JP4966057B2 - Toner, developer, toner container, process cartridge, image forming apparatus, and image forming method - Google Patents

Description

  The present invention relates to a toner for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing, and the like, a developer using the toner, a container containing the toner, a process cartridge, an image forming apparatus, and an image forming method. About.

  In the image formation by electrophotography, generally, an electric latent image is formed on a photoconductor produced using a photoconductive substance by various means. Next, after developing the latent image using a developer, the image formed by the developer is transferred to paper or the like as necessary, and then fixed by heating, pressing, or solvent vapor.

  The methods for developing electrical latent images can be broadly divided into a liquid development method using a liquid developer in which various pigments and dyes are finely dispersed in an insulating organic liquid, a cascade method, a magnetic brush method, and a powder cloud. And other dry development methods using a dry developer in which a colorant such as carbon black is dispersed in a resin (hereinafter also referred to as “toner”). in use.

  As a fixing method in the dry development method, a heating heat roller method is widely used because of its energy efficiency. In recent years, in order to save energy by fixing the toner at a low temperature, the thermal energy given to the toner at the time of fixing tends to be small. In the 1999 International Energy Agency (IEA) DSM (Demand-Side Management) program, there is a technology procurement project for next-generation copiers, and the required specifications are published. For copiers of 30 cpm or more, drastically reduced energy consumption compared to conventional copiers so that the standby time is within 10 seconds and the standby power consumption is 10 to 30 watts or less (depending on the copying speed). Achievement is required. As a method for achieving this requirement, a method of improving the temperature responsiveness of the toner by reducing the heat capacity of a fixing member such as a heating heat roller can be considered, but it is not fully satisfactory.

In order to achieve the above requirement and minimize the waiting time, it is considered to be an essential technical achievement matter to lower the fixing temperature of the toner itself and lower the toner fixing temperature when it can be used.
In order to cope with such low-temperature fixing, an attempt has been made to use a polyester resin having excellent low-temperature fixability and relatively good heat-preserving stability in place of the styrene-acrylic resin that has been widely used conventionally (Patent Document 1). Patent Document 2, Patent Document 3, Patent Document 4, Patent Document 5, and Patent Document 6). In addition, for the purpose of improving low-temperature fixability, an attempt to add a specific non-olefinic crystalline polymer to the binder (see Patent Document 7), an attempt to use a crystalline polyester (see Patent Document 8), and the like have been proposed. However, it cannot be said that the molecular structure and molecular weight of the polyester resin are optimized.

Further, even if these conventionally known techniques are applied, it is impossible to achieve the specifications of the DSM program, and it is necessary to establish a low-temperature fixing technique that is further advanced from the conventional technical field.
Therefore, it is necessary to control the thermal characteristics of the resin itself for further low-temperature fixing. However, if the glass transition temperature (Tg) is lowered too much, the heat-resistant storage stability is deteriorated, and the molecular weight is reduced. If the F1 / 2 temperature is lowered too much, there is a problem that the hot offset occurrence temperature is lowered. For this reason, by controlling the thermal characteristics of the resin itself, it has not been possible to obtain a toner having excellent low-temperature fixability and a high hot offset occurrence temperature.

Next, a method for producing a toner used for developing an electrostatic image is roughly classified into a pulverization method and a polymerization method.
In the pulverization method, a colorant, a charge control agent, an offset preventive agent, and the like are melt-mixed and uniformly dispersed in a thermoplastic resin, and a toner is manufactured by pulverizing and classifying the obtained toner composition. Yes. According to this pulverization method, a toner having some excellent characteristics can be produced, but there is a limitation in the selection of materials. That is, the toner composition obtained by melt mixing must be pulverized and classified by an economically usable apparatus. From this demand, the melt-mixed toner composition must be sufficiently brittle. For this reason, when the toner composition is actually pulverized into particles, a high-range particle size distribution is likely to be formed, and a copy image having good resolution and gradation can be obtained. The weight average particle size of the toner must be reduced, and fine powder with a particle size of 4 μm or less and coarse powder with a particle size of 15 μm or more must be removed by classification, resulting in a very low toner yield. In the pulverization method, it is difficult to uniformly disperse the colorant, the charge control agent and the like in the thermoplastic resin. As a result, the toner fluidity, developability, durability, image quality, etc. are adversely affected. There is a drawback of affecting.

In recent years, in order to overcome these problems in the pulverization method, a toner production method using a polymerization method has been proposed and implemented. For example, toner particles are obtained by a suspension polymerization method or an emulsion polymerization aggregation method (see Patent Document 9). However, in these toner production methods, it has been difficult to produce toner using a polyester resin superior in low-temperature fixability.
In order to solve this problem, for example, a toner made of a polyester resin in a spherical shape using a solvent in water (see Patent Document 10), a toner using an isocyanate reaction (see Patent Document 11), and the like have been proposed. Yes. However, none of these proposals can satisfy the low-temperature fixability and the toner productivity.

  Therefore, a toner that can achieve both excellent low-temperature fixing property and anti-offset performance and can form a good high-definition image and related technology have not yet been obtained, and its rapid provision is desired. is the current situation.

