JP6127537B2 - Toner, developer, and image forming apparatus - Google Patents

Description

  The present invention relates to a toner, a developer, and an image forming apparatus.

  In electrophotographic image formation, an electrostatic charge image (latent image) is formed on an electrostatic latent image carrier, charged toner is conveyed by a developer carrier, and the latent image is developed to form a toner image. After the formation, the toner image is transferred onto a recording medium such as paper and fixed by a method such as heating to obtain an output image. Further, the toner remaining on the electrostatic latent image carrier after the transfer is collected from the electrostatic latent image carrier by the cleaning member and discharged to a waste toner storage unit.

In the image formation, in order to continue developing the latent image faithfully, it is necessary to appropriately charge the toner, transport an appropriate amount to the development area, and appropriately replenish the toner consumed by the development. Further, it is necessary to appropriately discharge the toner collected from the electrostatic latent image carrier after the transfer to the waste toner storage unit.
Generally, in the toner, by controlling the toner particle size distribution and shape, and by attaching external additives having various functions to the surface of the toner base, the flow stability of the toner is controlled within a desired range. The requirement has been achieved. In particular, many studies have been made on external additives. For example, three types of external additives having different particle diameters that have been hydrophobized are added, and the compression bulk density, loose apparent density, and acceleration of the toner at a predetermined pressure are added. There has been proposed a toner in which the cohesion degree and the stress flow characteristic value are defined within a specific range (see Patent Document 1). According to this proposal, the cohesiveness at the time of transfer and compression of the toner and the fluidity at the time of non-compression are controlled, and it is possible to achieve good transferability and toner replenishment.
There has also been proposed a toner in which inorganic fine particles having different particle diameters are added as external additives to the surface of toner base particles (see Patent Document 2). In this proposal, the generation of toner aggregates due to the change in the amount of charge over time is suppressed by using a combination of high-charged large-sized inorganic fine particles and low-charged small-sized inorganic fine particles.
However, in these proposals, a sufficient effect is not obtained with respect to the burying of the external additive due to the stress on the toner in the developing machine over time, and in particular, a high-speed machine that increases the stress on the toner more. However, there is a problem that the toner is remarkably buried and a large number of toner aggregates are generated, so that the toner replenishment property and the waste toner conveyance property are deteriorated.

In order to solve the above problem, a toner has been proposed in which amorphous particles formed by combining a plurality of primary particles on the surface of toner base particles are added as external additives (see Patent Document 3). In this proposal, by using irregularly shaped particles as external additives, the release of external additives from the surface of the toner base particles and the embedding on the surface of the toner base particles due to stress in the developing machine over time are relatively suppressed. Therefore, deterioration of toner replenishment property and waste toner transportability due to generation of toner aggregates due to these can be relatively suppressed.
However, even in this proposal, sufficient consideration has not been given to the remarkable deterioration of toner cohesiveness caused by the high temperature and high humidity environment, especially after the exposure to the high temperature and high humidity environment for a long time. And waste toner transportability are remarkably deteriorated, and waste toner lock occurs. In the above proposal, the particle size distribution of the irregularly shaped particles and the crack resistance against stress are not taken into consideration, and the small particle size particles included in the irregularly shaped particles or the particles with insufficient coalescence. Deterioration of toner cohesion, deterioration of toner cohesion due to loss of function as irregular particles due to cracking of irregular particles when excessive stress over time, toner replenishment and waste toner transportability due to these However, there is a problem that waste toner lock occurs.

  Therefore, even when exposed to a high temperature and high humidity environment for a long period of time, it is possible to provide a toner capable of effectively suppressing deterioration of toner cohesion and maintaining good toner replenishability and waste toner transportability. Is desired.

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, according to the present invention, even when exposed to a high temperature and high humidity environment for a long period of time, it is possible to effectively suppress the deterioration of toner cohesion and maintain good toner replenishability and waste toner transportability. An object of the present invention is to provide a new toner.

The toner of the present invention as means for solving the above problems is a toner comprising toner base particles containing a binder resin and a colorant, and an external additive,
The external additive contains at least coalesced particles, and the coalesced particles are non-spherical secondary particles obtained by coalescing primary particles.
The loose apparent density ρ _{M of the} toner at 22 ° C. and 55% RH and the loose apparent density ρ _H after storing the toner in a constant temperature bath at 40 ° C. and 70% RH for 14 days are expressed as follows: ρ _H / ρ _M ≦ 0.10 is satisfied.

  According to the present invention, the conventional problems can be solved, the object can be achieved, and the deterioration of the cohesiveness of the toner can be effectively suppressed even when exposed to a high temperature and high humidity environment for a long period of time. A toner capable of maintaining good toner replenishability and waste toner transportability can be provided.

FIG. 1 is a photograph showing an example of an external additive in the toner of the present invention. FIG. 2 is a photograph showing another example of the external additive in the toner of the present invention. FIG. 3 is a photograph showing another example of the external additive in the toner of the present invention. FIG. 4 is a photograph showing an example of an external additive in which the ratio of cracked or disintegrated particles in 1,000 (fused) particles is 30% or less. FIG. 5 is a photograph showing an example of an external additive in which the ratio of cracked or disintegrated particles in 1,000 (fusing) particles exceeds 30%. FIG. 6 is a schematic view showing an example of the image forming apparatus of the present invention. FIG. 7 is a schematic view showing another example of the image forming apparatus of the present invention. FIG. 8 is a schematic view showing an example of a tandem color image forming apparatus as the image forming apparatus of the present invention. FIG. 9 is a partially enlarged schematic view of the image forming apparatus shown in FIG.

(toner)
The toner of the present invention comprises toner base particles containing a colorant and a binder resin, and an external additive. The external additive includes coalesced particles that are non-spherical secondary particles obtained by coalescing primary particles.

As a result of intensive studies in view of the above problems, the present inventors have determined that the external additive is at least a binder in a toner comprising a toner base particle containing a binder resin and a colorant and an external additive. Containing particles, the coalesced particles are non-spherical secondary particles formed by coalescing primary particles,
The loose apparent density ρ _{M of the} toner at 22 ° C. and 55% RH and the loose apparent density ρ _H after storing the toner in a constant temperature bath at 40 ° C. and 70% RH for 14 days are expressed as follows: By satisfying ρ _H / ρ _M ≦ 0.10, even when exposed to a high-temperature and high-humidity environment for a long time, deterioration of toner cohesiveness is effectively suppressed, toner replenishment property, and waste toner It was found that the transportability can be maintained well.

<External additive>
The external additive is not particularly limited as long as it contains at least coalesced particles, and can be appropriately selected according to the purpose.
By controlling the particle size distribution and cracking property of the coalesced particles within the following specific ranges, the coalesced particles on the toner surface are buried over time even in a high-speed machine where the agitation stress on the toner becomes larger. The toner can be held without being detached, and the deterioration of the toner cohesiveness can be effectively suppressed, and the toner replenishment property and the waste toner conveyance property can be maintained well.

<< coalescence particles >>
The coalesced particles are non-spherical secondary particles obtained by coalescing primary particles.
As shown in FIG. 1, the coalesced particles are particles having a coalesced portion in which a plurality of primary particles (reference numerals 1A to 1D) are united and the primary particles overlap each other. It is different from the state of aggregation while maintaining. The “cohesive particles” may be referred to as “secondary particles”.

-Primary particles-
The primary particles are not particularly limited and can be appropriately selected depending on the purpose. For example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, Tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride, etc. Inorganic fine particles, organic fine particles, and the like. These may be used alone or in combination of two or more. Among these, silica is preferable in that it can prevent the external additive from being buried and detached from the toner base particles.

  The number average particle diameter (Da) of the primary particles is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 20 nm to 150 nm, and more preferably 35 nm to 150 nm. When the number average particle size of the primary particles is less than 20 nm, the embedding of the external additive in the toner base particles due to external stress cannot be sufficiently suppressed, and the function as a spacer cannot be exhibited. The toner replenishment property and the toner replenishment property and the waste toner conveyance property are likely to deteriorate. On the other hand, if the thickness exceeds 150 nm, the toner is likely to be liberated and the filming of the photoconductor is likely to occur, which is not preferable.

  The number average particle size (Da) of the primary particles was measured based on the particle size of primary particles in the coalesced particles (the length of all arrows shown in FIG. 1). In the measurement, a sample obtained by dispersing the secondary particles in an appropriate solvent (such as THF) and then removing the solvent on a substrate to dry the sample was measured using a field emission scanning electron microscope (FE-SEM, acceleration). (Voltage: 5 kV to 8 kV, observation magnification: 8,000 to 10,000 times), and measuring the particle diameter of primary particles in the visual field. The primary particle size is measured by predicting the entire image from the outer frame of the coalesced particles and measuring the average value of the longest length of all images (the length of all arrows shown in FIG. 1). Number: 100 or more and 200 or less).

-Secondary particles-
The secondary particles are not particularly limited and can be appropriately selected according to the purpose. However, as shown by reference numeral 1 in FIG. Particles (secondary agglomerated particles) are preferable, and particles obtained by chemically bonding the primary particles by a sol-gel method are more preferable. Specific examples include sol-gel silica.

  The number average particle diameter (Db) of the secondary particles, that is, the number average particle diameter of the coalesced particles is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 80 nm to 200 nm, preferably 100 nm. -180 nm is more preferable, and 100 nm-160 nm is particularly preferable. When the number average particle size is less than 80 nm, the external additive cannot be sufficiently buried in the toner base particles due to external stress, and the function as a spacer cannot be exhibited. However, the toner replenishment property and the waste toner conveyance property may be easily deteriorated, which is not preferable. On the other hand, if it exceeds 200 nm, release from the toner is likely to occur, and photoconductor filming is likely to occur, which is not preferable.

  The number average particle diameter (Db) of the secondary particles is measured by dispersing the secondary particles in a suitable solvent (tetrahydrofuran (THF) or the like) and then removing the solvent on the substrate to dry the sample. By measuring the particle diameter of secondary particles in the field of view with a field emission scanning electron microscope (FE-SEM, acceleration voltage: 5 kV to 8 kV, observation magnification: 8,000 times to 10,000 times). Specifically, the entire image is predicted from the outer frame of the secondary particles that are attached, and the longest length of the entire image (the length of the arrow shown in FIG. 2) is measured (number of particles measured: 100 ) Or more.

-Manufacturing method of coalesced particles-
The method for producing the coalesced particles is not particularly limited and may be appropriately selected depending on the intended purpose. However, a method of producing by the sol-gel method is preferable, and specifically, the primary particles and the treatment agent are mixed. Or the method of manufacturing by the coalescence process which carries out the chemical bonding by baking and carries out the secondary aggregation and makes it a secondary particle (coating particle) is preferable. When synthesizing by the sol-gel method, coalescent particles may be prepared by a one-step reaction in the presence of the treatment agent. Although an example of a manufacture example is shown below, it is not restricted to this.

-Treatment agent-
There is no restriction | limiting in particular as said processing agent, According to the objective, it can select suitably, For example, a silane type processing agent, an epoxy type processing agent, etc. are mentioned. These may be used alone or in combination of two or more. When silica is used as the primary particles, the Si—O—Si bond formed by the silane-based treatment agent is more heated than the Si—O—C bond formed by the epoxy-based treatment agent. From the viewpoint of stability, a silane-based treatment agent is preferable. Moreover, you may use processing adjuvants (water, 1 mass% acetic acid aqueous solution, etc.) as needed.

--- Silane treatment agent ---
There is no restriction | limiting in particular as said silane type processing agent, According to the objective, it can select suitably, For example, alkoxysilanes (tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxy) Silane, dimethyldiethoxysilane, methyldimethoxysilane, methyldiethoxysilane, diphenyldimethoxysilane, isobutyltrimethoxysilane, decyltrimethoxysilane, etc.); silane coupling agents (γ-aminopropyltolethoxysilane, γ-glycidoxy) Propyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, vinyltriethoxysilane, methylvinyldi Methoxysilane, etc.); vinyltrichlorosilane, dimethyldichlorosilane, methylvinyldichlorosilane, methylphenyldichlorosilane, phenyltrichlorosilane, N, N′-bis (trimethylsilyl) urea, N, O-bis (trimethylsilyl) acetamide, dimethyltrimethylsilyl Examples thereof include a mixture of amine, hexamethyldisilazane, and cyclic silazane.

The silane-based treatment agent forms secondary agglomeration by chemically bonding the primary particles (for example, silica primary particles) as described below.
When the silica primary particles are treated using the alkoxysilanes, the silane coupling agent, or the like as the silane treatment agent, as shown in the following formula (A), a silanol group bonded to the silica primary particles And an alkoxy group bonded to the silane-based treatment agent react to form a new Si—O—Si bond by dealcoholization and secondary aggregation.
When the silica primary particles are treated with the chlorosilanes as the silane-based treatment agent, the chloro group of the chlorosilanes and the silanol group bonded to the silica primary particles are dehydrochlorinated to form new Si. The silanol group bonded to —O—Si forms a new Si—O—Si bond by the dehydration reaction, and secondarily aggregates. Further, when the silica primary particles are treated with the chlorosilanes as the silane-based treatment agent, when water coexists in the system, the chlorosilanes are first hydrolyzed into water to generate silanol groups, The silanol groups bonded to the silanol groups and the silica primary particles form a new Si—O—Si bond by the dehydration reaction, and are secondarily aggregated.
When the silica primary particles are treated with silazanes as the silane treatment agent, a new Si-O-Si bond is formed by deammoniation of the silanol groups bonded to the amino groups and the silica primary particles. Secondary aggregation.
However, in said formula (A), R shows an alkyl group.

--- Epoxy-based treatment agent ---
The epoxy-based treatment agent is not particularly limited and can be appropriately selected according to the purpose. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, Examples thereof include bisphenol A novolac type epoxy resin, biphenol type epoxy resin, glycidylamine type epoxy resin, and alicyclic epoxy resin.

As shown in the following formula (B), the epoxy treating agent chemically bonds the silica primary particles to form secondary aggregation. When the silica primary particles are treated using the epoxy-based treatment agent, silanol groups bonded to the silica primary particles add an epoxy group oxygen atom and a carbon atom bonded to the epoxy group of the epoxy-based treatment agent. Thus, a new Si—O—C bond is formed and secondary aggregation occurs.

  There is no restriction | limiting in particular as mixing mass ratio (primary particle: treatment agent) of the said processing agent and the said primary particle, Although it can select suitably according to the objective, 100: 0.01-100: 50 is preferable. . In addition, there exists a tendency for a coalescence degree to become high, so that there is much quantity of the said processing agent.

  There is no restriction | limiting in particular as a mixing method of the said processing agent and the said primary particle, According to the objective, it can select suitably, For example, the method of mixing with a well-known mixer (spray dryer etc.) etc. are mentioned. When mixing, the primary particles may be prepared and then mixed with the treatment agent, or when the primary particles are prepared, the treatment agent is allowed to coexist and prepared in a one-step reaction. May be.

  There is no restriction | limiting in particular as baking temperature of the said processing agent and the said primary particle, Although it can select suitably according to the objective, 100 to 2500 degreeC is preferable. In addition, it exists in the tendency for a coalescence degree to become high, so that the said baking temperature is high.

  There is no restriction | limiting in particular as baking time of the said processing agent and the said primary particle, Although it can select suitably according to the objective, 0.5 to 30 hours are preferable.

-Particle size distribution index of coalescence particles-
By using particles satisfying the following formula (2) as the particle size distribution index of the coalesced particles, the particle size distribution of the coalesced particles becomes sharp. As a result, the proportion of particles functioning as spacers is increased without being embedded in the toner base particles due to external stress, and the generation of toner aggregates can be more effectively suppressed. Thus, the toner replenishment property and the waste toner conveyance property can be maintained well.
However, in the formula (2), Db ₅₀ is the coalesced particles when the particle size (nm) of the coalesced particles is on the horizontal axis and the cumulative value (number%) of the coalesced particles is on the vertical axis. Represents the particle size of the coalesced particles having a cumulative value of 50% by number when drawn from the small particle side, and Db ₁₀ represents the particle size of the coalesced particles having the cumulative value of 10% by number. Represents particle size.

The Db ₅₀ is represented, for example, by the cumulative distribution of the coalesced particles when the horizontal axis is the particle size (nm) of the coalesced particles and the cumulative value (number%) of the coalesced particles is the vertical axis. If the measured number of the coalesced particles is 200, the particle size of the 100th particle, and if it is 150, the particle size of the 75th coalesced particle.

The Db ₅₀ is measured by dispersing the coalesced particles in an appropriate solvent (tetrahydrofuran (THF) or the like), removing the solvent on the substrate and drying the sample, and then using a field emission scanning electron microscope. (FE-SEM, acceleration voltage: 5 kV to 8 kV, observation magnification: 8,000 times to 10,000 times) The particle size of coalesced particles in the visual field is measured, and the cumulative value becomes 50%. This is done by measuring the particle size of the coalesced particles. The particle size of the coalesced particles is measured by measuring the longest length of aggregated particles (the length of the arrow shown in FIG. 2) (measured number of particles: 100 or more and 200 or less).

