrostatic image developers of Comparative Examples 1 to 13 were produced.

<Evaluation of developer>
The obtained developers of Examples 1 to 18 and Comparative Examples 1 to 13 were evaluated by the following test methods. The results are summarized in Table 3 below.

(1. Image fogging evaluation method)
Each developer in Examples 1 to 18 and Comparative Examples 1 to 13 is filled in a developer of a DocuCentreColor400CP remodeling machine manufactured by Fuji Xerox Co., Ltd., and an image formable area on A4 paper (J paper) manufactured by Fuji Xerox Co., Ltd. The toner paste amount was adjusted to 6 g / m ² at the tip of 10 cm to form an image. After image formation, the image was fixed using an external fixing device. The fog of a part 10 cm from the rear end of the solid part of the image after printing 10,000 sheets (non-image part) was visually confirmed and evaluated according to the following evaluation criteria.

-Evaluation criteria for image fogging-
A: Image fogging is not recognized at all.
○: Slight image fogging but no practical problem.
Δ: Slight image fogging is recognized but is in an allowable range.
X: Image fogging is recognized.

(2. Evaluation method of cleaning properties)
In the environment room of room temperature 28 ° C. and humidity 90% RH, each developer of Examples 1 to 18 and Comparative Examples 1 to 13 was changed to a DocuCentreColor 400CP remodeling machine (Fuji Xerox Co., Ltd.). The toner was adjusted to 6 g / m ² at the tip of the image forming area of A4 paper (J paper) manufactured by Fuji Xerox Co., Ltd. and adjusted to 6 g / m ^2. Then, 20,000 images were formed at a peripheral speed of the developer holding member of 2000 mm / sec. Every time 500 images were formed, the deposits on the surface of the photoreceptor were visually confirmed and evaluated according to the following evaluation criteria.

-Evaluation criteria for cleaning-
A: Adhering matter cannot be confirmed on the photosensitive member up to 10,000 sheets.
○: No deposit on the photoconductor can be confirmed up to 4,000 sheets.
Δ: At the time when 4,000 images were formed, streak deposits were confirmed. However, there is no practical problem.
X: Deposits are present in almost the entire area of the photoreceptor.

<3. Method for evaluating transfer efficiency>
In an environment of high temperature and high humidity (30 ° C., 80% RH), each developer of Examples 1 to 18 and Comparative Examples 1 to 13 was changed to a DocuCentreColor 400CP remodeling machine manufactured by Fuji Xerox Co., Ltd. (Developed to be controlled by external power control), and a 10,000 white solid image is output on Fuji Xerox Co., Ltd. A4 paper (J paper). The batch was developed, and a developed toner image on the surface of the photoreceptor was collected using the adhesiveness on the surface of the adhesive tape, and its mass (W1) was measured.

Similarly, the degree of unevenness was visually evaluated on the developed toner image on the surface of the photoreceptor on which the solid batch was developed.
Next, a similar developed toner image was transferred to the surface of paper (J paper), and the mass (W2) of the transferred image was measured. From these results, the transfer efficiency was determined by the following formula and evaluated according to the evaluation criteria described later.
Transfer efficiency (%) = (W2 / W1) × 100

-Evaluation criteria for transfer efficiency-
◎: Transfer efficiency is 95% or more ○: Transfer efficiency is 87.5% or more and less than 95% Δ: Transfer efficiency is 80% or more and less than 87.5% ×: Transfer efficiency is less than 80%

<4. Evaluation method for filming>
Each developer of Examples 1 to 18 and Comparative Examples 1 to 13 was charged in a developing device of a DocuCentreColor400CP remodeling machine manufactured by Fuji Xerox Co., Ltd. in an environmental chamber at room temperature of 28 ° C. and humidity of 90% RH. A sheet print test was conducted. Thereafter, the appearance of the deposit on the surface of the photoreceptor was visually confirmed and evaluated according to the following evaluation criteria.

-Evaluation criteria for filming-
A: The deposit cannot be confirmed on the photoreceptor.
○: Adhering matter can be confirmed on the photosensitive member, but it is slight.
Δ: Deposits grown in a stripe shape on the photoconductor can be confirmed, but slightly x: There are deposits almost all over the photoconductor.

  In Examples 1 to 18, there was no fogging of the image, the transferability was not impaired, the cleaning property was good, and no filming occurred. On the other hand, in Comparative Examples 1 to 13, it was confirmed that image fogging occurred, an image defect due to poor cleaning or filming occurred, or a decrease in transfer efficiency. In addition, color streaks occurred in the transferred image, and filming occurred in Comparative Example 1.