JP 60-90344 A JP-A 64-15755 Japanese Patent Laid-Open No. 2-82267 JP-A-3-229264 JP-A-3-41470 JP-A-11-305486 JP 62-63940 A Japanese Patent No. 2931899 Japanese Patent No. 2537503 JP-A-9-34167 JP-A-11-149180

  An object of the present invention is to solve the conventional problems in response to the above-mentioned demands and achieve the following object. That is, the present invention can achieve both excellent low-temperature fixability and offset resistance, and can form a good high-definition image, as well as a developer, a toner-containing container, and a process cartridge using the toner. An object of the present invention is to provide an image forming apparatus and an image forming method.

As a result of intensive studies by the present inventors in order to solve the above problems, the bisphenol-based polyester exhibits the catalytic functions of both the polymerization reaction (condensation polymerization) and the isocyanate modification reaction by using an Sn-based catalyst. Therefore, there is a great industrial advantage that it is not necessary to perform treatment such as catalyst removal and purification or addition of a new catalyst system according to the reaction. However, the bisphenol-based polyester has a problem that a gel-like component that is substantially insoluble in an organic solvent such as ethyl acetate is formed due to an increase in molecular weight.
On the other hand, when an aliphatic polyhydric alcohol mainly composed of ethylene glycol (EG) / polyethylene glycol (PG) is used as an alcohol component for condensation polymerization, even if a large molecular weight component is formed, polyester represented by ethyl acetate Therefore, it is possible to form a toner composition in a uniform system because it is easily soluble in an organic solvent. In addition, organic Sn-based catalysts that have been used for general purposes separately in the synthesis of polyester are desired to be replaced with other polymerization catalysts in view of social demands, particularly environmental and health aspects. With regard to such EG / PG system, it is possible to proceed the polyesterification reaction using a non-Sn polyester catalyst (for example, a Ti catalyst) without using a Sn catalyst. However, the Sn-based catalyst has a function as a polymerization catalyst and a catalytic function for an isocyanate reaction, whereas a Ti-based catalyst has difficulty in exhibiting such a multifunctional function as a catalyst. The isocyanate modification reaction could not proceed sufficiently.
Therefore, in the present invention, in the EG / PG system, a non-Sn isocyanate catalyst (for example, Bi catalyst) is used in the isocyanate modification reaction after the polyesterification reaction, which is difficult in the bisphenol system. The increase in the molecular weight of the non-gelled isocyanate-modified polyester can be used in a homogeneous oil phase.

The present invention is based on the above findings by the present inventors, and means for solving the above problems are as follows. That is,
<1> A solution or dispersion obtained by dissolving or dispersing a toner material containing at least an active hydrogen group-containing compound, a polymer having a site capable of reacting with the active hydrogen group-containing compound, and a colorant in an organic solvent. A toner obtained by emulsifying or dispersing in the active hydrogen group-containing compound and the polymer while reacting or reacting, and then removing the organic solvent,
The polymer includes at least a modified polyester, and the modified polyester has a bond portion derived from an isocyanate group,
The toner has a Sn content of 800 ppm or less, a non-Sn polyester-derived metal content from 10 ppm to 200 ppm, and a non-Sn isocyanate catalyst-derived metal content from 10 ppm to 10 ppm. The toner is characterized by 200 ppm.
<2> The content of Sn in the toner is 0 ppm to 500 ppm, the content of the non-Sn polyester-derived catalyst is 10 ppm to 200 ppm, and the content of the non-Sn isocyanate-derived metal The toner according to <1>, wherein the amount is 10 ppm to 200 ppm.
<3> The toner according to <1>, wherein the Sn content in the toner is 800 ppm or less, the Ti content is 10 ppm to 200 ppm, and the Bi content is 10 ppm to 200 ppm.
<4> The toner according to <3>, wherein the Sn content in the toner is 0 ppm to 500 ppm, the Ti content is 10 ppm to 200 ppm, and the Bi content is 10 ppm to 200 ppm.
<5> The toner according to any one of <1> to <4>, wherein the bond portion derived from the isocyanate group is at least one of a urea bond and a urethane bond.
<6> The modified polyester contains an isocyanate-terminated polyester, and the isocyanate-terminated polyester is obtained by reacting an unmodified polyester with a diisocyanate compound in the presence of an isocyanate catalyst that is non-Sn. The toner according to any one of <5>.
<7> The toner according to any one of <1> to <6>, wherein the unmodified polyester is polymerized using a polyesterification catalyst that is non-Sn.
<8> The toner according to any one of <6> to <7>, wherein the unmodified polyester includes only a non-crosslinked component.
<9> Any one of <6> to <8>, wherein the isocyanate terminal-modified polyester has an OH number of the unmodified polyester and an NCO number ratio of the diisocyanate compound (NCO / OH) of 2.0 to 2.5. The toner described in 1.
<10> The toner according to any one of <1> to <9>, wherein the toner contains a crosslinkable polyester.
<11> The crosslinkable polyester is the toner according to <10>, which is formed by a reaction between a modified polyester and an active hydrogen group-containing compound.
<12> The toner includes a binder resin different from the polymer having at least a site capable of reacting with an active hydrogen group-containing compound, and the glass transition temperature of the binder resin is 30 ° C. to 50 ° C. > To <11>.
<13> The toner according to <12>, wherein the acid value of the binder resin is 1 mgKOH / g to 30 mgKOH / g.
<14> The toner according to any one of <1> to <13>, wherein the toner has a glass transition temperature of 40 ° C to 70 ° C.
<15> The toner according to any one of <1> to <14>, wherein the toner has a weight average particle diameter of 3 μm to 8 μm, and the toner has a weight average particle diameter / number average particle diameter of 1.25 or less. is there.
<16> A developer comprising the toner according to any one of <1> to <15>.
<17> A toner-containing container filled with the toner according to any one of <1> to <15>.
<18> An electrostatic latent image carrier and an electrostatic latent image formed on the electrostatic latent image carrier are developed using the toner according to any one of <1> to <15> to be a visible image And a developing means for forming the process cartridge.
<19> An electrostatic latent image carrier, an electrostatic latent image forming unit that forms an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image of <1> to <15> Development means for forming a visible image by developing using any of the toners, 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 is characterized by having at least.
<20> An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image using the toner according to any one of <1> to <15> An image comprising at least a developing step for developing to form a visible image, a transferring step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium It is a forming method.