The Db ₁₀ is represented, for example, by the cumulative distribution of the coalesced particles when the horizontal axis is the particle size (nm) of the coalesced particles and the cumulative value (number%) of the coalesced particles is the vertical axis. If the measured number of the coalesced particles is 200, it means the 20th particle size, and if it is 150, the particle size of the 15th coalesced particle.

The measurement of the Db _{10 in} the coalesced particles is performed by measuring the electric field emission of a sample obtained by dispersing the coalesced particles in an appropriate solvent (tetrahydrofuran (THF) or the like) and then removing the solvent on the substrate to dry it. The particle diameter of coalesced particles in the field of view is measured with a scanning electron microscope (FE-SEM, acceleration voltage: 5 kV to 8 kV, observation magnification: 8,000 times to 10,000 times). The measurement is carried out by measuring the particle size of the coalesced particles to be 10%. The particle size of the coalesced particles is measured by measuring the longest length of aggregated particles (the length of the arrow shown in FIG. 2) (measured number of particles: 100 or more and 200 or less).

The “Db ₅₀ / Db ₁₀ ” is preferably 1.20 or less, and more preferably 1.15 or less. When the “Db ₅₀ / Db ₁₀ ” exceeds 1.20, the particle size distribution of the coalesced particles is wide and the number of particles having a small particle size increases. That is, “small particle A” (particles that are not coalesced and exist in the form of primary particles) or “small particle B” (coagulant is advancing, but primary particles This means that at least one of the particles having a small particle size is large. If the “small particle A” is large, the function as a non-spherical external additive cannot be achieved and the embedding resistance is inferior. This is not preferable because the toner replenishment property, the toner replenishment property and the waste toner conveyance property are deteriorated, and the waste toner lock is likely to occur. On the other hand, if the “small particle B” is large, the function as a spacer cannot be achieved. Therefore, deterioration of toner cohesiveness cannot be sufficiently suppressed, and toner replenishment property and waste toner can be reduced at an initial stage. Since it may become easy to produce deterioration of a conveyance property, it is not preferable. Therefore, it is necessary to reduce the “small particle A” and the “small particle B”.

  The method for reducing the “small particle A” and the “small particle B” is not particularly limited and may be appropriately selected depending on the intended purpose. A method of removing particles having a diameter is preferable.

-Crack resistance of coalesced particles-
The coalescing particles preferably satisfy the following formula (3), and more preferably satisfy the following formula (3-1). As a result, the cohesive force (cohesive force) between the primary particles constituting the coalesced particles is maintained even with agitation stress in the developing machine, so that the toner can be more effectively used without being embedded in the toner base particles. The generation of aggregates can be suppressed, and even in a high-speed machine having a large stirring stress, toner replenishability and waste toner transportability can be maintained well over time.
However, in the formula (3) and the formula (3-1), Nx represents the number of primary particles in 1,000 particles of the external additive. The number of primary particles in 1,000 particles was agitated with a mixing stirrer at 67 Hz for 10 minutes with respect to 0.5 g of the external additive and 49.5 g of the carrier placed in a 50 mL bottle. Then, it observes and measures with a scanning electron microscope.

  When the coalescence force of the coalesced particles is strong (as shown in FIG. 4, cracked or disintegrated particles occupying 1,000 (the coalesced) particles (for example, particles 4 shown in a black frame in FIG. 4)) If the ratio of the external additive is 30% or less), the external additive in the toner is less likely to crack or disintegrate due to the load of the developing device (cracking or disintegrating particles), and burying or rolling of the external additive is suppressed. The toner replenishment property and waste toner transportability can be maintained well over time, which is preferable.

  When the coalescing force of the coalesced particles is weak (as shown in FIG. 5, cracked or disintegrated particles occupying 1,000 (the coalesced) particles (for example, particles 4 shown in a black frame in FIG. 5)) If the ratio of the external additive exceeds 30%), the external additive in the toner increases the number of particles that are cracked or disintegrated by a load such as a developing device, the percentage of spherical particles increases, and the external additive moves or is buried. This is not preferable because the toner replenishment property and waste toner transportability over time and the occurrence of waste toner lock may not be suppressed.

-Condition (3)-
In the formula (3), the cracked or disintegrated particles refer to particles that are present alone as the primary particles, and are cracked or disintegrated after the coalesced particles are stirred under the stirring conditions using the rocking mill. And particles that have been present as the primary particles alone before the agitation, for example, particles shown in reference numeral 2 in FIG. 3 and black frames in FIGS. 4 to 5 4 and the like, the primary particles are not coalesced and the particles are present alone. In addition, the particle | grains shown with the code | symbol 1 of FIG. 3, and the code | symbol 3 of FIGS. 4-5 are secondary particles.
In the formula (3), the shape of the cracked or disintegrated particles is not particularly limited as long as the particles are not bonded to each other, and can be appropriately selected according to the purpose. As indicated by reference numeral 2, it is often present in a substantially spherical state.

In the formula (3), the method for confirming the presence of the cracked or disintegrated particles is not particularly limited and may be appropriately selected depending on the intended purpose. However, with a scanning electron microscope (SEM) A method of confirming the existence of particles alone by observing is preferable.
The method for measuring the average particle size of the cracked or disintegrated particles is not particularly limited and may be appropriately selected depending on the intended purpose. However, a scanning electron microscope (FE-SEM, acceleration voltage: 5 kV to 8 kV, observation magnification: (8,000 times to 10,000 times) by measuring the average value of the diameters of the cracked or disintegrated particles in the field of view (measured number of particles: 100 or more).

In the formula (3), as the measurement of cracks or collapsed particles occupying 1,000 particles, after stirring, the particles are observed with a scanning electron microscope, and the symbol 2 in FIG. 3 and FIGS. Like the particle 4 shown in the black frame, a particle present alone is measured as one cracked or disintegrated particle.
In the above formula (3), when measuring the number of cracked or disintegrated particles in 1,000 particles, coalescence particles formed by coalescing a plurality of particles were confirmed by the scanning electron microscope. In this case, the coalesced particles are measured as one particle.

In the formula (3), a rocking mill (manufactured by Seiwa Giken Co., Ltd.) is used as the mixing stirrer.
As the carrier used in the formula (3), a resin obtained by applying or drying a coating film forming solution of an acrylic resin and a silicone resin containing alumina particles on the surface of a fired ferrite powder (weight average particle size: 35 μm). Use a coated ferrite carrier.
In said Formula (3), there is no restriction | limiting in particular as said 50 mL bottle, According to the objective, it can select suitably, For example, the commercially available glass bottle (made by Nidec Rika Glass Co., Ltd.) etc. are mentioned.

-Characteristics of coalesced particles-
The degree of coalescence is the number average particle diameter (Db) of one coalesced particle (secondary particle) and the coalesced particle in the measurement of the primary particle size and the secondary particle size of the coalesced particle. The number average particle diameter (Da) of a plurality of primary particles can be obtained and calculated by the following formula.
Degree of coalescence (Db / Da) = number average particle size of coalesced particles / number average particle size of primary particles 100 or more coalesced particles were observed, and the degree of coalescence of each particle was determined. Find the average value.
There is no restriction | limiting in particular as an average value of the coalescence degree of the said coalesced particle, Although it can select suitably according to the objective, 1.5-4.0 are preferable. When the average value of the degree of coalescence is less than 1.5, the function as a non-spherical external additive cannot be achieved, and the coalesced particles are easily transferred to the concave portions on the surface of the toner base particles. In this case, the deterioration of the toner cohesiveness over time cannot be sufficiently suppressed, and the toner replenishment property and the waste toner transportability may be easily deteriorated. On the other hand, if it exceeds 4.0, the coalesced particles are easily peeled off from the toner base particles, and the carrier contamination and the photoconductor may be damaged, which may cause image defects over time.

  The content of the coalesced particles having a coalescence degree of less than 1.3 in the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10% by number or less. The degree of coalescence has a distribution in production, and the particles having the degree of coalescence of less than 1.3 are particles in which the coalescence has not progressed and are present in a nearly spherical state. . Therefore, it is difficult to perform the function as a non-spherical additive characterized for suppressing burial. The content of the coalesced particles having a coalescence degree of less than 1.3 is measured by the above-described method using the average primary particle size of the coalesced particles and the particle size of the secondary particles as 100. After measuring from 200 to 200, the degree of coalescence of each coalesced particle is calculated from the obtained measurement value, and the number of particles with the degree of coalescence less than 1.3 is divided by the number of measurements. .

  The method for confirming that the primary particles of the coalesced particles are coalesced is not particularly limited and can be appropriately selected according to the purpose, but is observed with a scanning electron microscope (SEM). Thus, a method of confirming that the primary particles are coalesced is preferable.

  The content of the coalesced particles is preferably 0.5 parts by mass to 4.0 parts by mass, and more preferably 1.0 parts by mass to 3.0 parts by mass with respect to 100 parts by mass of the toner base particles. When the content of the coalesced particles is less than 0.5 parts by mass, deterioration of toner cohesiveness cannot be sufficiently suppressed with respect to agitation stress over time, and toner replenishability and waste toner transportability. May deteriorate, which is not preferable. When the content of the coalesced particles exceeds 4.0 parts by mass, the fluidity of the toner is remarkably deteriorated, and it may be difficult to replenish the toner or waste toner lock may occur. .

-Other external additives-
In addition to the coalescing particles, the toner preferably contains inorganic fine particles having a number average primary particle size of 30 nm to 60 nm, more preferably 30 nm to 50 nm. By containing inorganic fine particles having a number average primary particle size in the above range, a decrease in the loose apparent density ρ _H of the toner after storage for 14 days in a high-temperature and high-humidity (70% RH at 40 ° C.) temperature is suppressed. This is preferable.

  The other external additive is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, silica fine particles, hydrophobized silica fine particles, fatty acid metal salts (for example, stearic acid) Zinc, aluminum stearate, etc.); metal oxides (for example, titania, alumina, tin oxide, antimony oxide, etc.) or their hydrophobized products, fluoropolymers, and the like. Among these, hydrophobized silica fine particles, titania particles, and hydrophobized titania fine particles are preferable.

Examples of the hydrophobized silica fine particles include HDK H2000T, HDK H2000 / 4, HDK H2050EP, HVK21, and HDK H1303VP (all manufactured by Clariant Japan); R972, R974, RX200, RY200, R202, R805, R812. (Both manufactured by Nippon Aerosil Co., Ltd.). Examples of the titania fine particles include P-25 (manufactured by Nippon Aerosil Co., Ltd.); STT-30, STT-65C-S (both manufactured by Titanium Industry Co., Ltd.); TAF-140 (manufactured by Fuji Titanium Industry Co., Ltd.). MT-150W, MT-500B, MT-600B, MT-150A (all manufactured by Teika Co., Ltd.) and the like.
Examples of the hydrophobized titanium oxide fine particles include T-805 (manufactured by Nippon Aerosil Co., Ltd.); STT-30A, STT-65S-S (both manufactured by Titanium Industry Co., Ltd.); TAF-500T, TAF- 1500T (all manufactured by Fuji Titanium Industry Co., Ltd.); MT-100S, MT-100T (all manufactured by Teika Co., Ltd.); IT-S (manufactured by Ishihara Sangyo Co., Ltd.), and the like.

  The content of the other external additive is not particularly limited and may be appropriately selected depending on the intended purpose. It is 0.3 to 3.0 parts by mass with respect to 100 parts by mass of the toner base particles. Is preferable, and 0.5 mass part-2.0 mass parts is more preferable.

The total coverage of the coalesced particles and other external additives on the toner base particles is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 50% to 90%, preferably 60%. -80% is more preferable. By setting the total coverage of the coalesced particles and other external additives to the toner base particles within the above range, the toner after storage for 14 days in a high-temperature, high-humidity (70% RH at 40 ° C.) This is preferable because a decrease in the loose apparent density ρ _H tends to be suppressed.

<Toner base particles>
The toner base particles contain a binder resin and a colorant, and further contain other components such as a release agent, a charge control agent, and a layered inorganic mineral as necessary.

<< Binder resin >>
The binder resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, polyester resin, silicone resin, styrene-acrylic resin, styrene resin, acrylic resin, epoxy resin, diene resin, phenol Examples thereof include resins, terpene resins, coumarin resins, amideimide resins, butyral resins, urethane resins, and ethylene vinyl acetate resins. These may be used individually by 1 type and may use 2 or more types together. Among these, polyester resin, polyester resin and the above-mentioned other binder resins are combined in that they have excellent low-temperature fixability, can smooth the image surface, and have sufficient flexibility even when the molecular weight is lowered. Resins are preferred.

-Polyester resin-
There is no restriction | limiting in particular as said polyester resin, Although it can select suitably according to the objective, An unmodified polyester resin and a modified polyester resin are preferable. These may be used individually by 1 type and may use 2 or more types together.

--Unmodified polyester resin--
There is no restriction | limiting in particular as said unmodified polyester resin, According to the objective, it can select suitably, For example, the polyol represented by following General formula (1), and poly represented by following General formula (2) Examples thereof include resins obtained by polyesterifying carboxylic acid and crystalline polyester resins. Even in a high-speed machine equipped with a toner having excellent low-temperature fixability using a crystalline polyester resin, the present invention easily causes toner agglomeration, and the deterioration of toner replenishment property and waste toner conveyance property becomes more remarkable. Similarly, it is possible to provide a toner capable of maintaining good toner replenishability and waste toner transportability over time.
However, in the said General formula (1), A represents the aromatic group or heterocyclic aromatic group which may have a C1-C20 alkyl group, an alkylene group, and a substituent, m is 2- Represents an integer of 4.
However, in said general formula (2), B represents the C1-C20 alkyl group, alkylene group, the aromatic group which may have a substituent, or a heterocyclic aromatic group, and n is 2-2. Represents an integer of 4.

  There is no restriction | limiting in particular as a polyol represented by the said General formula (1), According to the objective, it can select suitably, For example, ethylene glycol, diethylene glycol, triethylene glycol, 1, 2- propylene glycol, 1, 3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene Glycol, polypropylene glycol, polytetramethylene glycol, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, bisphenol A, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, hydrogenated bisphenol A, hydrogenated bisphenol A ethylene oxide adduct, hydrogenated bisphenol A propylene oxide adduct, and the like. These may be used alone or in combination of two or more.

  There is no restriction | limiting in particular as polycarboxylic acid represented by the said General formula (2), According to the objective, it can select suitably, For example, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalate Acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, malonic acid, n-dodecenyl succinic acid, isooctyl succinic acid, isododecenyl succinic acid, n-dodecyl succinic acid, isododecyl succinic acid , N-octenyl succinic acid, n-octyl succinic acid, isooctenyl succinic acid, isooctyl succinic acid, 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-di Ruboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, empor trimer Examples include acids, etc., cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, butanetetracarboxylic acid, diphenylsulfonetetracarboxylic acid, ethylene glycol bis (trimellitic acid), and the like. These may be used alone or in combination of two or more.

--- Crystalline polyester resin ---
A crystalline polyester resin can be contained as the polyester resin.
The crystalline polyester resin is, for example, a C2-C12 saturated aliphatic diol compound as an alcohol component and a C2-C12 dicarboxylic acid having a double bond (C = C bond) as an acid component, or carbon. A crystalline polyester synthesized using a saturated dicarboxylic acid of 2 to 12 is preferable.
Examples of the saturated aliphatic diol compound having 2 to 12 carbon atoms as the alcohol component include 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1, Examples thereof include 12-dodecanediol, and derivatives thereof.
Examples of the dicarboxylic acid having 2 to 12 carbon atoms or a saturated dicarboxylic acid having 2 to 12 carbon atoms having a double bond (C═C bond) as the acid component include fumaric acid, 1,4-butanedioic acid, Examples include 1,6-hexanedioic acid, 1,8-octanedioic acid, 1,10-decanedioic acid, 1,12-dodecanedioic acid, and derivatives thereof.

  Among these, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,1 in terms of reducing the difference between the endothermic peak temperature and the endothermic shoulder temperature. Any one alcohol component of 12-dodecanediol, fumaric acid, 1,4-butanedioic acid, 1,6-hexanedioic acid, 1,8-octanedioic acid, 1,10-decanedioic acid, 1 , 12-dodecanedioic acid is preferably composed of only one dicarboxylic acid component.

  As a method for controlling the crystallinity and softening point of the crystalline polyester resin, a trivalent or higher polyhydric alcohol such as glycerin is used as an alcohol component and a trivalent or higher polyvalent such as trimellitic anhydride is used as an acid component during polyester synthesis. Examples thereof include a method of designing and using a non-linear polyester subjected to condensation polymerization by adding a carboxylic acid.

  The molecular structure of the crystalline polyester resin can be confirmed by X-ray diffraction, GC / MS, LC / MS, IR measurement, etc. in addition to NMR measurement by solution or solid.