  DESCRIPTION OF SYMBOLS 100: Toner, 102: Toner mother particle, 104: Organic resin particle, 200: Image forming apparatus, 201,307: Electrostatic latent image holding body, 202,308: Charger (charging means), 203: Image writing apparatus (Electrostatic latent image forming means), 204: rotary developing device (toner image forming means), 204Y, 204M, 204C, 204K, 204R: developing device, 205: primary transfer roll (transfer means), 206, 313: cleaning device 207: Intermediate transfer member 208, 209, 210: Support roll 211: Secondary transfer roll 212: Conveyor belt 213: Heating roll 214: Pressure roll 215, 315: Fixing device 300: Process cartridge 311: Developing device 312: Transfer device 316: Mounting rail 317: Opening portion 318 : Opening, P: Recording paper (recording medium)

Claims (9)

The volume average particle size formed by crosslinking a polymer obtained by polymerizing a (meth) acrylate monomer on the surface of toner base particles containing a binder resin with a crosslinking component is in the range of 200 to 500 nm. The organic resin particles are fixed in a state in which a part thereof is buried and the remaining part protrudes, and the toner has an average circularity in the range of 0.950 to 0.975,
Any monomer selected from (meth) acrylic acid ester and (meth) acrylic acid having a cycloalkyl group in the side chain on the surface of the core material, and (meth) acryl having a nitrogen atom in the side chain A carrier formed by coating a resin coating layer containing a copolymer with an acid ester monomer;
A developer for developing an electrostatic charge image, comprising: In the organic resin particles fixed to the toner, the polymer used for crosslinking the polymer with respect to 100 parts by mass of the polymer obtained by polymerizing a (meth) acrylate monomer. 2. The developer for developing an electrostatic charge image according to claim 1, wherein the ratio of the crosslinking component is in the range of 1 to 70 parts by mass. The copolymerization ratio of at least one monomer selected from (meth) acrylic acid ester and (meth) acrylic acid having a cycloalkyl group in the side chain in the copolymer contained in the resin coating layer of the carrier. 3. The developer for developing an electrostatic charge image according to claim 1, wherein the developer is within a range of 85 to 99.5% on a mass basis. An aggregating step of mixing the binder resin particle dispersion, the colorant dispersion, and the release agent dispersion, adding an aggregating agent thereto, and agglomerating to prepare an aggregated particle dispersion;
Next, organic resin particles having a particle diameter in the range of 200 to 500 nm obtained by crosslinking a polymer obtained by polymerizing a (meth) acrylic acid ester monomer with a crosslinking component, and a binder resin particle dispersion And adhering to the aggregated particle dispersion, and adhering to the aggregated particles to obtain adhered resin aggregated particles,
Next, a fusion step of heating the dispersion and fusing the adhered resin aggregated particles,
The method for producing a developer for developing an electrostatic charge image according to any one of claims 1 to 3, wherein the toner is produced by a production method comprising: The method for producing a developer for developing an electrostatic charge image according to claim 4, wherein the binder resin particle dispersion is a polyester resin particle dispersion. The acid value of the organic resin particles added and mixed in the adhesion step is in the range of 10 to 20 mg KOH / g, and the acid value is higher than the acid value of the binder resin in the binder resin particle dispersion. The method for producing a developer for developing an electrostatic image according to claim 4 or 5. An electrostatic latent image holding member that is detachable from an image forming apparatus and can hold an electrostatic latent image formed on a surface thereof, and the developer for developing an electrostatic charge image according to any one of claims 1 to 3. And a toner image forming means for forming a toner image by supplying toner in the developer for developing an electrostatic charge image to the electrostatic latent image formed on the surface of the electrostatic latent image holding member. Process cartridge characterized by. An electrostatic latent image holding member capable of holding an electrostatic latent image formed on the surface; charging means for charging the surface of the electrostatic latent image holding member; An electrostatic latent image forming means for forming a latent image and the electrostatic latent image developing developer according to any one of claims 1 to 3, and an electrostatic latent image formed on the surface of the electrostatic latent image holding member. A toner image forming unit that forms a toner image by supplying toner in the developer for developing an electrostatic image to the image, a transfer unit that transfers the toner image to a recording medium, and a transfer image that is transferred to the recording medium An image forming apparatus comprising: fixing means for fixing the toner; and cleaning means for removing and cleaning the untransferred toner of the electrostatic latent image holding member remaining after transfer. An electrostatic latent image holding member capable of holding an electrostatic latent image formed on the surface; charging means for charging the surface of the electrostatic latent image holding member; An electrostatic latent image forming means for forming a latent image, a toner image forming means for forming a toner image by supplying toner to the electrostatic latent image formed on the surface of the electrostatic latent image holding member, and the toner image Transfer means for transferring to a recording medium, fixing means for fixing the transferred image transferred to the recording medium, and cleaning means for removing and cleaning the untransferred toner of the electrostatic latent image holding member remaining after transfer With
8. An image forming apparatus comprising the process cartridge according to claim 7, wherein the electrostatic latent image holding member and the toner image forming unit are detachably mounted.

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