The toner of the present invention is a solution or dispersion in which a toner material containing at least an active hydrogen group-containing compound, a polymer having a site capable of reacting with the active hydrogen group-containing compound, and a colorant is dissolved or dispersed in an organic solvent. Is obtained by removing an organic solvent while reacting or reacting the active hydrogen group-containing compound and the polymer, and the polymer is at least a modified polyester. And the modified polyester has a bond portion derived from an isocyanate group,
The toner has a Sn content of 800 ppm or less, a non-Sn polyester-derived metal content from 10 ppm to 200 ppm, and a non-Sn isocyanate catalyst-derived metal content from 10 ppm to 10 ppm. In this case, the Sn content in the toner is preferably 800 ppm or less, the Ti content is 10 ppm to 200 ppm, and the Bi content is preferably 10 ppm to 200 ppm.
In the toner of the present invention, by having the above-described configuration, both excellent low-temperature fixability and offset resistance can be achieved, and a good high-definition image can be formed.

  The developer of the present invention contains the toner of the present invention. For this reason, when an image is formed by electrophotography using the developer, both excellent low-temperature fixability and offset resistance can be achieved, and a high-quality image can be obtained.

  The toner-containing container of the present invention contains the toner of the present invention in a container. Therefore, when image formation is performed by electrophotography using the toner contained in the toner-containing container, it is possible to achieve both excellent low-temperature fixability and anti-offset performance and form a good high-definition image. Can do.

  The process cartridge of the present invention comprises an electrostatic latent image carrier and developing means for developing a latent image formed on the electrostatic latent image carrier using the toner of the present invention to form a visible image. At least. The process cartridge is attachable to and detachable from the image forming apparatus, is excellent in convenience, and uses the toner of the present invention. As a result, it is possible to achieve both excellent low-temperature fixability and anti-offset performance. A high-quality image can be obtained.

  The image forming apparatus of 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. In the image forming apparatus, the electrostatic latent image forming unit forms an electrostatic latent image on the electrostatic latent image carrier. The developing means develops the electrostatic latent image using the toner of the present invention to form a visible image. The transfer means transfers the visible image to a recording medium. The fixing unit fixes the transferred image transferred to the recording medium. As a result, both excellent low-temperature fixability and anti-offset performance can be achieved, and a high-quality electrophotographic image can be formed.

  The image forming method of the present invention includes at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step. In the image forming method, an electrostatic latent image is formed on the electrostatic latent image carrier in the electrostatic latent image forming step. In the developing step, the electrostatic latent image is developed using the toner of the present invention to form a visible image. In the transferring step, the visible image is transferred to a recording medium. In the fixing step, the transferred image transferred to the recording medium is fixed. As a result, both excellent low-temperature fixability and anti-offset performance can be achieved, and a high-quality electrophotographic image can be formed.

  According to the present invention, the conventional problems can be solved, both excellent low-temperature fixability and anti-offset performance can be achieved, and a good high-definition image can be formed, and the toner is used. A developer, a container containing toner, a process cartridge, an image forming apparatus, and an image forming method can be provided.

(toner)
The toner of the present invention includes at least an active hydrogen group-containing compound, a polymer having a site capable of reacting with the active hydrogen group-containing compound, a binder resin different from a polymer having a site capable of reacting with the active hydrogen group-containing compound, In addition, a solution or dispersion obtained by dissolving or dispersing a toner material containing a colorant in an organic solvent is emulsified or dispersed in an aqueous medium, and the active hydrogen group-containing compound and the polymer are reacted, or After the reaction, it is obtained by removing the organic solvent.