  There is no restriction | limiting in particular as content in the said toner of the said crystalline polyester resin, Although it can select suitably according to the objective, 3 mass%-15 mass% are preferable, and 5 mass%-10 mass% are more. preferable. When the content is less than 3% by mass, the effect on the low-temperature fixability may not be sufficiently obtained. When the content exceeds 15% by mass, the toner transportability and replenishment with time may be deteriorated, or the waste toner lock may be lost. It tends to occur easily.

--Modified polyester resin--
There is no restriction | limiting in particular as said modified polyester resin, According to the objective, it can select suitably, For example, polyester (henceforth "polyester prepolymer" which can react with an active hydrogen group containing compound and the said active hydrogen group containing compound) And a resin obtained by an extension reaction or a crosslinking reaction. The extension reaction or crosslinking reaction may be stopped by a reaction terminator (blocked monoamine such as diethylamine, dibutylamine, butylamine, laurylamine, ketimine compound, etc.) as necessary.

--- Active hydrogen group-containing compound ---
The active hydrogen group-containing compound acts as an elongation agent, a crosslinking agent or the like when the polyester prepolymer undergoes an elongation reaction, a crosslinking reaction, or the like in an aqueous phase.

  The active hydrogen group-containing compound is not particularly limited as long as it has an active hydrogen group, and can be appropriately selected according to the purpose. However, when the polyester prepolymer is an isocyanate group-containing polyester prepolymer described later. An amine is preferable in that a high molecular weight can be obtained.

  There is no restriction | limiting in particular as said active hydrogen group, According to the objective, it can select suitably, For example, a hydroxyl group (alcoholic hydroxyl group or phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group etc. are mentioned. These may be contained singly or in combination of two or more.

The amines that are the active hydrogen group-containing compounds are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diamines, trivalent or higher polyamines, amino alcohols, amino mercaptans, amino acids, and the like. Examples include those obtained by blocking the amino group of amines.
Examples of the diamine include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′-dimethyldicyclohexylmethane, diamines). Cyclohexane, isophorone diamine, etc.); aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine, etc.) and the like.
Examples of the trivalent or higher polyamine include diethylenetriamine and triethylenetetramine.
Examples of the amino alcohol include ethanolamine and hydroxyethylaniline.
Examples of the amino mercaptan include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid include aminopropionic acid and aminocaproic acid.
Examples of the blocked amino groups of these amines include, for example, any of these amines (diamine, trivalent or higher polyamine, amino alcohol, amino mercaptan, amino acid, etc.) and ketones (acetone, methyl ethyl ketone, And ketimine compounds obtained from methyl isobutyl ketone and the like, and oxazolidone compounds.
These may be used individually by 1 type and may use 2 or more types together. Among these, the amines are particularly preferably diamine and a mixture of a diamine and a small amount of a trivalent or higher polyamine.

--- Polymer capable of reacting with active hydrogen group-containing compound ---
The polymer capable of reacting with the active hydrogen group-containing compound is not particularly limited as long as it is a polymer having at least a group capable of reacting with the active hydrogen group-containing compound, and can be appropriately selected according to the purpose. However, it has excellent fluidity and transparency when melted, it is easy to adjust the molecular weight of the polymer component, and it is excellent in oilless low-temperature fixability and releasability in dry toners. ) Is preferred, and an isocyanate group-containing polyester prepolymer is more preferred.

  The isocyanate group-containing polyester prepolymer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a polycondensate of a polyol and a polycarboxylic acid, a reactive hydrogen group-containing polyester resin is reacted with a polyisocyanate. And the like.

  The polyol is not particularly limited and may be appropriately selected depending on the intended purpose. For example, alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.), alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.), alicyclic diol (1,4-cyclohexanedimethanol, Hydrogenated bisphenol A, etc.), bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.), alkylene oxides of the above alicyclic diols (ethylene oxide, propylene oxide) Diol, butylene oxide etc.) adducts, diols such as alkylene oxide (ethylene oxide, propylene oxide, butylene oxide etc.) adducts of the above bisphenols; polyhydric aliphatic alcohols (glycerin, trimethylol ethane, trimethylol propane, pentaerythritol) , Sorbitol, etc.) Trivalent or higher valent phenols (phenol novolak, cresol novolak, etc.), Trivalent or higher polyols such as alkylene oxide adducts of trivalent or higher polyphenols; Mixtures of diol and trivalent or higher polyols; Etc. These may be used individually by 1 type and may use 2 or more types together. Among these, the polyol is preferably the diol alone or a mixture of the diol and a small amount of the trivalent or higher polyol. Examples of the diol include alkylene glycols having 2 to 12 carbon atoms, alkylene oxide adducts of bisphenols (bisphenol A ethylene oxide 2 mol adduct, bisphenol A propylene oxide 2 mol adduct, bisphenol A propylene oxide 3 mol adduct, etc.) Is preferred.

  There is no restriction | limiting in particular as content in the isocyanate group containing polyester prepolymer of the said polyol, Although it can select suitably according to the objective, For example, 0.5 mass%-40 mass% are preferable, and 1 mass%- 30 mass% is more preferable, and 2 mass%-20 mass% is especially preferable. When the content is less than 0.5% by mass, the hot offset resistance is deteriorated, and it may be difficult to achieve both the storage stability of the toner and the low-temperature fixability. Fixability may deteriorate.

  There is no restriction | limiting in particular as said polycarboxylic acid, According to the objective, it can select suitably, For example, alkylene dicarboxylic acid (succinic acid, adipic acid, sebacic acid, etc.); Alkenylene dicarboxylic acid (maleic acid, fumaric acid, etc.) ); Aromatic dicarboxylic acid (terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, etc.); trivalent or higher polycarboxylic acid (trimellitic acid, pyromellitic acid, etc., C9-20 aromatic polycarboxylic acid, etc.), etc. Is mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, the polycarboxylic acid is preferably an alkenylene dicarboxylic acid having 4 to 20 carbon atoms and an aromatic dicarboxylic acid having 8 to 20 carbon atoms. In place of the polycarboxylic acid, an anhydride of polycarboxylic acid, a lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.) may be used.

  The mixing ratio of the polyol and the polycarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. The mixing ratio of the hydroxyl group [OH] of the polyol and the carboxyl group [COOH] of the polycarboxylic acid is not limited. The equivalent ratio [OH] / [COOH] is preferably 2/1 to 1/1, more preferably 1.5 / 1 to 1/1, and particularly preferably 1.3 / 1 to 1.02 / 1.

  The polyisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, aliphatic polyisocyanate (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, octamethylene Diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, tetramethylhexane diisocyanate, etc .; alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); aromatic diisocyanates (tolylene diisocyanate, diphenylmethane, etc.) Diisocyanate, 1,5-naphthylene diisocyanate, diphenylene-4, '-Diisocyanate, 4,4'-diisocyanato-3,3'-dimethyldiphenyl, 3-methyldiphenylmethane-4,4'-diisocyanate, diphenyl ether-4,4'-diisocyanate, etc .; araliphatic diisocyanate (α, α , Α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates (tris-isocyanatoalkyl-isocyanurate, triisocyanatocycloalkyl-isocyanurate, etc.); these phenol derivatives; blocked with oximes, caprolactam, etc. And the like. These may be used alone or in combination of two or more.

  The mixing ratio of the polyisocyanate and the active hydrogen group-containing polyester resin (hydroxyl group-containing polyester resin) is not particularly limited and may be appropriately selected depending on the intended purpose. ] And the equivalent ratio [NCO] / [OH] of hydroxyl group [OH] of the hydroxyl group-containing polyester resin is preferably 5/1 to 1/1, more preferably 4/1 to 1.2 / 1, and 3 / 1-1.5 / 1 is particularly preferred. When the equivalent ratio [NCO] / [OH] is less than 1/1, the offset resistance may be deteriorated, and when it exceeds 5/1, the low-temperature fixability may be deteriorated.

  There is no restriction | limiting in particular as content of the said polyisocyanate in the said isocyanate group containing polyester prepolymer, Although it can select suitably according to the objective, 0.5 mass%-40 mass% are preferable, and 1 mass% -30% by mass is more preferable, and 2% by mass to 20% by mass is particularly preferable. When the content is less than 0.5% by mass, the hot offset resistance is deteriorated, and it may be difficult to achieve both storage stability and low-temperature fixability. May get worse.

  There is no restriction | limiting in particular as an average number of the isocyanate group contained per molecule of the said isocyanate group containing polyester prepolymer, Although 1 or more are preferable, 1.2-5 are preferable. More preferably, 1.5-4 is still more preferable. When the average number is less than 1, the molecular weight of the polyester resin (RMPE) modified with a urea bond-forming group is lowered, and the hot offset resistance may be deteriorated.

  The mixing ratio of the isocyanate group-containing polyester prepolymer and the amines is not particularly limited and may be appropriately selected depending on the intended purpose. The isocyanate group [NCO] in the isocyanate group-containing polyester prepolymer is not limited. The mixing equivalent ratio [NCO] / [NHx] of amino groups [NHx] in the amines is preferably 1/3 to 3/1, more preferably 1/2 to 2/1, and 1/1. 5-1.5 / 1 is particularly preferred. If the mixing equivalent ratio ([NCO] / [NHx]) is less than 1/3, the low-temperature fixability may be reduced. If it exceeds 3/1, the molecular weight of the urea-modified polyester resin is reduced. Hot offset resistance may deteriorate.

--- Method for synthesizing polymer capable of reacting with active hydrogen group-containing compound ---
The method for synthesizing the polymer capable of reacting with the active hydrogen group-containing compound is not particularly limited and can be appropriately selected according to the purpose. For example, in the case of the isocyanate group-containing polyester prepolymer, the polyol and the Polycarboxylic acid is produced in the presence of a known esterification catalyst (titanium tetrabutoxide, dibutyltin oxide, etc.), heated to 150 ° C. to 280 ° C. while appropriately reducing the pressure as necessary, and water is distilled off to contain a hydroxyl group Examples thereof include a method of synthesizing the polyester by reacting the hydroxyl group-containing polyester with the polyisocyanate at 40 ° C. to 140 ° C. after obtaining the polyester.

There is no restriction | limiting in particular as a weight average molecular weight (Mw) of the polymer which can react with the said active hydrogen group containing compound, Although it can select suitably according to the objective, Tetrahydrofuran (THF) soluble GPC (gel) The molecular weight distribution by permeation chromatography) is preferably 3,000 to 40,000, and more preferably 4,000 to 30,000. When the weight average molecular weight (Mw) is less than 3,000, the storage stability may be deteriorated, and when it exceeds 40,000, the low temperature fixability may be deteriorated.
The weight average molecular weight (Mw) can be measured, for example, as follows. First, the column was stabilized in a 40 ° C. heat chamber, and at this temperature, tetrahydrofuran (THF) was flowed as a column solvent at a flow rate of 1 mL / min to adjust the sample concentration to 0.05 mass% to 0.6 mass%. Measurement is performed by injecting 50 μL to 200 μL of a resin tetrahydrofuran sample solution. In measuring the molecular weight of the sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of the calibration curve prepared by several monodisperse polystyrene standard samples and the number of counts.
As a standard polystyrene sample for preparing a calibration curve, Pressure Chemical Co. Or Tosoh molecular weight of KK is ^{6 × 10 2, 2.1 × 10} 2, 4 × 10 2, 1.75 × 10 4, 1.1 × 10 5, 3.9 × 10 5, 8.6 × It is preferable to use 10 ⁵ , 2 × 10 ⁶ , and 4.48 × 10 ⁶ and use at least about 10 standard polystyrene samples. An RI (refractive index) detector can be used as the detector.

-Colorant-
There is no restriction | limiting in particular as said coloring agent, According to the objective, it can select suitably from well-known coloring agents.
The color of the colorant of the toner is not particularly limited and can be appropriately selected according to the purpose, and can be at least one selected from black toner, cyan toner, magenta toner, and yellow toner, The toner of each color can be obtained by appropriately selecting the type of colorant, but a color toner is preferable.

  For black, for example, carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, copper, iron (CI pigment black 11), titanium oxide And organic pigments such as aniline black (CI Pigment Black 1).

  Examples of magenta coloring pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 48: 1, 49, 50, 51, 52, 53, 53: 1, 54, 55, 57, 57: 1, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 150, 163, 177, 179, 184, 202, 206, 207, 209, 211, 269; I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, and the like.

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

  Examples of the color pigment for yellow include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 55, 65, 73, 74, 83, 97, 110, 139, 151, 154, 155, 180, 185; I. Bat yellow 1, 3, 20, orange 36, and the like.

  The content of the colorant in the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1% by mass to 15% by mass, and more preferably 3% by mass to 10% by mass. When the content is less than 1% by mass, the coloring power of the toner may be reduced. When the content is more than 15% by mass, poor dispersion of the pigment in the toner may occur. The characteristics may be degraded.

  The colorant may be used as a master batch combined with a resin. Such a resin is not particularly limited. However, from the viewpoint of compatibility with the binder resin in the present invention, it is preferable to use the binder resin or a resin having a structure similar to the binder resin.

  The masterbatch can be produced by applying a high shear force and mixing or kneading the resin and the colorant. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the colorant and the resin. Also, the so-called flushing method is preferable in that the wet cake of the colorant can be used as it is, and there is no need to dry it. The flushing method is a method in which an aqueous paste containing water of a colorant is mixed or kneaded together with a resin and an organic solvent, and the colorant is transferred to the resin side to remove water and the organic solvent. For mixing or kneading, for example, a high shear dispersion device such as a three-roll mill can be used.

-Release agent-
The release agent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include plant waxes (carnauba wax, cotton wax, wood wax, rice wax, etc.), animal waxes (honey beeswax, lanolin). Waxes and waxes such as mineral wax (such as ozokerite and cercin), petroleum wax (such as paraffin, microcrystalline, and petrolatum); synthetic hydrocarbon wax (such as Fischer-Tropsch wax and polyethylene wax), and synthetic wax ( Esters, ketones, ethers, etc.) other than natural waxes; 1,2-hydroxystearic amide, stearic amide, phthalic anhydride, fatty acid amides such as chlorinated hydrocarbons; low molecular weight crystalline polymers Some polymethacrylate n-stearyl, polymethacrylate n Crystalline polymers having a long chain alkyl group in the side chain of the homopolymer or copolymer (acrylic acid n- stearyl over ethyl methacrylate copolymer, etc.) and the like polyacrylates lauryl and the like; and the like. These may be used individually by 1 type and may use 2 or more types together.
Among these, since it can act effectively as a release agent between the fixing roller and the toner interface, high temperature offset resistance can be improved without applying a release agent such as oil to the fixing roller. A wax having a melting point of 50 ° C. to 120 ° C. is preferable because it can be used.

There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, 50 to 120 degreeC is preferable and 60 to 90 degreeC is more preferable. When the melting point is less than 50 ° C., the release agent may adversely affect storage stability. When the melting point exceeds 120 ° C., cold offset may easily occur during fixing at a low temperature.
The melting point of the release agent is determined, for example, by measuring the maximum endothermic peak using a differential scanning calorimeter (TG-DSC system, TAS-100, manufactured by Rigaku Corporation).

  There is no restriction | limiting in particular as melt viscosity of the said mold release agent, Although it can select suitably according to the objective, As a measured value in temperature 20 degreeC higher than melting | fusing point of the said mold release agent, 5 cps-1,000 cps are. Preferably, 10 cps to 100 cps is more preferable. If the melt viscosity is less than 5 cps, the releasability may be lowered, and if it exceeds 1,000 cps, the effect of improving hot offset resistance and low-temperature fixability may not be obtained.

  The release agent is preferably present in a dispersed state in the toner base particles, and for this purpose, the release agent and the binder resin are preferably incompatible with each other. The method for finely dispersing the release agent in the toner base particles is not particularly limited and may be appropriately selected depending on the purpose. For example, the release agent is dispersed by applying a kneading shear force during toner production. The method etc. are mentioned.

  The dispersion state of the release agent can be confirmed by observing a thin film slice of toner particles with a transmission electron microscope (TEM). The dispersion diameter of the release agent is preferably small, but if it is too small, there are cases where bleeding during fixing is insufficient. Therefore, if the release agent can be confirmed at a magnification of 10,000, the release agent is present in a dispersed state. When the release agent cannot be confirmed at 10,000 times, even when finely dispersed, the dyeing at the time of fixing becomes insufficient.

  There is no restriction | limiting in particular as content in the said toner of the said release agent, Although it can select suitably according to the objective, 1 mass%-20 mass% are preferable, and 3 mass%-10 mass% are more preferable. . If the content is less than 1% by mass, the hot offset resistance tends to deteriorate, and if it exceeds 20% by mass, the heat resistant storage stability, chargeability, transferability, and stress resistance tend to deteriorate. Therefore, it is not preferable.

-Charge control agent-
Further, in order to impart an appropriate charging ability to the toner, a charge control agent can be contained in the toner as necessary.
The charge control agent is not particularly limited, and any known charge control agent can be used. Since the color tone may change when a colored material is used, a colorless or nearly white material is preferable. For example, a triphenylmethane dye, a molybdate chelate pigment, a rhodamine dye, an alkoxyamine, a quaternary ammonium salt (fluorine) Modified quaternary ammonium salts), alkylamides, phosphorus alone or compounds thereof, tungsten alone or compounds thereof, fluorine-based activators, metal salts of salicylic acid, metal salts of salicylic acid derivatives, and the like. These may be used individually by 1 type and may use 2 or more types together.

  The content of the charge control agent is determined by the toner production method including the type of the binder resin and the dispersion method, and is not uniquely limited, but is 0% relative to the binder resin. 0.01 mass%-5 mass% are preferable, and 0.02 mass%-2 mass% are more preferable. When the content exceeds 5% by mass, the chargeability of the toner is too high, the effect of the charge control agent is diminished, the electrostatic attraction with the developing roller is increased, the flowability of the developer is reduced, and the image The density may be lowered, and if it is less than 0.01% by mass, the charge start-up property and the charge amount are not sufficient, and the toner image may be easily affected.

-Layered inorganic mineral-
The layered inorganic mineral is not particularly limited as long as it is an inorganic mineral in which a layer having a thickness of several nm is laminated, and can be appropriately selected according to the purpose. For example, montmorillonite, bentonite, hectorite, attapulgite, Sepiolite, a mixture thereof, and the like. These may be used alone or in combination of two or more. Among these, a modified layered inorganic mineral is preferable because it can be modified when the toner is granulated, has a charge control function, and is excellent in low-temperature fixing, and a layered inorganic mineral having a montmorillonite-based basic crystal structure is an organic cation. Organic modified montmorillonite and bentonite are particularly preferred from the viewpoint that the modified layered inorganic mineral modified with the above is more preferable, and the viscosity can be easily adjusted without affecting the toner characteristics.

  The modified layered inorganic compound preferably modifies at least part of the layered inorganic mineral with organic ions. By modifying at least a part of the layered inorganic mineral with organic ions, the layer has an appropriate hydrophobicity, the oil phase containing the toner composition and / or the toner composition precursor has a non-Newtonian viscosity, Can be modified.

  There is no restriction | limiting in particular as content in the said toner of the said modified | denatured layered inorganic mineral, Although it can select suitably according to the objective, 0.05 mass%-5 mass% are preferable.

<< Toner Production Method >>
The method for producing the toner of the present invention is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a kneading and pulverizing method and a so-called chemical method of granulating toner particles in an aqueous medium.
Examples of the chemical method include a suspension polymerization method, an emulsion polymerization method, a seed polymerization method, a dispersion polymerization method, etc., in which a monomer is used as a starting material; a resin or a resin precursor is dissolved in an organic solvent and the like in an aqueous medium. Dispersing or emulsifying dissolution suspension method; in the dissolution suspension method, an oil phase composition containing a resin precursor (reactive group-containing prepolymer) having a functional group capable of reacting with an active hydrogen group is contained in resin fine particles. A method of emulsifying or dispersing in an aqueous medium and reacting the active hydrogen group-containing compound and the reactive group-containing prepolymer in the aqueous medium (production method (I)); Phase inversion emulsification method in which water is added to a solution composed of an emulsifier; the resin particles obtained by these methods are aggregated in a state of being dispersed in an aqueous medium and granulated into particles of a desired size by heating and melting. Aggregation And the like. Among these, the toner obtained by the dissolution suspension method, the production method (I), and the aggregation method is preferable from the viewpoint of granulation properties (particle size distribution control, particle shape control, etc.) by the crystalline resin, and the production method described above. The toner obtained in (I) is more preferable.

  The kneading and pulverizing method is, for example, a method of producing the toner base particles by pulverizing and classifying a melt-kneaded toner material having a colorant, a binder resin, and a release agent.

  In the melt kneading, the toner materials are mixed, and the mixture is charged into a melt kneader and melt kneaded. As the melt kneader, for example, a uniaxial or biaxial continuous kneader or a batch kneader using a roll mill can be used. For example, a KTK type twin screw extruder manufactured by Kobe Steel, a TEM type extruder manufactured by Toshiba Machine Co., Ltd., a twin screw extruder manufactured by Casey Kay, a PCM type twin screw extruder manufactured by Ikegai Iron Works, a Kneader manufactured by Buss, etc. are suitable. Used. This melt-kneading is preferably performed under appropriate conditions so as not to cause the molecular chains of the binder resin to be broken. Specifically, the melt-kneading temperature is determined with reference to the softening point of the binder resin. If the temperature is higher than the softening point, cutting is severe, and if the temperature is too low, dispersion may not proceed.

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

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

  In the dissolution suspension method, for example, an oil phase composition in which a toner composition containing at least a binder resin or a resin precursor, a colorant, and a release agent is dissolved or dispersed in an organic solvent is used. In this method, toner base particles are produced by dispersing or emulsifying in a medium.

The organic solvent used for dissolving or dispersing the toner composition is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal of the solvent later.
The organic solvent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, ester solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, and ethyl cellosolve acetate Ether solvents such as diethyl ether, tetrahydrofuran, dioxane, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, cyclohexanone, methanol, ethanol, n- Alcohol solvents such as propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexyl alcohol, benzyl alcohol, etc. It is below. These may be used individually by 1 type and may use 2 or more types together.

In the dissolution suspension method, when the oil phase composition is dispersed or emulsified in an aqueous medium, an emulsifier or a dispersant may be used as necessary.
There is no restriction | limiting in particular as said emulsifier or a dispersing agent, According to the objective, it can select suitably, For example, surfactant, water-soluble polymer, etc. are mentioned.
There is no restriction | limiting in particular as said surfactant, According to the objective, it can select suitably, For example, anionic surfactant (alkylbenzenesulfonic acid, phosphate ester, etc.), cationic surfactant (quaternary ammonium salt type) , Amine salt type, etc.), amphoteric surfactants (carboxylate type, sulfate ester type, sulfonate type, phosphate ester type, etc.), nonionic surfactants (AO addition type, polyhydric alcohol type, etc.) ), Etc. These may be used individually by 1 type and may use 2 or more types together.

There is no restriction | limiting in particular as said water-soluble polymer, According to the objective, it can select suitably, For example, a cellulose compound (For example, methylcellulose, ethylcellulose, hydroxyethylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose, hydroxypropylcellulose, and those Saponified products), gelatin, starch, dextrin, gum arabic, chitin, chitosan, polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, polyethyleneimine, polyacrylamide, acrylic acid (salt) -containing polymer (sodium polyacrylate, polyacrylic acid) Potassium, ammonium polyacrylate, sodium hydroxide partially neutralized polyacrylic acid, sodium acrylate-acrylate ester Coalescence), styrene - sodium hydroxide maleic anhydride copolymer (partially) neutralized product water-soluble polyurethane (polyethylene glycol, reaction products of polycaprolactone diol and polyisocyanate), and the like.
Moreover, the said organic solvent, a plasticizer, etc. can also be used together as an auxiliary agent of emulsification or dispersion.

  The toner of the present invention comprises at least a binder resin, a binder resin precursor having a functional group capable of reacting with an active hydrogen group (reactive group-containing prepolymer), a colorant, and a release agent in a dissolution suspension method. The oil phase composition is dispersed or emulsified in an aqueous medium containing resin fine particles, the active hydrogen group-containing compound contained in the oil phase composition and / or the aqueous medium, and the reactive group-containing prepolymer, It is preferable to obtain the toner base particles by a method of reacting them (production method (I)).

The resin fine particles are not particularly limited and can be formed using a known polymerization method, but it is preferable to obtain the resin fine particles as an aqueous dispersion.
Examples of the method for preparing the aqueous dispersion of resin fine particles include the methods shown in the following (a) to (h).
(A) A method in which an aqueous dispersion of resin fine particles is directly prepared from a vinyl monomer as a starting material by any one of a suspension polymerization method, an emulsion polymerization method, a seed polymerization method and a dispersion polymerization method. (B) After dispersing a precursor of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin (monomer, oligomer, etc.) or a solvent solution thereof in an aqueous medium in an aqueous medium, A method of preparing an aqueous dispersion of resin fine particles by heating or adding a curing agent to cure.
(C) Polyaddition or condensation resin precursors (monomers, oligomers, etc.) such as polyester resins, polyurethane resins, and epoxy resins, or solvent solutions thereof (preferably liquids, which may be liquefied by heating). A method for preparing an aqueous dispersion of resin fine particles by dissolving a suitable emulsifier in the mixture and then adding water to effect phase inversion emulsification.
(D) A resin synthesized in advance by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is pulverized and classified using a mechanical rotary type or jet type fine pulverizer. A method of preparing an aqueous dispersion of resin fine particles by obtaining resin fine particles and then dispersing in water in the presence of an appropriate dispersant.
(E) Fine resin particles are formed by spraying a resin solution in which a resin synthesized in advance by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is dissolved in a solvent. Then, resin fine particles are dispersed in water in the presence of a suitable dispersant to prepare an aqueous dispersion of resin fine particles.
(F) A poor solvent is added to a resin solution prepared by previously dissolving a resin synthesized by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent, or heated to a solvent in advance. By cooling the dissolved resin solution, the resin fine particles are precipitated, the solvent is removed to form the resin fine particles, and then the resin fine particles are dispersed in water in the presence of an appropriate dispersant to disperse the resin fine particles in water. A method for preparing a liquid.
(G) A resin solution obtained by dissolving a resin previously synthesized by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent in the presence of an appropriate dispersant. A method of preparing an aqueous dispersion of resin fine particles by dispersing in a solvent and then removing the solvent by heating, decompression or the like.
(H) A suitable emulsifier is dissolved in a resin solution prepared by previously dissolving a resin synthesized by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent, and then water To prepare an aqueous dispersion of resin fine particles by phase inversion emulsification.

  There is no restriction | limiting in particular in the volume average particle diameter of the said resin fine particle, Although it can select suitably according to the objective, 10 to 300 nm is preferable and 30 to 120 nm is more preferable. When the volume average particle size of the resin fine particles is less than 10 nm or more than 300 nm, the particle size distribution of the toner may be deteriorated.

  The solid content concentration of the oil phase is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 40% by mass to 80% by mass. If the solid content concentration is too high, dissolution or dispersion becomes difficult, and the viscosity becomes high and difficult to handle. If the solid content concentration is too low, the productivity of the toner may be lowered.

  The toner composition other than the binder resin such as the colorant and the release agent, and the masterbatch thereof are individually dissolved or dispersed in an organic solvent, and then mixed with the binder resin solution or dispersion. May be.

  As the aqueous medium, water alone may be used, but a solvent miscible with water may be used in combination. Examples of the miscible solvent include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.), and the like.

  The method of dispersion or emulsification in the aqueous medium is not particularly limited and may be appropriately selected depending on the intended purpose. For example, low-speed shearing type, high-speed shearing type, friction type, high-pressure jet type, ultrasonic wave, Etc. Among these, the high-speed shearing method is preferable from the viewpoint of reducing the particle size of the particles. When the high-speed shearing disperser is used, the rotation speed is not particularly limited and can be appropriately selected according to the purpose, preferably 1,000 rpm to 30,000 rpm, more preferably 5,000 rpm to 20,000 rpm. preferable. There is no restriction | limiting in particular as temperature at the time of dispersion | distribution, Although it can select suitably according to the objective, 0 to 150 degreeC (under pressurization) is preferable and 20 to 80 degreeC is more preferable.

  In order to remove the organic solvent from the obtained emulsified dispersion, there is no particular limitation, and a known method can be used. For example, the whole system is gradually raised while stirring the whole system under normal pressure or reduced pressure. A method of warming and completely evaporating and removing the organic solvent in the droplets can be employed.

  As a method for washing and drying the toner base particles dispersed in the aqueous medium, a known technique is used. That is, after solid-liquid separation with a centrifuge, a filter press, etc., the obtained toner cake is redispersed in ion exchange water at about room temperature to about 40 ° C., and after adjusting the pH with acid or alkali as necessary, After removing the impurities and surfactants by repeating the process of solid-liquid separation again and again, the toner powder is obtained by drying with an air dryer, circulating dryer, vacuum dryer, vibration fluid dryer, etc. . At this time, the fine particle component of the toner may be removed by centrifugation or the like, and a desired particle size distribution can be obtained using a known classifier after drying, if necessary.

  In the agglomeration method, for example, a toner base particle is produced by mixing and aggregating a resin fine particle dispersion comprising at least a binder resin, a colorant particle dispersion, and a release agent particle dispersion as necessary. is there. The resin fine particle dispersion is obtained by a known method, for example, emulsion polymerization, seed polymerization, phase inversion emulsification, etc., and the colorant particle dispersion or the release agent particle dispersion is a known wet dispersion. It can be obtained by dispersing a colorant or a release agent in an aqueous medium by a method or the like.

For the control of the aggregation state, methods such as applying heat, adding a metal salt, and adjusting pH are preferably used.
There is no restriction | limiting in particular as said metal salt, According to the objective, it can select suitably, For example, the monovalent metal which comprises salts, such as sodium and potassium; The bivalent which comprises salts, such as calcium and magnesium; Metal; trivalent metal constituting a salt such as aluminum, and the like.
Examples of the anion constituting the salt include chloride ion, bromide ion, iodide ion, carbonate ion, sulfate ion, and the like. Among these, magnesium chloride, aluminum chloride, and composites and multimers thereof are preferable.
Also, heating between the agglomeration and after completion of the agglomeration can promote fusion between the resin fine particles, which is preferable from the viewpoint of toner uniformity. Furthermore, the shape of the toner can be controlled by heating. Normally, the toner becomes more spherical when heated further.

  As a method for washing and drying the toner base particles dispersed in the aqueous medium, the above-described method can be used.

Further, in order to improve the fluidity, storage stability, developability, and transferability of the toner, the coalesced particles are added to and mixed with the toner base particles produced as described above. Inorganic fine particles may be added and mixed.
For mixing the additives, a general powder mixer is used, but it is preferable to equip a jacket or the like to adjust the internal temperature. In order to change the load history applied to the additive, the additive may be added midway or gradually. In this case, you may change the rotation speed, rolling speed, time, temperature, etc. of a mixer. Alternatively, a strong load may be applied first, then a relatively weak load, or vice versa. Examples of the mixing equipment that can be used include a V-type mixer, a rocking mixer, a Roedige mixer, a Nauter mixer, a Henschel mixer, and the like. Next, the toner is obtained by passing through a sieve of 250 mesh or more to remove coarse particles and aggregated particles.

-Apparent loose toner density-
In the toner of the present invention, the loose apparent density ρ _M at 22 ° C. and 55% RH and the loose apparent density ρ _H after storage for 14 days in a constant temperature bath at 40 ° C. and 70% RH satisfy the following formula (1). It is necessary to satisfy the following formula (1-1).
1-ρ _H / ρ _M ≦ 0.10 (1)
1-ρ _H / ρ _M ≦ 0.05 (1-1)
The apparent density of looseness of the toner is an index representing the fluidity of the toner. By satisfying the above formula (1), the toner is stored in a constant temperature bath at 40 ° C. and 70% RH (high temperature and high humidity) even after storage for 14 days. The toner fluidity can be maintained before storage, that is, at the same temperature as that of a 55% RH (room temperature and humidity) environment at 22 ° C., and the generation of toner aggregates can be suppressed. In addition, it is possible to maintain good waste toner transportability.

  The means for satisfying the formula (1) is not particularly limited and may be appropriately selected depending on the intended purpose. As the external additive, coalesced particles formed by coalescing a plurality of the primary particles are used. It is particularly effective to use coalesced particles in which the particle size distribution index of the coalesced particles satisfies the formula (2). This is because the coalesced particles adhere to the surface of the toner base particles softened under the influence of temperature and humidity in a high-temperature and high-humidity environment to suppress the embedding, and the adhesion state on the surface of the toner base particles is reduced. This is considered to be because it can be maintained well. Moreover, it is considered that, by satisfying the formula (2), the ratio of particles that effectively function as coalesced particles is increased, and the effect is further increased.

The loose apparent density ρ _M of the toner at 22 ° C. and 55% RH (normal temperature and normal humidity) is not particularly limited and may be appropriately selected depending on the intended purpose, but is 0.25 g / cm ^{3 to} 0.50 g / cm ³ is preferable, and 0.30 g / cm ^{3 to} 0.45 g / cm ³ is more preferable. The loose apparent density ρ _M is the shape of toner base particles, the content of coalesced particles and other external additives, the particle size of the coalesced particles and other external additives, the coalesced particles and other external additives. It can be controlled by the type of surface treatment agent used for the toner, the addition conditions (mixing conditions) of the external additive to the toner base particles, and the like.