Sn in the toner is derived from a polymerization catalyst of a binder resin different from the polymer having a site capable of reacting with the active hydrogen group-containing compound, and the Sn content is 800 ppm or less, preferably 0 ppm or more and 500 ppm or less. Thus, it is in line with social needs to reduce Sn content as much as possible.
The content of the non-Sn polyester-derived catalyst metal in the toner is 10 ppm to 200 ppm, preferably 100 ppm to 200 ppm. When the content is less than 10 ppm, the polymerization reaction of the polyester may be insufficient, and when it exceeds 200 ppm, it is economically disadvantageous.
Examples of the non-Sn polyesterification catalyst include a Ti-based catalyst, an Sb-based catalyst, and an Al-based catalyst, and a Ti-based catalyst is particularly preferable. The content of Ti in the toner when the Ti-based catalyst is used is preferably 10 ppm to 200 ppm, and more preferably 100 ppm to 200 ppm.

The content of the non-Sn isocyanate-derived metal in the toner is 10 ppm to 200 ppm, preferably 100 ppm to 200 ppm. If the content is less than 10 ppm, the isocyanate addition reaction may be insufficient, and if it exceeds 200 ppm, it is economically disadvantageous.
Examples of the non-Sn isocyanate catalyst include Bi-based catalysts and Zr-based catalysts, and Bi-based catalysts are particularly preferable. When the Bi-based catalyst is used, the Bi content in the toner is preferably 10 ppm to 200 ppm, more preferably 100 ppm to 200 ppm.

The content (Sn, Bi, Ti, etc.) of the catalyst-derived metal in the toner can be measured by, for example, a fluorescent X-ray measurement apparatus.
Specifically, a calibration curve is prepared with a fluorescent X-ray analyzer using toner base particles with a clear inorganic compound content, and the inorganic compound content in the toner base particles is determined using the calibration curve. Obtained by line analysis. For example, ZSX-100E manufactured by Rigaku Corporation can be used as the fluorescent X-ray analyzer. Further, when two or more inorganic compounds were used, the total of the analytical values of the inorganic compound content was used as the inorganic compound content in the toner base particles.

  The polymer having a site capable of reacting with the compound having an active hydrogen group contains at least a modified polyester, and the modified polyester has a bond part derived from an isocyanate group, and the bond part derived from the isocyanate group is a urea bond. And at least one of urethane bonds. As a result, the modified polyester reacts with the active hydrogen-containing compound to form a crosslinkable polyester.

The isocyanate terminal-modified polyester is obtained by reacting an unmodified polyester with a diisocyanate compound in the presence of a non-Sn isocyanate catalyst (for example, a Bi-based catalyst).
Examples of the Bi-based catalyst include Neostan U-600 (manufactured by Nitto Kasei Co., Ltd.).
The amount of the Bi-based catalyst used is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1 to 1.0 part by mass with respect to 100 parts by mass of the unmodified polyester.

The unmodified polyester is obtained by condensation polymerization of an acid component and at least one diol compound selected from an aliphatic diol and an alicyclic diol in the presence of a non-Sn polyesterification catalyst (for example, a Ti-based catalyst). Obtained.
Examples of the diol compound include 1,4-butanediol, propylene glycol, ethylene glycol, diethylene glycol, neopentyl glycol, 1,6-hexanediol, and the like. You may use individually by 1 type and may use 2 or more types together.
As the acid component, at least one of terephthalic acid and isophthalic acid is suitable.
Examples of the Ti-based catalyst include titanium tetrabutoxide.
There is no restriction | limiting in particular as the usage-amount of the said Ti type catalyst, According to the objective, it can select suitably.

The mixing ratio for the polycondensation reaction between the diol compound and the acid component is not particularly limited and may be appropriately selected depending on the purpose. For example, the hydroxyl group [OH] in the diol compound, The equivalent ratio ([OH] / [COOH]) to the carboxyl group [COOH] in the acid component is usually preferably 2/1 to 1/1, and preferably 1.5 / 1 to 1/1. Is more preferable, and it is especially preferable that it is 1.3 / 1-1.02 / 1.
As described above, the unmodified polyester is preferably composed of only non-crosslinked components from the viewpoint of NCO addition reaction.

As the modified polyester resin obtained by modifying the unmodified polyester with a diisocyanate compound, an isocyanate group-containing polyester prepolymer (A) is particularly preferable.
There is no restriction | limiting in particular as said isocyanate group containing polyester prepolymer (A), According to the objective, it can select suitably, For example, the said acid component, at least 1 selected from aliphatic diol and alicyclic diol Examples thereof include those obtained by reacting a polyester resin obtained by condensation polymerization of a seed diol compound in the presence of a catalyst with polyisocyanate (PIC).