Here, the loose apparent density ρ _M of the toner at 22 ° C. and 55% RH can be measured by the following method.
The loose apparent density ρ _H after storing the toner in a constant temperature bath at 40 ° C. and 70% RH for 14 days is determined by measuring the toner used for measurement in a constant temperature bath at 40 ° C. and 70% RH. For 14 days and then measured by the following method.
Using a 100 mL graduated cylinder, toner was gradually added to 100 mL. At that time, no vibration was applied. From the weight difference (toner weight) before and after putting the toner in the measuring cylinder, the apparent density of loosening of the toner can be calculated by the following formula.
Toner loose apparent density (g / cm ³ ) = toner weight (g / 100 mL) ÷ 100

  The shape, size, etc. of the toner are not particularly limited and can be appropriately selected according to the purpose. The average circularity, volume average particle size, volume average particle size and number are as follows. It is preferable to have a ratio (volume average particle diameter / number average particle diameter) to the average particle diameter.

The average circularity is a value obtained by dividing the circumference of an equivalent circle having the same projected shape as the shape of the toner by the circumference of the actual particles. For example, 0.950 to 0.980 is preferable, and 0.960 to 0 is preferable. .975 is more preferred. In addition, it is preferable that the particles having an average circularity of less than 0.95 are 15% or less.
When the average circularity is less than 0.950, satisfactory transferability and a high-quality image free from dust may not be obtained. When the average circularity exceeds 0.980, image formation employing blade cleaning or the like is employed. In the system, defective cleaning on the photoconductor and transfer belt occurs, and in the case of image formation with a high image area ratio such as photographic images, an untransferred image is formed due to poor paper feed, etc. The accumulated toner may become a transfer residual toner on the photoconductor, resulting in background smearing of the image, or it may contaminate the charging roller for charging the photoconductor in contact with the original charging ability. It may become impossible to demonstrate.

The average circularity is measured using a flow particle image analyzer (“FPIA-2100”, manufactured by Sysmex Corporation), and analyzed using analysis software (FPIA-2100 Data Processing Program for FPIA version 00-10). It was. Specifically, 10% by weight surfactant (alkylbenzene sulfonate, Neogen SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is added to a glass 100 mL beaker, and each toner 0 0.1 g to 0.5 g was added, and the mixture was stirred with a micropartel, and then 80 mL of ion-exchanged water was added. The obtained dispersion was subjected to a dispersion treatment for 3 minutes with an ultrasonic disperser (manufactured by Honda Electronics Co., Ltd.). The shape and distribution of the toner were measured with the FPIA-2100 until the concentration of the dispersion was 5,000 / μL to 15,000 / μL. In this measurement method, it is important that the concentration of the dispersion is 5,000 / μL to 15,000 / μL from the viewpoint of measurement reproducibility of the average circularity.
In order to obtain the dispersion concentration, it is necessary to change the conditions of the dispersion, that is, the amount of surfactant to be added and the amount of toner. The amount of the surfactant varies depending on the hydrophobicity of the toner as in the measurement of the toner particle diameter described above. If it is added in a large amount, noise due to bubbles is generated, and if it is too small, the toner cannot be sufficiently wetted. It will be enough. The amount of toner added varies depending on the particle size, and is small when the particle size is small, and needs to be increased when the particle size is large. When the toner particle size is 3 μm to 10 μm, the toner amount is 0.1 g to 0.00. By adding 5 g, the dispersion concentration can be adjusted to 5,000 / μL to 15,000 / μL.

  There is no restriction | limiting in particular as a volume average particle diameter of the said toner, Although it can select suitably according to the objective, For example, 3 micrometers-10 micrometers are preferable, and 4 micrometers-7 micrometers are more preferable. When the volume average particle size is less than 3 μm, in the case of a two-component developer, the toner may be fused to the surface of the carrier during a long period of stirring in the developing device, and the charging ability of the carrier may be reduced. Therefore, it becomes difficult to obtain a high-resolution and high-quality image, and when the balance of the toner in the developer is performed, the variation in the toner particle size may increase.

The ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) in the toner is not particularly limited and may be appropriately selected depending on the intended purpose. 1.25 is preferable, and 1.00 to 1.15 is more preferable.
The volume average particle diameter and the ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) are measured using a particle size measuring device (“Multisizer III”, manufactured by Beckman Coulter, Inc.). Then, measurement was performed with an aperture diameter of 100 μm, and analysis was performed with analysis software (Beckman Coulter Multisizer 3 Version 3.51).
Specifically, 0.5 mL of 10% by weight surfactant (alkylbenzene sulfonate, Neogen SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is added to a 100 mL glass beaker, and 0.5 g of each toner is added. The mixture was stirred with a micropartel, and then 80 ml of ion exchange water was added. The obtained dispersion was subjected to a dispersion treatment for 10 minutes with an ultrasonic disperser (W-113MK-II, manufactured by Honda Electronics Co., Ltd.). The dispersion was measured using the Multisizer III and Isoton III (manufactured by Beckman Coulter, Inc.) as the measurement solution. In the measurement, the toner sample dispersion was dropped so that the concentration indicated by the apparatus was 8% ± 2%. In this measurement method, it is important that the concentration is 8% ± 2% from the viewpoint of the reproducibility of the particle size. Within this concentration range, no error occurs in the particle size.

(Developer)
The developer of the present invention contains at least the toner of the present invention, and other components such as a carrier selected as appropriate. The developer may be a one-component developer or a two-component developer. However, when it is used for a high-speed printer or the like corresponding to the recent improvement in information processing speed, the life is improved. In view of the above, the two-component developer is preferable.

  In the case of the one-component developer using the toner, toner aggregation does not easily occur over time against stress caused by the developing means, and toner filming on the developing roller as the developer carrying member The toner is not fused to a layer thickness regulating member such as a blade for thinning the toner, the toner transportability is maintained well, and good and stable developability and images can be obtained. In addition, in the case of the two-component developer using the toner, toner aggregation does not easily occur over time even against agitation stress by the developing unit, and the toner transportability and replenishment properties are maintained well. Thus, waste toner lock does not occur, and good and stable developability and images can be obtained.

<Career>
There is no restriction | limiting in particular as said carrier, Although it can select suitably according to the objective, What has a core particle and the resin layer (coating layer) which coat | covers this core particle is preferable.

<< Core particle >>
The core particles are not particularly limited as long as they are magnetic core particles, and can be appropriately selected according to the purpose. Examples thereof include ferromagnetic metals such as iron and cobalt; oxidation of magnetite, hematite, ferrite, and the like. Iron; resin particles in which magnetic materials such as various alloys and compounds are dispersed in a resin. Among these, Mn-based ferrite, Mn-Mg-based ferrite, Mn-Mg-Sr-based ferrite and the like are preferable from the viewpoint of environmental considerations.

-Weight average particle diameter Dw of core particles-
The weight average particle diameter Dw of the core particles refers to the particle diameter at an integrated value of 50% in the particle size distribution of the core particles obtained by a laser diffraction or scattering method. There is no restriction | limiting in particular as the weight average particle diameter Dw of the said core particle, Although it can select suitably according to the objective, 10 micrometers-80 micrometers are preferable, and 20 micrometers-65 micrometers are more preferable.

The weight average particle diameter Dw of the core particles is measured by using a microtrac particle size distribution meter (HRA9320-X100, manufactured by Honeywell) as a particle diameter distribution (relationship between number frequency and particle diameter) of particles measured on a number basis. And measured under the conditions described below, and calculated using the following formula (III). Each channel represents a length for dividing the particle size range in the particle size distribution chart into measurement width units, and the lower limit value of the particle size stored in each channel is adopted as the representative particle size.
Dw = {1 / Σ (nD ³ )} × {Σ (nD ⁴ )} (III)
However, in said formula (III), D represents the representative particle diameter (micrometer) of the core particle which exists in each channel, and n represents the total number of the core particle which exists in each channel.
[Measurement condition]
[1] Particle size range: 100 μm to 8 μm
[2] Channel length (channel width): 2 μm
[3] Number of channels: 46
[4] Refractive index: 2.42

<< Coating layer >>
The coating layer contains at least a resin, and may contain other components such as a filler as necessary.

-Resin-
The resin for forming the carrier coating layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, polyolefin (for example, polyethylene, polypropylene, etc.) and modified products thereof, polystyrene, acrylic resin, acrylonitrile, Crosslinkable copolymer containing vinyl acetate, vinyl alcohol, vinyl chloride, vinyl carbazole, vinyl ether, etc .; silicone resin consisting of organosiloxane bond or modified product thereof (for example, alkyd resin, polyester resin, epoxy resin, polyurethane, polyimide, etc.) Modified products); polyamides; polyesters; polyurethanes; polycarbonates; urea resins; melamine resins; benzoguanamine resins; epoxy resins; ionomer resins; That. These may be used individually by 1 type and may use 2 or more types together. Among these, a silicone resin is preferable.

There is no restriction | limiting in particular as said silicone resin, According to the objective from the generally known silicone resin, it can select suitably, For example, straight silicone resin which consists only of organosiloxane bonds, alkyd, polyester , Silicone resins modified with epoxy, acrylic, urethane, and the like.
Examples of the straight silicone resin include KR271, KR272, KR282, KR252, KR255, KR152 (manufactured by Shin-Etsu Chemical Co., Ltd.), SR2400, SR2405, SR2406 (manufactured by Toray Dow Corning Silicone). Examples of the modified silicone resin include epoxy-modified product: ES-1001N, acrylic-modified silicone: KR-5208, polyester-modified product: KR-5203, alkyd-modified product: KR-206, and urethane-modified product: KR-305. (Shin-Etsu Chemical Co., Ltd.), epoxy-modified product: SR2115, alkyd-modified product: SR2110 (manufactured by Toray Dow Corning Silicone), and the like.

  The silicone resin can be used alone, but a crosslinking reactive component, a charge amount adjusting component, and the like can be used at the same time. Examples of the cross-linking reactive component include a silane coupling agent. Examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, octyltrimethoxysilane, aminosilane coupling agent, and the like.

-Filler-
There is no restriction | limiting in particular as said filler, According to the objective, it can select suitably, For example, a conductive filler, a nonelectroconductive filler, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, it is preferable to contain a conductive filler and a non-conductive filler in the coating layer.

The conductive filler refers to a filler having a powder specific resistance value of 100 Ω · cm or less.
The said nonelectroconductive filler points out the filler whose powder specific resistance value exceeds 100 ohm * cm.
The powder specific resistance value of the filler is measured by a powder resistance measurement system (MCP-PD51, manufactured by Dia Instruments) and a resistivity meter (4-terminal 4-probe method, Loresta-GP, manufactured by Mitsubishi Chemical Analytech Co., Ltd.). ) Was measured under the conditions of a sample of 1.0 g, an electrode interval of 3 mm, a sample radius of 10.0 mm, and a load of 20 kN.

--Conductive filler--
The conductive filler is not particularly limited and may be appropriately selected depending on the intended purpose. For example, tin oxide or oxide may be applied to a substrate such as aluminum oxide, titanium oxide, zinc oxide, barium sulfate, silicon oxide, or zirconium oxide. Examples thereof include a conductive filler formed using indium as a layer; a conductive filler formed using carbon black, and the like. Among these, a conductive filler containing aluminum oxide, titanium oxide, and barium sulfate is preferable.

--Non-conductive filler--
There is no restriction | limiting in particular as said nonelectroconductive filler, According to the objective, it can select suitably, For example, it forms using aluminum oxide, titanium oxide, barium sulfate, zinc oxide, silicon dioxide, zirconium oxide etc. Non-conductive filler, etc. are mentioned. Among these, non-conductive fillers containing aluminum oxide, titanium oxide, and barium sulfate are preferable.

<Carrier manufacturing method>
There is no restriction | limiting in particular as a manufacturing method of the said carrier, Although it can select suitably according to the objective, The said resin and the said filler are contained in the surface of the said core particle using a fluid bed type coating apparatus. The method of manufacturing by apply | coating a coating layer forming solution is preferable. In addition, when apply | coating the said coating layer forming solution, you may advance condensation of the resin contained in the said coating layer, and after apply | coating the said coating layer forming solution, condensation of the resin contained in the said coating layer You may proceed. There is no restriction | limiting in particular as the condensation method of the said resin, According to the objective, it can select suitably, For example, the method etc. which give a heat | fever, light, etc. to the said coating layer formation solution, etc. are mentioned. .

-Weight average particle diameter Dw of carrier-
The weight average particle diameter Dw of the carrier refers to the particle diameter at an integrated value of 50% in the particle size distribution of the core particles obtained by a laser diffraction / scattering method. There is no restriction | limiting in particular as the weight average particle diameter Dw of the said carrier, Although it can select suitably according to the objective, 10 micrometers-80 micrometers are preferable, and 20 micrometers-65 micrometers are more preferable.

For the measurement of the weight average particle diameter Dw of the carrier, the particle size distribution (relationship between the number frequency and the particle diameter) of the particles measured on the basis of the number is used using a Microtrac particle size distribution meter (HRA9320-X100, manufactured by Honeywell). Measured under the conditions described below, and calculated using the following formula (V). Each channel represents a length for dividing the particle size range in the particle size distribution chart into measurement width units, and the lower limit value of the particle size stored in each channel is adopted as the representative particle size.
Dw = {1 / Σ (nD ³ )} × {Σ (nD ⁴ )} (V)
In the above formula (V), D represents the representative particle size (μm) of carriers present in each channel, and n represents the total number of carriers present in each channel.
[Measurement condition]
[1] Particle size range: 100 μm to 8 μm
[2] Channel length (channel width): 2 μm
[3] Number of channels: 46
[4] Refractive index: 2.42

  When the developer is a two-component developer, the mixing ratio of the toner and the carrier in the two-component developer is not particularly limited and can be appropriately selected according to the purpose. The ratio is preferably 2.0% by mass to 12.0% by mass, and more preferably 2.5% by mass to 10.0% by mass.

(Image forming method and image forming apparatus)
The image forming method used in the present invention includes at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step, and further includes other steps appropriately selected as necessary.
The image forming apparatus according to the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing unit, and other types appropriately selected as necessary. Having means.

<Electrostatic latent image forming step and electrostatic latent image forming means>
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier.
There are no particular restrictions on the material, shape, structure, size, etc. of the electrostatic latent image carrier (hereinafter also referred to as “electrophotographic photoreceptor” or “photoreceptor”), and there are no known limitations. The shape can be suitably selected from among those, and the shape is preferably a drum shape. Examples of the material include inorganic photoconductors such as amorphous silicon and selenium, and organic photoconductors (OPC) such as polysilane and phthalopolymethine. ), Etc. Among these, amorphous silicon is preferable from the viewpoint of long life.

The formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then performing imagewise exposure, and is performed by electrostatic latent image forming means. Can do.
The electrostatic latent image forming unit includes, for example, a charging unit (charger) that uniformly charges the surface of the electrostatic latent image carrier, and an exposure that exposes the surface of the electrostatic latent image carrier imagewise. Means (exposure unit).

The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charger.
The charger is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charging device including a conductive or semiconductive roll, brush, film, rubber blade, etc. And non-contact chargers utilizing corona discharge such as corotrons and corotrons.
The charger is preferably one that is arranged in contact or non-contact with the electrostatic latent image carrier and charges the surface of the electrostatic latent image carrier by applying a direct current and an alternating voltage.
Further, the charger is a charging roller disposed in a non-contact proximity to the electrostatic latent image carrier via a gap tape, and the electrostatic latent image is carried by applying a direct current and an alternating voltage to the charging roller. Those that charge the body surface are preferred.

The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure device.
The exposure device is not particularly limited as long as it can expose the surface of the electrostatic latent image carrier charged by the charger so as to form an image to be formed, and is appropriately selected according to the purpose. For example, various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system can be used.
In the present invention, a back light system in which imagewise exposure is performed from the back side of the electrostatic latent image carrier may be employed.

<Development process and development means>
The developing step is a step of developing the electrostatic latent image using the developer to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image using the developer, and can be performed by the developing unit.
The developing means preferably has, for example, at least a developing unit that accommodates the developer and can apply the developer to the electrostatic latent image in a contact or non-contact manner, and includes a developer-containing container. More preferred is a developing device.

The developing device may be a single color developing device or a multicolor developing device.For example, a stirrer for charging the developer by friction stirring and a rotatable magnet roller. What has is mentioned suitably.
In the developing device, for example, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier (photoconductor), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted. It moves to the surface of the electrostatic latent image carrier (photoconductor) by force. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier (photoconductor).

<Transfer process and transfer means>
The transfer step is a step of transferring the visible image onto a recording medium. After the primary transfer of the visible image onto the intermediate transfer member using an intermediate transfer member, the visible image is transferred onto the recording medium. A primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer body using two or more colors, preferably full color toner as the toner, and a composite transfer image; A mode including a secondary transfer step of transferring the transfer image onto the recording medium is more preferable.
The transfer can be performed, for example, by charging the latent electrostatic image bearing member (photoconductor) of the visible image using a transfer charger, and can be performed by the transfer unit. The transfer means includes a primary transfer means for transferring a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. Embodiments are preferred.
The intermediate transfer member is not particularly limited and may be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.