There is no restriction | limiting in particular as said polyisocyanate (PIC), Although it can select suitably according to the objective, For example, aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic diisocyanate, araliphatic diisocyanate, isocyanurate And those blocked with phenol derivatives, oximes, caprolactams, and the like.
Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, Examples include tetramethylhexane diisocyanate. Examples of the alicyclic polyisocyanate include isophorone diisocyanate and cyclohexylmethane diisocyanate. Examples of the aromatic diisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, diphenylene-4,4′-diisocyanate, 4,4′-diisocyanato-3,3′-dimethyldiphenyl, 3- Examples thereof include methyldiphenylmethane-4,4′-diisocyanate, diphenyl ether-4,4′-diisocyanate and the like. Examples of the araliphatic diisocyanate include α, α, α ′, α′-tetramethylxylylene diisocyanate. Examples of the isocyanurates include tris-isocyanatoalkyl-isocyanurate and triisocyanatocycloalkyl-isocyanurate. These can be used alone or in combination of two or more.

  The mixing ratio when the polyisocyanate (PIC) and the unmodified polyester resin are reacted is a mixing equivalent of the isocyanate group [NCO] in the polyisocyanate (PIC) and the hydroxyl group [OH] in the polyester resin. The ratio ([NCO] / [OH]) is usually preferably 2.0 to 2.5. When the ratio ([NCO] / [OH]) is less than 2.0, a monofunctional prepolymer is produced, and hot offset resistance may be insufficient due to insufficient elongation reaction. The amount of NCO monomer increases, and the durability of the toner may decrease.

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

  The isocyanate group content based on JIS K1603 in the modified polyester resin is preferably 2.0% by mass or less, and more preferably 1.0% by mass to 2.0% by mass. When the free isocyanate group content exceeds 2.0% by mass, the low-temperature fixing performance may not be exhibited. Here, the said free isocyanate group content rate (NCO%) can be measured by the method based on JISK1603, for example.

The weight average molecular weight of the modified polyester resin is preferably 10,000 to 100,000, and more preferably 10,000 to 50,000. If the weight average molecular weight is less than 10,000, low temperature fixability may not be exhibited, and if it exceeds 100,000, the viscosity becomes too high and granulation may be difficult.
Here, the said weight average molecular weight can be performed as follows by the molecular weight distribution measurement by GPC (gel permeation chromatography) of tetrahydrofuran (THF) soluble content.
That is, first, the column is stabilized in a 40 ° C. heat chamber. At this temperature, tetrahydrofuran (THF) as a column solvent is allowed to flow at a flow rate of 1 ml / min, and 50 to 200 μl of a tetrahydrofuran sample solution of a resin whose sample concentration is adjusted to 0.05 to 0.6 mass% is injected and measured. . 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 created by several monodisperse polystyrene standard samples and the count number. Examples of standard polystyrene samples for preparing the calibration curve include Pressure Chemical Co. Or the molecular weights made by Toyo Soda Industry Co., Ltd. are 6 × 10 ² , 2.1 × 10 ² , 4 × 10 ² , 1.75 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8. It is preferable to use 6 × 10 ⁵ , 2 × 10 ⁶ , and 4.48 × 10 ⁶ , and use at least about 10 standard polystyrene samples. As the detector, an RI (refractive index) detector can be used.

The glass transition temperature (Tg) of the modified polyester resin is preferably 10 ° C to 50 ° C, more preferably 30 ° C to 50 ° C.
The hydroxyl value of the modified polyester resin is preferably 30 mgKOH / g or less, more preferably 10 mgKOH / g to 25 mgKOH / g.
The acid value of the modified polyester resin is preferably 0 mgKOH / g to 10 mgKOH / g, and more preferably 0 mgKOH / g to 5 mgKOH / g.
Here, the acid value and the hydroxyl value can be measured by a method defined in JIS K0070.

  Here, the modified polyester resin includes, for example, a diol compound, an acid component, and a non-Sn polyesterification catalyst (for example, a Ti-based catalyst) in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe. The reaction is carried out at 230 ° C. for 8 hours under normal pressure, then for 5 hours at a reduced pressure of 10 mmHg to 15 mmHg, and further reacted with an isocyanate group-containing compound and a non-Sn isocyanate catalyst (for example, Bi-based catalyst). Can be obtained.

  Next, the toner material includes at least an adhesive base obtained by reacting at least an active hydrogen group-containing compound and the modified polyester resin, which is a polymer that can react with the active hydrogen group-containing compound, It contains a binder resin different from the polymer having a site capable of reacting with the active hydrogen group-containing compound, a colorant, and, if necessary, other components such as a release agent, resin fine particles, and a charge control agent.

-Adhesive substrate-
The adhesive substrate exhibits adhesiveness to a recording medium such as paper, and reacts the active hydrogen group-containing compound and the modified polyester resin which is a polymer capable of reacting with the active hydrogen group-containing compound in the aqueous medium. It is preferable to include a binder resin different from the polymer having at least the adhesive polymer formed and having a site capable of reacting with the active hydrogen group-containing compound.

There is no restriction | limiting in particular as a weight average molecular weight of the said adhesive base material, Although it can select suitably according to the objective, For example, 1,000 or more are preferable and 2,000-10,000,000 are more preferable. 3,000 to 1,000,000 are particularly preferred.
When the weight average molecular weight is less than 1,000, the hot offset resistance may be deteriorated.