The transfer means (the primary transfer means and the secondary transfer means) is a transfer for peeling and charging the visible image formed on the electrostatic latent image carrier (photoconductor) to the recording medium side. It is preferable to have at least a vessel. The number of the transfer means may be one, or two or more.
Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is not particularly limited and can be appropriately selected from known recording media (recording paper).

<Fixing process and fixing means>
The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing device, and may be performed each time the developer of each color is transferred to the recording medium, or the developer of each color. On the other hand, it may be carried out at the same time in a state where these are laminated.
There is no restriction | limiting in particular as said fixing device, Although it can select suitably according to the objective, A well-known heating-pressing means is suitable. Examples of the heating and pressing means include a combination of a heating roller and a pressing roller, a combination of a heating roller, a pressing roller, and an endless belt.
The fixing device includes a heating body including a heating element, a film in contact with the heating body, and a pressure member in pressure contact with the heating body through the film, and the film and the pressure member It is preferably a unit that heats and fixes a recording medium on which an unfixed image is formed. There is no restriction | limiting in particular in the heating in the said heating-pressing means, Although it can select suitably according to the objective, 80 to 200 degreeC is preferable.
In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing step and the fixing unit depending on the purpose.

<Other processes and other means>
Examples of the other processes include a static elimination process, a cleaning process, a recycling process, and a control process.
Examples of the other means include a static elimination means, a cleaning means, a recycling means, and a control means.

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

-Cleaning process and cleaning means-
The cleaning step is a step of removing the toner remaining on the electrostatic latent image carrier and can be suitably performed by a cleaning unit.
The cleaning means is not particularly limited, and may be appropriately selected from known cleaners as long as the toner remaining on the electrostatic latent image carrier can be removed. For example, a magnetic brush cleaner Suitable examples include electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, web cleaners, and the like.

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

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

  Here, FIG. 6 shows an example of the image forming apparatus of the present invention. The image forming apparatus 100A includes a photosensitive drum 10, a charging roller 20, an exposure device (not shown), a developing device 40, an intermediate transfer belt 50, a cleaning device 60 having a cleaning blade, and a static elimination lamp 70. Prepare.

  The intermediate transfer belt 50 is an endless belt stretched by three rollers 51 arranged on the inner side, and can move in the direction of the arrow in FIG. A part of the three rollers 51 also functions as a transfer bias roller that can apply a transfer bias (primary transfer bias) to the intermediate transfer belt 50. Further, a cleaning device 90 having a cleaning blade is disposed in the vicinity of the intermediate transfer belt 50. Further, a transfer roller 80 capable of applying a transfer bias (secondary transfer bias) for transferring the toner image to the transfer paper 95 is disposed to face the intermediate transfer belt 50. Further, around the intermediate transfer belt 50, a corona charging device 58 for applying a charge to the toner image transferred to the intermediate transfer belt 50 is connected to the photosensitive drum 10 with respect to the rotation direction of the intermediate transfer belt 50. It is disposed between the contact portion of the intermediate transfer belt 50 and the contact portion of the intermediate transfer belt 50 and the transfer paper 95.

  The developing device 40 includes a developing belt 41 and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C provided around the developing belt 41. Each color developing unit 45 includes a developer container 42, a developer supply roller 43, and a developing roller (developer carrier) 44. Further, the developing belt 41 is an endless belt stretched by a plurality of belt rollers, and can move in the arrow direction in FIG. Further, a part of the developing belt 41 is in contact with the photosensitive drum 10.

  Next, a method for forming an image using the image forming apparatus 100A will be described. First, the charging roller 20 is used to uniformly charge the surface of the photosensitive drum 10, and then the exposure light L is exposed to the photosensitive drum 10 using an exposure device (not shown) to form an electrostatic latent image. Form. Next, the electrostatic latent image formed on the photosensitive drum 10 is developed with the toner supplied from the developing device 40 to form a toner image. Further, after the toner image formed on the photosensitive drum 10 is transferred (primary transfer) onto the intermediate transfer belt 50 by the transfer bias applied from the roller 51, the transfer bias applied from the transfer roller 80 is used. Then, it is transferred (secondary transfer) onto the transfer paper 95. On the other hand, the photosensitive drum 10 on which the toner image is transferred to the intermediate transfer belt 50 is discharged by the discharging lamp 70 after the toner remaining on the surface is removed by the cleaning device 60.

  FIG. 7 shows another example of the image forming apparatus used in the present invention. In this image forming apparatus 100B, the black developing unit 45K, the yellow developing unit 45Y, the magenta developing unit 45M, and the cyan developing unit 45C are directly disposed around the photosensitive drum 10 without providing the developing belt 41. Except for this, the configuration is the same as that of the image forming apparatus 100A.

FIG. 8 shows another example of the image forming apparatus used in the present invention. The image forming apparatus 100C is a tandem color image forming apparatus, and includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.
An intermediate transfer belt 50 provided at the center of the copying apparatus main body 150 is an endless belt stretched around three rollers 14, 15 and 16, and can move in the direction of the arrow in FIG. . In the vicinity of the roller 15, a cleaning device 17 having a cleaning blade for removing toner remaining on the intermediate transfer belt 50 on which the toner image has been transferred onto the recording paper is disposed. The image forming units 120Y, 120C, 120M, and 120K for yellow, cyan, magenta, and black are juxtaposed along the conveying direction while facing the intermediate transfer belt 50 stretched by the rollers 14 and 15. An exposure device 21 is disposed in the vicinity of the image forming unit 120. Further, the secondary transfer belt 24 is disposed on the side of the intermediate transfer belt 50 opposite to the side on which the image forming unit 120 is disposed. The secondary transfer belt 24 is an endless belt stretched around a pair of rollers 23, and the recording paper and the intermediate transfer belt 50 conveyed on the secondary transfer belt 24 are between the rollers 16 and 23. Can touch. Further, in the vicinity of the secondary transfer belt 24, a fixing device 25 is provided with a fixing belt 26 that is an endless belt stretched between a pair of rollers, and a pressure roller 27 that is arranged to be pressed against the fixing belt 26. Is arranged. A sheet reversing device 28 for reversing the recording paper when an image is formed on both sides of the recording paper is disposed in the vicinity of the secondary transfer belt 24 and the fixing device 25.

  Next, a method for forming a full-color image using the image forming apparatus 100C will be described. First, a color document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and a color document is set on the contact glass 32 of the scanner 300 to automatically convey the document. The device 400 is closed. When a start switch (not shown) is pressed, when an original is set on the automatic document feeder 400, the original is conveyed and moved onto the contact glass 32, and then the original is set on the contact glass 32. In this case, the scanner 300 is immediately driven, and the first traveling body 33 including the light source and the second traveling body 34 including the mirror travel. At this time, the reflected light from the original surface of the light irradiated from the first traveling body 33 is reflected by the second traveling body 34 and then received by the reading sensor 36 via the imaging lens 35, whereby the original is received. It is read and image information of black, yellow, magenta and cyan is obtained.

The image information for each color is transmitted to the image forming unit 120 for each color, and a toner image for each color is formed. As shown in FIG. 9, the image forming units 120 for each color each include a photosensitive drum 10, a charging roller 160 that uniformly charges the photosensitive drum 10, and image information for each color. An exposure device that exposes the exposure light L to form an electrostatic latent image of each color; a developing device 61 that develops the electrostatic latent image with a developer of each color to form a toner image of each color; A transfer roller 62 for transferring onto the transfer belt 50, a cleaning device 63 having a cleaning blade, and a static elimination lamp 64 are provided.
The toner images of the respective colors formed by the image forming units 120 of the respective colors are sequentially transferred (primary transfer) onto the intermediate transfer body 50 that is stretched and moved by the rollers 14, 15, and 16, and superimposed to form a composite toner image. It is formed.

  On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed recording paper from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143, and one sheet at a time by the separation roller 145. The paper is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 to stop. Alternatively, the paper feed roller is rotated to feed out the recording paper on the manual feed tray 54, separated one by one by the separation roller 52, guided to the manual paper feed path 53, and abutted against the registration roller 49 and stopped. The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied in order to remove paper dust from the recording paper. Next, by rotating the registration roller 49 in synchronization with the composite toner image formed on the intermediate transfer belt 50, the recording paper is sent between the intermediate transfer belt 50 and the secondary transfer belt 24, and the composite toner image is sent. The toner image is transferred onto the recording paper (secondary transfer). The toner remaining on the intermediate transfer belt 50 to which the composite toner image has been transferred is removed by the cleaning device 17.

  The recording paper on which the composite toner image has been transferred is conveyed by the secondary transfer belt 24 and then the composite toner image is fixed by the fixing device 25. Next, the conveyance path of the recording paper is switched by the switching claw 55, and the recording paper is discharged onto the paper discharge tray 57 by the discharge roller 56. Alternatively, the recording path of the recording paper is switched by the switching claw 55, reversed by the sheet reversing device 28, an image is similarly formed on the back side, and then discharged onto the discharge tray 57 by the discharge roller 56. .

  The image forming apparatus and the image forming method of the present invention effectively suppress the deterioration of toner cohesion even when exposed to a high temperature and high humidity environment for a long time, and have good toner replenishment property and waste toner transportability. Since the toner of the present invention that can be maintained at a high level is used, a high-quality image can be provided over a long period of time.

Examples of the present invention will be described below, but the present invention is not limited to these examples. However, Examples 4, 5, and 14-22 are read as reference examples.

(External Additive Production Examples 1-12)
<Manufacture of external additives 1-12>
The production of the external additives 1 to 10 is carried out by mixing primary particles of silica having various average particle diameters and a treatment agent with a spray dryer and firing them under the conditions described in Table 1-1. After the primary particles were coalesced to produce coalesced particles, classification treatment was performed with a classifier to obtain a sharp particle size distribution.
In addition, the external additives 11 to 12 were produced by subjecting the primary particles of silica having various average particle diameters to a hydrophobization treatment, but without the treatment with the treatment agent.
The treating agent was prepared by adding 0.1 part by mass of a processing aid (water or 1% by mass acetic acid aqueous solution) to 1 part by mass of methyltrimethoxysilane. Tables 1-1 and 1-2 show the average particle diameter, shape, and the like of secondary particles produced by coalescing the primary particles.

<Particle size distribution index of coalesced particles (Db ₅₀ / Db ₁₀ )>
For Db ₅₀ in the coalesced particles (secondary particles), the particle size of the coalesced particles was measured, and the particle size at which the cumulative value was 50% by number when the cumulative distribution was drawn from the small particle side was determined. Db ₁₀ was obtained by measuring the particle size of coalesced particles and obtaining a particle size with a cumulative value of 10% by number when a cumulative distribution was drawn from the small particle side.
The number average particle diameter (Db) of the coalesced particles (secondary particles) is a measurement of the longest length of aggregated particles (the length of the arrow shown in FIG. 2) (measured number of particles: 150). The number average particle diameter (Da) of the primary particles of the coalesced particles is predicted from the outer frame of the fused silica, and the longest length of all the images (the lengths of all arrows shown in FIG. 1). Was measured (number of particles measured: 150).
The particle diameter of each of these particles is measured by dispersing the coalesced particles in an appropriate solvent (tetrahydrofuran (THF), etc.), and then removing the solvent on the substrate to dry the sample. The measurement was performed by measuring the particle diameter in the field of view with a scanning electron microscope (FE-SEM, acceleration voltage: 5 kV to 8 kV, observation magnification: 8,000 times to 10,000 times).

<Fitting degree>
The degree of coalescence is the number average particle diameter (Db) of one coalesced particle (secondary particle) in the measurement of the primary particle size and secondary particle size of the coalesced particle, and constitutes the coalesced particle. The number average particle diameter (Da) of a plurality of primary particles to be obtained was determined and calculated by the following formula.
Degree of coalescence (Db / Da) = number average particle size of coalesced particles / number average particle size of primary particles 100 or more coalesced particles were observed, and the degree of coalescence of each particle was determined. The average value was obtained.

<Evaluation of cracking or disintegration of external additives>
0.5 g of each of the external additives 1 to 12 placed in a 50 mL bottle (manufactured by Nidec Rika Glass Co., Ltd.) and the carrier 1 prepared in Carrier Production Example 1 described below into a developer 50 g consisting of 49.5 g On the other hand, the mixture was stirred at 67 Hz for 10 minutes using a rocking mill (manufactured by Seiwa Giken Co., Ltd.). The stirred developer was diluted and dispersed in tetrahydrofuran (THF), and the external additive was separated on the supernatant liquid side, followed by observation with a field emission scanning electron microscope (FE-SEM). By the FE-SEM observation, crackability (%), which is the ratio of the number of cracks or disintegrated particles in 1,000 particles of the external additive, was determined. FIG. 4 shows a photograph of a measurement result in which the ratio of the number of cracked or disintegrated particles is 30% or less, and FIG. 5 shows a photograph of a measurement result in which the ratio of the number of cracked or disintegrated particles exceeds 30%. In the measurement, the particles present alone as shown by reference numeral 2 in FIG. 3 and the particles present alone as shown in the black frame in FIGS. The ratio was counted by counting as “cracked or disintegrated particles”.

(Synthesis Example 1)
<Manufacture of crystalline polyester resin 1>
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 202 parts by mass (1.00 mol) of sebacic acid, 154 parts by mass (1.30 mol) of 1,6-hexanediol, and tetrabutoxy as a condensation catalyst. 0.5 parts by mass of titanate was added, and the reaction was carried out for 8 hours at 180 ° C. while distilling off the generated water under a nitrogen stream. Next, while gradually raising the temperature to 220 ° C., the reaction was carried out for 4 hours while distilling off the water and 1,6-hexanediol produced under a nitrogen stream, and the weight average molecular weight Mw under reduced pressure of 5 mmHg to 20 mmHg. The reaction was carried out until the value reached approximately 15,000 to obtain [Crystalline Polyester Resin 1]. The obtained [Crystalline Polyester Resin 1] had a weight average molecular weight Mw of 14,000 and a melting point of 66 ° C.

(Synthesis Example 2)
<Production of Amorphous Polyester Resin 1 (Unmodified Polyester Resin)>
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 222 parts by mass of bisphenol A EO 2 mol adduct, 129 parts by mass of bisphenol A PO 2 mol adduct, 150 parts by mass of terephthalic acid, 15 parts by mass of adipic acid, and tetra Butoxytitanate 0.5 mass part was put, and it was made to react for 8 hours, distilling off the water to produce | generate at 230 degreeC and a normal pressure under nitrogen stream. Next, the reaction was carried out under reduced pressure of 5 to 20 mmHg. When the acid value reached 2 mgKOH / g, the mixture was cooled to 180 ° C., 35 parts by mass of trimellitic anhydride was added, and the mixture was reacted at normal pressure for 3 hours. Crystalline polyester resin 1] was obtained. The obtained [Amorphous polyester resin 1] had a weight average molecular weight Mw of 6,000 and a glass transition temperature Tg of 54 ° C.

(Synthesis Example 3)
<Manufacture of non-crystalline polyester resin 2 (unmodified polyester resin)>
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, 212 parts by mass of bisphenol A EO 2 mol adduct, 116 parts by mass of bisphenol A PO 2 mol adduct, 166 parts by mass of terephthalic acid, and 0.5 mass of tetrabutoxy titanate. The reaction was allowed to proceed for 8 hours while distilling off the water produced at 230 ° C. and normal pressure under a nitrogen stream. Subsequently, it was made to react under reduced pressure of 5-20 mmHg, and it reacted until the weight average molecular weight Mw reached about 15,000, and [Non-crystalline polyester resin 2] was obtained. The obtained [Amorphous polyester resin 2] had a weight average molecular weight Mw of 14,000 and a glass transition temperature Tg of 60 ° C.

(Synthesis Example 3)
<Manufacture of non-crystalline polyester resin 3 (unmodified polyester resin)>
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 204 parts by mass of bisphenol A EO 2 mol adduct, 106 parts by mass of bisphenol A PO 2 mol adduct, 166 parts by mass of terephthalic acid, and 0.5 mass of tetrabutoxy titanate. The reaction was allowed to proceed for 8 hours while distilling off the water produced at 230 ° C. and normal pressure under a nitrogen stream. Subsequently, it was made to react under reduced pressure of 5-20 mmHg, and it reacted until the weight average molecular weight Mw reached about 40,000, and [Amorphous polyester resin 3] was obtained. The obtained [Amorphous polyester resin 3] had a weight average molecular weight Mw of 38,000 and a glass transition temperature Tg of 62 ° C.