-Active hydrogen group-containing compound-
The active hydrogen group-containing compound acts as an extender, a crosslinking agent, etc. when the modified polyester resin, which is a polymer that can react with the active hydrogen group-containing compound, undergoes an extension reaction, a crosslinking reaction, etc. in the aqueous medium. To do.
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. For example, it is a polymer that can react with the active hydrogen group-containing compound. When the modified polyester resin is the isocyanate group-containing polyester prepolymer (A), the isocyanate group-containing polyester prepolymer (A) can be increased in molecular weight by a reaction such as an extension reaction or a crosslinking reaction. Amines (B) are preferred.
There is no restriction | limiting in particular as said active hydrogen group, According to the objective, it can select suitably, For example, a hydroxyl group (alcoholic hydroxyl group or phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, an alcoholic hydroxyl group is particularly preferable.

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

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

  In addition, a reaction terminator can be used to stop the elongation reaction, the crosslinking reaction, and the like between the active hydrogen group-containing compound and the modified polyester resin that is a polymer that can react with the active hydrogen group-containing compound. Use of the reaction terminator is preferable in that the molecular weight and the like of the adhesive substrate can be controlled within a desired range. Examples of the reaction terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.) or those blocked (ketimine compounds).

As a mixing ratio of the amines (B) and the isocyanate group-containing polyester prepolymer (A), the isocyanate group [NCO] in the isocyanate group-containing prepolymer (A) and the amines (B) The mixing equivalent ratio ([NCO] / [NHx]) of the amino group [NHx] is preferably 1/3 to 3/1, more preferably 1/2 to 2/1, It is particularly preferably 1.5 to 1.5 / 1.
If the mixing equivalent ratio ([NCO] / [NHx]) is less than 1/3, the low-temperature fixability may decrease. If it exceeds 3/1, the molecular weight of the urea-modified polyester resin will be low. The hot offset resistance may be deteriorated.

--Binder resin different from polymer having site capable of reacting with active hydrogen group-containing compound--
The binder resin different from the polymer having a site capable of reacting with the active hydrogen group-containing compound is not particularly limited and can be appropriately selected according to the purpose. Polyol (PO) and polycarboxylic acid (PC) And polycondensates thereof.

The weight average molecular weight (Mw) of the binder resin different from the polymer having a site capable of reacting with the active hydrogen group-containing compound is a molecular weight distribution by GPC (gel permeation chromatography) soluble in tetrahydrofuran (THF), 1,000 to 30,000 are preferable, and 1,500 to 15,000 are more preferable. When the weight average molecular weight (Mw) is less than 1,000, the heat resistant storage stability may be deteriorated. Therefore, as described above, the content of the component having the weight average molecular weight (Mw) of less than 1,000. Needs to be 8 mass% to 28 mass%. On the other hand, when the weight average molecular weight (Mw) exceeds 30,000, the low-temperature fixability may be deteriorated.
The glass transition temperature of the binder resin different from the polymer having a site capable of reacting with the active hydrogen group-containing compound is preferably 30 ° C to 50 ° C. When the glass transition temperature is less than 30 ° C., the heat resistant storage stability of the toner may be deteriorated, and when it exceeds 50 ° C., the low-temperature fixability may be insufficient.
The hydroxyl value of the binder resin different from the polymer having a site capable of reacting with the active hydrogen group-containing compound is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g to 120 mgKOH / g, and 20 mgKOH / g to 80 mgKOH. / G is more preferable. If the hydroxyl value is less than 5 mgKOH / g, it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability.
The acid value of the binder resin different from the polymer having a site capable of reacting with the active hydrogen group-containing compound is preferably 1.0 mgKOH / g to 30.0 mgKOH / g. Generally, it becomes easy to be negatively charged by giving the toner an acid value.

-Method of measuring acid value-
The acid value is measured under the following conditions based on the measurement method described in JIS K0070-1992.
Sample preparation: 0.5 g of toner (0.3 g for ethyl acetate-soluble component) is added to 120 ml of toluene and dissolved by stirring for about 10 hours at room temperature (23 ° C.). Furthermore, 30 ml of ethanol is added to prepare a sample solution.
The measurement can be calculated by the apparatus described above, but specifically, the calculation is performed as follows. Titrated with a standardized N / 10 caustic potassium alcohol solution in advance, and the acid value is determined from the consumption of the alcohol potassium solution by the following formula.
Acid value = KOH (ml) x N x 56.1 / sample mass (where N is a factor of N / 10 KOH)

-Measurement method of hydroxyl value-
Weigh accurately 0.5 g of sample into a 100 ml volumetric flask and add 5 ml of acetylating reagent correctly. Then, it is immersed in a bath at 100 ° C. ± 5 ° C. and heated. After 1-2 hours, the flask is removed from the bath, allowed to cool, water is added and shaken to decompose acetic anhydride. Next, in order to complete the decomposition, the flask is again heated in a bath for 10 minutes or more and allowed to cool, and then the wall of the flask is thoroughly washed with an organic solvent. This solution is subjected to potentiometric titration with an N / 2 potassium hydroxide ethyl alcohol solution using the electrode to determine the OH value (according to JIS K0070-1966).

When the toner contains a binder resin different from the polymer having a site capable of reacting with the active hydrogen group-containing compound, the mixing mass ratio of the modified polyester component and the binder resin is 5/95 to 25-25. / 75 is preferable, and 10/90 to 25/75 is more preferable.
When the mixing mass ratio of the binder resin exceeds 95, the hot offset resistance is deteriorated, and it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability. When it is less than 25, the glossiness is deteriorated. There are things to do.

-Colorant-
The colorant is not particularly limited and may be appropriately selected from known dyes and pigments according to the purpose. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Lead Red, Lead Red, Cadmium Red, Cad Muum Mercury Red, Antimon Zhu, Permanent Red 4R, PA Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oh Lured, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal-Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Oxidation Chrome, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Ash Examples include green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, and lithobon. These may be used individually by 1 type and may use 2 or more types together.

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

  The colorant may be used as a master batch combined with a resin. The resin is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, styrene or a substituted polymer thereof, a styrene copolymer, polymethyl methacrylate, polybutyl methacrylate , Polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic hydrocarbon resin, alicyclic ring Aromatic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin, and the like. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the polymer of styrene or a substituted product thereof include polyester resin, polystyrene, poly p-chlorostyrene, polyvinyl toluene, and the like. Examples of the styrene copolymer include a styrene-p-chlorostyrene copolymer, a styrene-propylene copolymer, a styrene-vinyltoluene copolymer, a styrene-vinylnaphthalene copolymer, and a styrene-methyl acrylate copolymer. Polymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene- Butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene An acrylonitrile-indene copolymer, Styrene - maleic acid copolymer, styrene - maleic acid ester copolymer, and the like.

  The masterbatch can be produced by mixing or kneading the masterbatch resin and the colorant under high shear. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the colorant and the resin. 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. This flushing method is a method of mixing or kneading an aqueous paste containing water of a colorant together with a resin and an organic solvent, and transferring the colorant to the resin side to remove moisture and organic solvent components. For the mixing or kneading, for example, a high shear dispersion device such as a three-roll mill is preferably used.

-Other ingredients-
The other components are not particularly limited and may be appropriately selected depending on the purpose. For example, a release agent, a charge control agent, inorganic fine particles, a fluidity improver, a cleaning property improver, a magnetic material, a metal Soap and the like.

There is no restriction | limiting in particular as said mold release agent, According to the objective, it can select suitably from well-known things, For example, waxes etc. are mentioned suitably.
Examples of the waxes include carbonyl group-containing waxes, polyolefin waxes, long chain hydrocarbons, and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, a carbonyl group-containing wax is preferable.
Examples of the carbonyl group-containing wax include polyalkanoic acid esters, polyalkanol esters, polyalkanoic acid amides, polyalkylamides, dialkyl ketones, and the like. Examples of the polyalkanoic acid ester include carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, and 1,18-octadecane. Examples thereof include diol distearate. Examples of the polyalkanol ester include tristearyl trimellitic acid and distearyl maleate. Examples of the polyalkanoic acid amide include dibehenyl amide. Examples of the polyalkylamide include trimellitic acid tristearylamide. Examples of the dialkyl ketone include distearyl ketone. Of these carbonyl group-containing waxes, polyalkanoic acid esters are particularly preferred.
Examples of the polyolefin wax include polyethylene wax and polypropylene wax.
Examples of the long chain hydrocarbon include paraffin wax and sazol wax.

There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, 40 to 160 degreeC is preferable, 50 to 120 degreeC is more preferable, and 60 to 90 degreeC is especially preferable. preferable.
When the melting point is less than 40 ° C., the wax may adversely affect the heat-resistant storage stability, and when it exceeds 160 ° C., cold offset may easily occur during fixing at a low temperature.
The melt viscosity of the release agent is preferably 5 cps to 1,000 cps, more preferably 10 cps to 100 cps, as measured at a temperature 20 ° C. higher than the melting point of the wax.
If the melt viscosity is less than 5 cps, the releasability may be lowered, and if it exceeds 1,000 cps, the effect of improving hot offset resistance and low-temperature fixability may not be obtained.

  There is no restriction | limiting in particular as content in the said toner of the said mold release agent, Although it can select suitably according to the objective, 0 mass%-40 mass% are preferable, and 3 mass%-30 mass% are more preferable. . When the content exceeds 40% by mass, the fluidity of the toner may be deteriorated.