(Synthesis Example 4)
<Manufacture of polyester prepolymer>
720 parts by mass of bisphenol A EO 2 mol adduct, 90 parts by mass of bisphenol A PO2 mol adduct, 290 parts by mass of terephthalic acid, and 1 part by mass of tetrabutoxy titanate in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe. The reaction was allowed to proceed for 8 hours while distilling off the water produced at 230 ° C. and normal pressure under a nitrogen stream. Subsequently, it was made to react under reduced pressure of 10-15 mmHg for 7 hours, and [Intermediate polyester 1] was obtained. The obtained [Intermediate polyester 1] had a number average molecular weight Mn3,200 and a weight average molecular weight Mw9,300.
Next, 400 parts by mass of the obtained [intermediate polyester 1], 95 parts by mass of isophorone diisocyanate, and 500 parts by mass of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe. The mixture was reacted at 80 ° C. for 8 hours under an air stream to obtain a 50% by mass ethyl acetate solution of [Polyester Prepolymer 1] having an isocyanate group at the terminal. [Polyester prepolymer 1] had a free isocyanate mass% of 1.47%.

(Synthesis Example 5)
<Production of graft polymer>
In a reaction vessel in which a stir bar and a thermometer are set, 480 parts by mass of xylene and 100 parts by mass of low molecular weight polyethylene (manufactured by Sanyo Chemical Industries, Sunwax LEL-400, softening point 128 ° C.) are sufficiently dissolved. , 740 parts by mass of styrene, 100 parts by mass of acrylonitrile, 60 parts by mass of butyl acrylate, 36 parts by mass of di-t-butylperoxyhexahydroterephthalate, and 100 parts by mass of xylene at 170 ° C. The solution was dropped for a period of time to polymerize, and further maintained at this temperature for 30 minutes. Next, the solvent was removed to synthesize [graft polymer].
The obtained [graft polymer] had a weight average molecular weight Mw of 24,000 and a glass transition temperature Tg of 67 ° C.

(Production Example 1 of toner base particles)
<Production of toner base particles 1 (ester elongation method)>
-Preparation of release agent dispersion 1-
In a container equipped with a stirring bar and a thermometer, 50 parts by mass of paraffin wax (HNP-9, Nippon Seiki Co., Ltd., melting point 75 ° C.), 30 parts by mass of [graft polymer], and 420 parts by mass of ethyl acetate are added. The mixture was heated to 80 ° C. with stirring and held at 80 ° C. for 5 hours, then cooled to 30 ° C. in 1 hour, and a liquid feed rate of 1 kg / hr using a bead mill (Ultra Visco Mill, manufactured by IMEX). The disk peripheral speed was 6 m / sec, 80% by volume of zirconia beads having a diameter of 0.5 mm were filled, and dispersion was performed under conditions of 3 passes to obtain [Partitioner Dispersion Liquid 1].

-Production of master batch 1-
Non-crystalline polyester resin 1 ... 100 parts by mass Carbon black (Printex 35, manufactured by Degussa) ... 100 parts by mass (DBP oil absorption: 42 mL / 100 g, pH: 9.5)
-Ion exchange water ... 50 mass parts Said raw material was mixed using the Henschel mixer (made by Mitsui Mining Co., Ltd.). The obtained mixture was kneaded using two rolls. The kneading temperature started kneading from 90 ° C., and then gradually cooled to 50 ° C. The obtained kneaded material was pulverized with a pulverizer (manufactured by Hosokawa Micron Corporation) to prepare [Masterbatch 1].

-Production of oil phase 1-
In a container equipped with a thermometer and a stirrer, 107 parts by weight of [Non-crystalline polyester resin 1], 75 parts by weight of [Releasing agent dispersion 1], 18 parts by weight of [Masterbatch 1], and 73 parts by weight of ethyl acetate And then pre-dispersed with a stirrer, and then stirred with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at a rotational speed of 5,000 rpm to uniformly dissolve and disperse [oil Phase 1] was obtained.

―Manufacture of aqueous dispersion of resin fine particles―
In a reaction vessel equipped with a stirrer and a thermometer, 600 parts by mass of water, 120 parts by mass of styrene, 100 parts by mass of methacrylic acid, 45 parts by mass of butyl acrylate, sodium salt of alkylallylsulfosuccinate (Eleminol JS-2, Sanyo Kasei) 10 parts by weight manufactured by Kogyo Co., Ltd. and 1 part by weight of ammonium persulfate were charged and stirred for 20 minutes at 400 rpm, and a white emulsion was obtained. This emulsion was heated to raise the temperature in the system to 75 ° C. and reacted for 6 hours. Furthermore, 30 parts by mass of a 1% by mass aqueous ammonium persulfate solution was added and aged at 75 ° C. for 6 hours to obtain [Aqueous dispersion of resin fine particles]. The volume average particle diameter of the particles contained in this [resin fine particle aqueous dispersion] was 60 nm, the weight average molecular weight Mw of the resin component was 140,000, and the glass transition temperature Tg was 73 ° C.

-Preparation of aqueous phase 1-
990 parts by weight of water, 83 parts by weight of an aqueous dispersion of resin fine particles, 37 parts by weight of a 48.5% by weight aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries, Ltd.), and 90 ethyl acetate Mass parts were mixed and stirred to obtain [Aqueous Phase 1].

―Emulsification or dispersion―
To 273 parts by mass of [Oil Phase 1], 45 parts by mass of an ethyl acetate solution of [Polyester Prepolymer 1] and 3 parts by mass of a 50% by mass ethyl acetate solution of isophoronediamine were added. Co., Ltd.) was stirred at a rotational speed of 5,000 rpm, and uniformly dissolved and dispersed to obtain [Oil Phase 1 ′]. Next, 400 parts by mass of [Aqueous Phase 1] is put into another container in which a stirrer and a thermometer are set, and while stirring at 13,000 rpm with a TK homomixer (made by Tokushu Kika Kogyo Co., Ltd.) [Oil phase 1 ′] was added and emulsified for 1 minute to obtain [Emulsified slurry 1].

-Solvent removal-Cleaning-Drying-
[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 8 hours to obtain [Slurry 1]. The obtained [Slurry 1] was filtered under reduced pressure, and then the following washing treatment was performed.
(1) 100 parts by mass of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (5 minutes at a rotation speed of 6,000 rpm), and then filtered.
(2) 100 parts by mass of a 10% by mass aqueous sodium hydroxide solution was added to the filter cake of (1) and mixed with a TK homomixer (rotation speed: 6,000 rpm for 10 minutes), followed by filtration under reduced pressure.
(3) 100 parts by mass of 10 mass% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (5 minutes at a rotation speed of 6,000 rpm), and then filtered.
(4) Add 300 parts by mass of ion-exchanged water to the filter cake of (3), mix with a TK homomixer (5 minutes at 6,000 rpm), and then filter twice to obtain filter cake 1 It was.
The obtained filter cake 1 was dried at 45 ° C. for 48 hours with a circulating dryer. Thereafter, the toner base particles 1 were produced by sieving with a 75 μm mesh.

(Production Example 2 of toner base particles)
<Production of toner base particles 2 (ester elongation method)>
-Preparation of crystalline polyester resin dispersion 1-
In a container in which a stir bar and a thermometer are set, 100 parts by mass of [Crystalline Polyester Resin 1] and 400 parts by mass of ethyl acetate are heated and dissolved at 75 ° C. with stirring. Cool and use a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.) to disperse for 5 hours under the conditions of a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 80% by volume of 0.5 mm zirconia beads. [Crystalline polyester resin dispersion liquid 1] was obtained.

-Production of oil phase 2-
In a container equipped with a thermometer and a stirrer, 93 parts by mass of [Non-crystalline polyester resin 1], 68 parts by mass of [Crystalline polyester resin dispersion 1], 75 parts by mass of [Releasing agent dispersion 1], [ Master batch 1] Put 18 parts by mass and 19 parts by mass of ethyl acetate, pre-disperse with a stirrer, and then stir at a rotational speed of 5,000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). And uniformly dissolved and dispersed to obtain [Oil Phase 2].

―Emulsification or dispersion―
To 273 parts by mass of [Oil Phase 2], 45 parts by mass of an ethyl acetate solution of [Polyester Prepolymer 1] and 3 parts by mass of a 50% by mass ethyl acetate solution of isophoronediamine are added. Co., Ltd.) was stirred at a rotational speed of 5,000 rpm, and was uniformly dissolved and dispersed to obtain [Oil Phase 2 ′]. Next, 400 parts by mass of [Aqueous Phase 1] is put into another container in which a stirrer and a thermometer are set, and while stirring at 13,000 rpm with a TK homomixer (made by Tokushu Kika Kogyo Co., Ltd.) [Oil phase 2 ′] was added and emulsified for 1 minute to obtain [Emulsified slurry 2].

-Solvent removal, washing, drying-
[Emulsion slurry 2] was subjected to solvent removal, washing, drying, and air sieving under the same conditions as in [Emulsion slurry 1] to prepare toner base particles 2.

(Production Example 3 of toner base particles)
<Production of toner base particles 3 (dissolution suspension method)>
-Preparation of oil phase 3-
In a container equipped with a thermometer and a stirrer, 107 parts by mass of [Non-crystalline polyester resin 1], 23 parts by mass of [Amorphous polyester resin 3], 75 parts by mass of [Releasing agent dispersion 1], [Master Batch 1] Put 18 parts by mass and 97 parts by mass of ethyl acetate, pre-disperse with a stirrer, and then stir at a rotational speed of 5,000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). And uniformly dissolved and dispersed to obtain [Oil Phase 3].

―Emulsification or dispersion―
Put 400 parts by mass of [Aqueous Phase 1] in another container with a stirrer and thermometer, and stir at 13,000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Phase 3] was added and emulsified for 1 minute to obtain [Emulsified slurry 3].

-Solvent removal-Cleaning-Drying-
[Emulsion slurry 3] was subjected to solvent removal, washing, drying, and air sieving under the same conditions as in [Emulsion slurry 1] to prepare toner base particles 3.

(Production Example 4 of toner base particles)
<Production of toner base particles 4 (dissolution suspension method)>
-Production of oil phase 4-
In a container equipped with a thermometer and a stirrer, 93 parts by mass of [Non-crystalline polyester resin 1], 23 parts by mass of [Non-crystalline polyester resin 3], 68 parts by mass of [Crystalline polyester resin dispersion 1], [ Release agent dispersion liquid 1] 75 parts by mass, [Masterbatch 1] 18 parts by mass, and 43 parts by mass of ethyl acetate were added and pre-dispersed with a stirrer, and then TK homomixer (Special Machine Industries Co., Ltd.) The product was stirred at a rotational speed of 5,000 rpm, uniformly dissolved, and dispersed to obtain [Oil Phase 4].

―Emulsification or dispersion―
In another container in which a stirrer and a thermometer are set, 400 parts by mass of [Aqueous Phase 1] is placed, and stirred at 13,000 rpm with a TK homomixer (manufactured by Special Machine Industries Co., Ltd.) [Oil phase 4] was added and emulsified for 1 minute to obtain [Emulsified slurry 4].

-Solvent removal-Cleaning-Drying-
[Emulsion slurry 4] was subjected to solvent removal, washing, drying, and air sieving under the same conditions as in [Emulsion slurry 1] to prepare toner base particles 4.

(Production Example 5 of toner base particles)
<Production of toner base particles 5 (emulsion aggregation method)>
-Preparation of amorphous polyester resin dispersion 2-
[Amorphous polyester resin 2] 60 parts by mass of ethyl acetate was added to 60 parts by mass and dissolved. Next, 120 parts by weight of water, 2 parts by weight of an anionic surfactant (Neogen R, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 2.4 parts by weight of a 2% by weight aqueous sodium hydroxide solution were mixed in [Aqueous Phase]. After adding 120 parts by mass of the resin solution and emulsifying with a homogenizer (manufactured by IKA, Ultra Tarrax T50), the mixture was emulsified with a Manton Gorin high-pressure homogenizer (manufactured by Gorin) to obtain an [emulsified slurry].
Next, the [emulsified slurry] was charged into a container equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 4 hours to obtain [Amorphous polyester resin dispersion 2]. It was 0.15 micrometer when the volume average particle diameter of the particle | grains in the obtained [amorphous polyester resin dispersion liquid 2] was measured with the particle size distribution analyzer (LA-920, Horiba, Ltd. make).

-Preparation of amorphous polyester resin dispersion 3-
In the production of [Non-crystalline polyester resin dispersion liquid 2], [Non-crystalline polyester resin dispersion liquid 3] was similarly obtained except that [Non-crystalline polyester resin 2] was replaced with [Non-crystalline polyester resin 3]. ] Was obtained. It was 0.16 micrometer when the volume average particle diameter of the particle | grains in the obtained [amorphous polyester resin dispersion liquid 3] was measured with the particle size distribution analyzer (LA-920, Horiba, Ltd. make).

-Preparation of release agent dispersion 2-
25 parts by mass of paraffin wax (HNP-9, manufactured by Nippon Seiki Co., Ltd., melting point 75 ° C.), 1 part by mass of an anionic surfactant (Neogen R, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 200 parts by mass of water are mixed. It was melted at 90 ° C. Next, this melt was emulsified with a homogenizer (IKA, Ultra Tarrax T50) and then emulsified with a Menton Gorin high-pressure homogenizer (Gorin) to obtain [Releasing Agent Dispersion 2].

-Preparation of Colorant Dispersion 1-
Carbon black (Printtex 35, manufactured by Degussa) 20 parts by mass, anionic surfactant (Neogen R, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 parts by mass, and water 80 parts by mass are mixed, and a TK homomixer (special [Colorant Dispersion Liquid 1] was obtained.

―Agglomeration―
In a container equipped with a thermometer and a stirrer, 235 parts by mass of [Amorphous polyester resin dispersion 2], 57 parts by mass of [Amorphous polyester resin dispersion 3], and 45 parts by weight of [Releasing agent dispersion 2] Part, [Colorant dispersion 1] 26 parts by mass, and 600 parts by mass of water were added and stirred at 30 ° C. for 30 minutes. The dispersion was adjusted to pH 10 by adding a 2% by weight aqueous sodium hydroxide solution.
Next, while stirring this dispersion at 5,000 rpm with a homogenizer (manufactured by IKA, Ultra Turrax T50), 50 parts by mass of a 5% by mass magnesium chloride aqueous solution was gradually dropped and heated to 45 ° C. The agglomerated particles were maintained at 45 ° C. until the volume average particle diameter grew to 5.3 μm. While heating at 90 ° C. while maintaining pH 9 by adding a 2% by weight aqueous sodium hydroxide solution to this, holding in this state for 2 hours, cooling to 20 ° C. at 1 ° C./min. Obtained.

-Solvent removal-Cleaning-Drying-
[Slurry 5] was washed, dried, and air-sieved under the same conditions as [Slurry 1] to prepare toner base particles 5.

(Production Example 6 of Toner Base Particles)
<Production of toner base particles 6 (emulsion aggregation method)>
-Preparation of crystalline polyester resin dispersion 2-
[Crystalline Polyester Resin 1] 60 parts by mass of ethyl acetate was added to 60 parts by mass and mixed and stirred at 60 ° C. to dissolve. Next, 120 parts by weight of water, 2 parts by weight of an anionic surfactant (Neogen R, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 2.4 parts by weight of a 2% by weight aqueous sodium hydroxide solution were mixed in [Aqueous Phase]. After adding 120 parts by mass of the resin solution and emulsifying with a homogenizer (manufactured by IKA, Ultra Tarrax T50), the mixture was emulsified with a Manton Gorin high-pressure homogenizer (manufactured by Gorin) to obtain an [emulsified slurry].
Next, the [emulsified slurry] was charged into a container equipped with a stirrer and a thermometer, and the solvent was removed at 60 ° C. for 4 hours to obtain [Crystalline Polyester Resin Dispersion 2]. It was 0.17 micrometer when the volume average particle diameter of the particle | grains in the obtained [crystalline polyester resin dispersion liquid 2] was measured with the particle size distribution analyzer (LA-920, Horiba, Ltd. make).

―Agglomeration―
In a container equipped with a thermometer and a stirrer, 207 parts by mass of [Amorphous polyester resin dispersion 2], 57 parts by mass of [Amorphous polyester resin dispersion 3], [Crystalline polyester resin dispersion 2] 28 Part by mass, 45 parts by mass of [Releasing agent dispersion 2], 26 parts by mass of [Colorant dispersion 1], and 600 parts by mass of water were added and stirred at 30 ° C. for 30 minutes. The dispersion was adjusted to pH 10 by adding a 2% by weight aqueous sodium hydroxide solution. Next, while stirring this dispersion at 5,000 rpm with a homogenizer (manufactured by IKA, Ultra Turrax T50), 50 parts by mass of a 5% by mass magnesium chloride aqueous solution was gradually dropped and heated to 45 ° C. The agglomerated particles were maintained at 45 ° C. until the volume average particle diameter grew to 5.3 μm. This was cooled to 20 ° C. to obtain [Slurry 6].

-Solvent removal-Cleaning-Drying-
[Slurry 6] was washed, dried, and air sieved under the same conditions as in [Slurry 1] to prepare toner base particles 6.

(Production Example 7 of toner base particles)
<Manufacture of toner base particles 7 (pulverization method)>
-Production of master batch 2-
Non-crystalline polyester resin 2 ... 100 parts by mass Carbon black (Printex35, manufactured by Degussa) ... 100 parts by mass (DBP oil absorption: 42 mL / 100 g, pH: 9.5)
-Ion exchange water ... 50 mass parts Said raw material was mixed using the Henschel mixer (made by Mitsui Mining Co., Ltd.). The obtained mixture was kneaded using two rolls. The kneading temperature started kneading from 90 ° C., and then gradually cooled to 50 ° C. The obtained kneaded material was pulverized with a pulverizer (manufactured by Hosokawa Micron Corporation) to prepare [Masterbatch 2].

-Melt kneading, grinding, classification-
[Amorphous polyester resin 2] 49 parts by mass, [Amorphous polyester resin 3] 40 parts by mass, paraffin wax (HNP-9, Nippon Seiki Co., Ltd., melting point 75 ° C.) 6 parts by mass, and [Masterbatch 2] After premixing 12 parts by mass using a Henschel mixer (Henschel 20B, manufactured by Mitsui Mining Co., Ltd.) for 3 minutes at 1,500 rpm, a single-screw kneader (compact bus co-kneader, manufactured by Buss) The mixture was melted and kneaded under the conditions of the set temperature (inlet part 90 ° C.), outlet part (60 ° C.), and feed amount (10 kg / hr). The obtained kneaded product was rolled and cooled, and coarsely pulverized with a pulperizer (manufactured by Hosokawa Micron Corporation). Next, in a type I mill (made by Nippon Pneumatic Co., Ltd., IDS-2 type), using a flat collision plate, the air pressure (6.0 atm / cm ² ) and feed amount (0.5 kg / hr) were set. The resultant was finely pulverized and further classified by a classifier (manufactured by Alpine, 132MP) to obtain [Mother toner particles 7].

(Manufacturing Example 8 of Toner Base Particles)
<Manufacture of toner base particles 8 (pulverization method)>
-Melt kneading, grinding, classification-
[Amorphous Polyester Resin 2] 54 parts by mass, [Amorphous Polyester Resin 3] 27 parts by mass, [Crystalline Polyester Resin 1] 8 parts by mass, paraffin (HNP-9, Nippon Seiki Co., Ltd., melting point 75 ° C) 6 parts by mass and [Masterbatch 2] 12 parts by mass were premixed at 1,500 rpm for 3 minutes using a Henschel mixer (Henschel 20B, manufactured by Mitsui Mining Co., Ltd.). It was melted and kneaded under the conditions of a set temperature (inlet part 90 ° C.), outlet part (60 ° C.), and feed amount (10 kg / hr) using a bus co-kneader (manufactured by Buss). The obtained kneaded product was rolled and cooled, and coarsely pulverized with a pulperizer (manufactured by Hosokawa Micron Corporation). Next, in an I-type mill (made by Nippon Pneumatic Co., Ltd., IDS-2 type), using a flat collision plate, air pressure (6.0 atm / cm ² ), feed amount (0.5 kg / hr) conditions Was further pulverized and further classified by a classifier (manufactured by Alpine, 132MP) to obtain [Mother toner particles 8].

(Toner Production Examples 1 to 26)
<Preparation of Toners 1 to 26>
A predetermined amount of a predetermined external additive is added to 100 parts by mass of the obtained [Toner Base Particles 1] to [Toner Base Particles 8] according to Table 2, and further, titanium oxide (trade name “JMT-150IB”) is added. The toner 1 to the toner 26 were obtained by adding 0.6 parts by mass (made by Teica) and mixing with a Henschel mixer (made by Mitsui Mining Co., Ltd.) and passing through a sieve having a mesh size of 500 mesh.
For each of the toner obtained, as follows, to measure the loose apparent density [rho _M and [rho _H of toner. The results are shown in Table 2.

<Measurement method of apparent density of loose toner>
The loose apparent density ρ _M of the toner at 22 ° C. and 55% RH was measured by the following method.
In addition, the loose apparent density ρ _H after storing the toner in a constant temperature bath of 70% RH at 40 ° C. for 14 days was measured by placing the toner used for measurement in a constant temperature bath of 40 ° C. and 70% RH. It was stored for 14 days and then measured by the following method.
Using a 100 mL graduated cylinder, toner was gradually added to 100 mL. At that time, no vibration was applied.
The apparent density of loose toner was calculated from the following formula using the weight difference (toner weight) before and after the toner in the measuring cylinder.
Toner loose apparent density (g / cm ³ ) = toner weight (g / 100 mL) ÷ 100

(Carrier Production Example 1)
<Preparation of carrier 1>
26 parts by mass of a silicone resin solution (solid content 23% by mass, SR2410, manufactured by Toray Dow Corning), acrylic resin (Hitaroid 3001, solid content 50% by mass, manufactured by Hitachi Chemical Co., Ltd.) 2.5 parts by mass, benzoguanamine type 5 parts by mass of resin (My Coat 106, solid content 77% by mass, manufactured by Mitsui Cytec Co., Ltd.), 18 parts by mass of alumina particles (particle size 0.3 μm, specific resistance 10 ¹⁴ Ω · cm), titanium diisopropoxybis as a catalyst (Ethyl acetoacetate) TC-750 (manufactured by Matsumoto Fine Chemical Co., Ltd.) 2 parts by mass, SH6020 (manufactured by Toray Dow Corning Co., Ltd.) 0.2 part by mass as a silane coupling agent was diluted with toluene, and homomixed for 10 minutes. Dispersion was performed to obtain a resin solution having a solid content of 10% by mass.
The obtained resin solution was baked ferrite powder [(MgO) _1.8 (MnO) _49.5 (Fe ₂ O ₃ ) _48.0 , weight average particle size: 35 μm] on 1,000 parts by mass of the core particle surface. It was applied with a Spira coater (manufactured by Okada Seiko Co., Ltd.) so that the thickness of the coating layer was 0.15 μm and dried to obtain a coated ferrite powder. The obtained coated ferrite powder was fired at 180 ° C. for 2 hours in an electric furnace. After cooling, the ferrite powder bulk was crushed using a sieve having an aperture of 106 μm to obtain a carrier 1 having a weight average particle diameter of 35 μm.

(Examples 1 to 22 and Comparative Examples 1 to 4)
<Preparation of developers 1 to 26>
According to Table 2, 70 parts by mass of any one of toner 1 to toner 26 and 930 parts by mass of carrier 1 were placed in a commercially available ointment bottle, and mixed for 5 minutes at 81 rpm with a tumbler mixer. And the developers 1-26 of Comparative Examples 1-4 were produced.

  Next, for the obtained toners 1 to 26 and developers 1 to 26, toner replenishability (medium speed machine), toner replenishability (high speed machine), waste toner transportability (medium speed machine) are as follows. Evaluation of waste toner transportability (high speed machine) and low-temperature fixability was made, and a comprehensive judgment was made. The results are shown in Table 2.

<Toner replenishability>
(1) Toner replenishability (medium speed machine)
The toners of Examples and Comparative Examples were set in an evaluation machine in which the toner supply unit of a commercially available digital full-color printer (image MPC6000, A4 size horizontal color 50 sheets / minute, manufactured by Ricoh Co., Ltd.) was modified, After storage in the environment, the image was output until the toner end detection functioned (until the toner supply amount ceased).
The toner used was stored for 14 days in a thermostatic bath set at 40 ° C. ± 2 ° C. and 70% ± 5% RH before the evaluation.

(2) Toner replenishment (high speed machine)
The evaluation of toner replenishment (medium speed machine) except that an evaluation machine in which the toner supply unit of a commercially available digital full color printer (RICOH Pro C901, 90 sheets of A4 size horizontal color / min, manufactured by Ricoh Co., Ltd.) was used was used. It implemented by the same method.
[Evaluation criteria]
◎: Very good, ○: Good, Δ: Acceptable, ×: Unusable level for practical use, ◎, ○, △ were accepted, and x was rejected.
◎: No change in replenishability until toner end, less than 1 g of residual toner in toner storage container at toner end ○: No change in replenishment ability until toner end, but remaining toner in toner storage container at toner end Amount 1 g or more and 5 g or less Δ: Toner end is lit with toner remaining in the storage container, but recovers by vibrating the storage container ×: Toner with toner remaining in the storage container The end lights up, but does not recover by vibrating the container

<Waste toner transportability>
(1) Waste toner transportability (medium speed machine)
Using a commercially available digital full-color printer (image MPC6000, A4 size horizontal color 50 sheets / minute, manufactured by Ricoh Co., Ltd.), 20% chart paper is continuously output for 5 hours at 32 ° C in a 54% RH environment. The state of the toner in the later waste toner conveyance path was observed.
The toner used was stored for 14 days in a thermostatic bath set at 40 ° C. ± 2 ° C. and 70% ± 5% RH before the evaluation.

(2) Waste toner transportability (high speed machine)
Except for using a commercially available digital full-color printer (RICOH Pro C901, 90 sheets of A4 size horizontal color / min, manufactured by Ricoh Co., Ltd.), the same method as in the evaluation of waste toner transportability (medium speed machine) was used.
[Evaluation criteria]
◎: Very good, ○: Good, Δ: Acceptable, ×: Unusable level for practical use, ◎, ○, △ were accepted, and x was rejected.
A: The toner is not completely solidified. ○: The toner is loosely solidified. Δ: The toner is slightly solidified. X: The toner is solidified firmly.

<Low temperature fixability>
A copy test was performed on recording paper (type 6200, manufactured by Ricoh Co., Ltd.) using a device in which the fixing part of a commercially available digital full-color printer (image MPC6000, A4 size horizontal color 50 sheets / min, manufactured by Ricoh Co., Ltd.) was modified. It was. Specifically, the cold offset temperature (fixing lower limit temperature) was determined by changing the fixing temperature. The evaluation conditions for the minimum fixing temperature were a paper feed linear velocity of 260 mm / second to 280 mm / second, a surface pressure of 1.2 kgf / cm ² , and a nip width of 11 mm. Evaluation of low-temperature fixability was evaluated according to the following criteria. The lower the fixing minimum temperature, the better the low-temperature fixability.
[Evaluation criteria]
◎: Very good, ○: Good, Δ: Acceptable, ×: Unusable level for practical use, ◎, ○, △ were accepted, and x was rejected.
A: Lower limit fixing temperature is less than 120 ° C. O: Lower limit fixing temperature is 120 ° C. or higher and lower than 130 ° C. Δ: Lower limit fixing temperature is 130 ° C. or higher and lower than 140 ° C. ×: Lower limit fixing temperature is 140 ° C. or higher and lower than 150 ° C.

<Comprehensive judgment>
◎: Very good, ○: Good, Δ: Acceptable, ×: Unusable level for practical use, ◎, ○, △ were accepted, and x was rejected.
◎: There are two or more ◎, and Δ, × None ○: One ◎ and Δ, × None △: Two or more Δ, ◎, × None ×: One or more ×

The detailed contents of other external additives in Table 2-2 are as follows.
* NX90G (hydrophobized silica fine particles, manufactured by Nippon Aerosil Co., Ltd.)
* HDK H2000T (hydrophobized silica fine particles, manufactured by Clariant Japan)
* HDK H1303VP (hydrophobized silica fine particles, manufactured by Clariant Japan)
* NAX50 (hydrophobized silica fine particles, manufactured by Nippon Aerosil Co., Ltd.)

  From the results of Tables 2-1 to 2-3, Examples 1 to 22 have toner replenishability and waste toner transportability in medium speed machines and toner replenishment characteristics in high speed machines as compared with Comparative Examples 1 to 4. In addition, it was found that good results can be obtained for the waste toner transportability.

As an aspect of this invention, it is as follows, for example.
<1> A toner comprising toner base particles containing a binder resin and a colorant, and an external additive,
The external additive contains at least coalesced particles, and the coalesced particles are non-spherical secondary particles obtained by coalescing primary particles.
The loose apparent density ρ _{M of the} toner at 22 ° C. and 55% RH and the loose apparent density ρ _H after storing the toner in a constant temperature bath at 40 ° C. and 70% RH for 14 days are expressed as follows: The toner satisfies ρ _H / ρ _M ≦ 0.10.
<2> The toner according to <1>, wherein the toner satisfies the following formula: 1−ρ _H / ρ _M ≦ 0.05.
<3> The toner according to any one of <1> to <2>, wherein the external additive further contains inorganic fine particles having a number average primary particle size of 30 nm to 60 nm.
<4> The toner according to any one of <1> to <3>, wherein a particle size distribution index of the coalesced particles is represented by the following formula (2).
However, in the formula (2), Db ₅₀ is the coalesced particles when the particle diameter (nm) of the coalesced particles is on the horizontal axis and the cumulative value (number%) of the coalesced particles is on the vertical axis. Represents the particle diameter of the coalesced particles having a cumulative value of 50% by number when drawn from the small particle side, and Db ₁₀ represents the particle size of the coalesced particles having the cumulative value of 10% by number. Represents the particle size.
<5> The toner according to any one of <1> to <4>, wherein the external additive satisfies the following formula (3).
In the formula (3), Nx represents the number of cracked or disintegrated particles in 1,000 particles of the external additive, and the Nx represents 0. 0 of the external additive in a 50 mL bottle. 5 g and 49.5 g of carrier are stirred with a mixing stirrer at 67 Hz for 10 minutes, and then observed and measured with a scanning electron microscope.
<6> The toner according to any one of <1> to <5>, wherein the number average particle diameter of the coalesced particles is 80 nm to 200 nm.
<7> The toner according to any one of <1> to <6>, wherein the binder resin contains a crystalline polyester resin.
<8> A developer containing the toner according to any one of <1> to <7>.
<9> An electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image with toner to make it visible An image forming apparatus having at least developing means for forming an image, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transferred image transferred to the recording medium,
An image forming apparatus, wherein the toner is the toner according to any one of <1> to <7>.

DESCRIPTION OF SYMBOLS 10 Process cartridge 11 Photoconductor 12 Charging apparatus 13 Developing apparatus 14 Cleaning apparatus 20 Electrostatic latent image carrier (photosensitive body)
21 toner 23 carrier 24a, 24b driving roller 26 exposure light source 32 before cleaning 32 charging device 33 exposure device 40 developing device 41 developing sleeve 42 developer accommodating member 43 doctor blade 44 support case 45 toner hopper 46 developer accommodating portion 47 developer agitating mechanism 48 toner agitator 49 toner replenishing mechanism 50 transfer device 60 cleaning device 61 cleaning blade 64 brush-like cleaning means 70 static elimination device

Japanese Patent No. 3909939 Japanese Patent No. 3328013 Japanese Patent No. 4894476

Claims (9)

A toner comprising toner base particles containing a binder resin and a colorant, and an external additive,
The external additive contains at least coalesced particles and inorganic fine particles,
The coalesced particles, I Oh secondary particles of non-spherical between primary particles formed by bonding a number average particle diameter of the coalesced particles are 80 nm to 200 nm,
The inorganic fine particles are silica fine particles having a number average primary particle size of 30 nm to 60 nm,
The loose apparent density ρ _{M of the} toner at 22 ° C. and 55% RH and the loose apparent density ρ _H after storing the toner in a constant temperature bath at 40 ° C. and 70% RH for 14 days are expressed as follows: A toner satisfying ρ _H / ρ _M ≦ 0.07 . The toner according to claim 1, wherein the toner satisfies the following formula: 1−ρ _H / ρ _M ≦ 0.05. The toner according to claim 1, wherein the silica fine particles are hydrophobic silica fine particles. The toner according to claim 1, wherein the particle size distribution index of the coalesced particles is represented by the following formula (2).
However, in the formula (2), Db ₅₀ is the coalesced particles when the particle diameter (nm) of the coalesced particles is on the horizontal axis and the cumulative value (number%) of the coalesced particles is on the vertical axis. Represents the particle diameter of the coalesced particles having a cumulative value of 50% by number when drawn from the small particle side, and Db ₁₀ represents the particle size of the coalesced particles having the cumulative value of 10% by number. Represents the particle size. The toner according to claim 1, wherein the external additive satisfies the following formula (3).
In the formula (3), Nx represents the number of cracked or disintegrated particles in 1,000 particles of the external additive, and the Nx represents 0. 0 of the external additive in a 50 mL bottle. 5 g and 49.5 g of carrier are stirred with a mixing stirrer at 67 Hz for 10 minutes, and then observed and measured with a scanning electron microscope. The toner according to claim 1, wherein the number average particle diameter of the coalesced particles is 100 nm to 160 nm.   The toner according to claim 1, wherein the binder resin contains a crystalline polyester resin.   A developer containing the toner according to claim 1. An electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image with toner to form a visible image An image forming apparatus having at least developing means for transferring, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transferred image transferred to the recording medium,
The image forming apparatus according to claim 1, wherein the toner is the toner according to claim 1.