The charge control agent is not particularly limited and may be appropriately selected from known ones according to the purpose. However, since a color tone may change when a colored material is used, a colorless or nearly white material may be used. Preferably, for example, triphenylmethane dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus alone or compounds thereof, tungsten Examples thereof include a single substance or a compound thereof, a fluorine-based activator, a metal salt of salicylic acid, and a metal salt of a salicylic acid derivative. These may be used individually by 1 type and may use 2 or more types together.
Commercially available products may be used as the charge control agent. Examples of the commercially available products include quaternary ammonium salt Bontron P-51, oxynaphthoic acid metal complex E-82, and salicylic acid metal complex. E-84, E-89 of a phenol-based condensate (above, manufactured by Orient Chemical Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP-415 (above, manufactured by Hodogaya Chemical Co., Ltd.), Copy charge PSY VP2038 of quaternary ammonium salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, boron complex LR-147 (Nippon Carlit Co., Ltd.), quinacridone, azo pigment, other sulfone Group, a carboxyl group, polymer compounds having a functional group such as quaternary ammonium salts, and the like.
The charge control agent may be melted and kneaded with the master batch and then dissolved or dispersed, or may be added together with the toner components when directly dissolving or dispersing in the organic solvent, or The toner particles may be fixed on the toner surface after production.

  The content of the charge control agent in the toner varies depending on the type of the binder resin, the presence / absence of an additive, a dispersion method, and the like, and cannot be generally specified. On the other hand, 0.1 mass part-10 mass parts are preferable, and 0.2 mass part-5 mass parts are more preferable. When the content is less than 0.1 parts by mass, the charge controllability may not be obtained. When the content exceeds 10 parts by mass, the chargeability of the toner becomes too large, and the effect of the main charge control agent is reduced. As a result, the electrostatic attractive force with the developing roller increases, which may lead to a decrease in developer fluidity and a decrease in image density.

-Resin fine particles-
The resin fine particle is not particularly limited as long as it is a resin that can form an aqueous dispersion in an aqueous medium, and can be appropriately selected from known resins according to the purpose, and may be a thermoplastic resin. It may be a thermosetting resin, for example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate. Examples of the resin include vinyl resins. Of these, vinyl resins are particularly preferable.
These may be used individually by 1 type and may use 2 or more types together. Among these, at least one selected from vinyl resins, polyurethane resins, epoxy resins, and polyester resins is preferable because an aqueous dispersion of fine spherical resin particles can be easily obtained.
The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer. For example, styrene- (meth) acrylic acid ester resin, styrene-butadiene copolymer, (meth) acrylic acid-acrylic acid ester polymer. Styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- (meth) acrylic acid copolymer, and the like.
Moreover, as the resin fine particles, a copolymer comprising a monomer having at least two unsaturated groups can be used.
The monomer having at least two unsaturated groups is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a sodium salt of ethylene oxide methacrylate adduct sulfate (“Eleminol RS-30”). ", Sanyo Chemical Industries, Ltd.), divinylbenzene, 1,6-hexanediol acrylate, and the like.

  The resin fine particles can be obtained by polymerization according to a known method appropriately selected according to the purpose, but is preferably obtained as an aqueous dispersion of the resin fine particles. The method for preparing the aqueous dispersion of the resin fine particles is, for example, (1) In the case of the vinyl resin, a vinyl monomer is used as a starting material and is selected from suspension polymerization, emulsion polymerization, seed polymerization, and dispersion polymerization. (2) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., a precursor (monomer, oligomer). Or the like, or a solvent solution thereof is dispersed in an aqueous medium in the presence of an appropriate dispersant, and then heated or added with a curing agent to be cured to produce an aqueous dispersion of resin fine particles (3) ) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., it may be a precursor (monomer, oligomer, etc.) or a solvent solution thereof (liquid). (4) Preliminary polymerization reaction (addition polymerization, ring-opening polymerization, polyaddition, addition) After the resin prepared by any polymerization reaction mode such as condensation and condensation polymerization is pulverized using a mechanical pulverizer or jet type pulverizer and then classified to obtain resin fine particles , A method of dispersing in water in the presence of an appropriate dispersant, (5) prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) (6) A polymerization reaction (addition polymerization) in advance, in which resin fine particles are obtained by spraying a resin solution in which the resin is dissolved in a solvent to obtain resin fine particles and then dispersing the resin fine particles in water in the presence of an appropriate dispersant. , Ring-opening polymerization, polyaddition, addition condensation The resin fine particles can be obtained by adding a poor solvent to a resin solution obtained by dissolving a resin prepared in a solvent by a polymerization reaction method such as condensation polymerization or by cooling a resin solution previously dissolved in a solvent by heating. And then removing the solvent to obtain resin particles, and then dispersing the resin particles in water in the presence of a suitable dispersant. (7) Polymerization reaction (addition polymerization, ring-opening polymerization, heavy polymerization) in advance (Any polymerization reaction mode such as addition, addition condensation, and condensation polymerization may be used.) A resin solution prepared by dissolving a resin prepared in a solvent in a solvent is dispersed in an aqueous medium and then heated or heated. (8) A resin prepared in advance by a polymerization reaction (which may be any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation or condensation polymerization) is used as a solvent. In the dissolved resin solution A method of dissolving a suitable emulsifier and then adding water to carry out phase inversion emulsification is preferable.

  Examples of the toner include toners produced by a known suspension polymerization method, emulsion aggregation method, emulsion dispersion method, etc., and can react with an active hydrogen group-containing compound and the active hydrogen group-containing compound. The toner material containing the modified polyester resin as a polymer is dissolved in an organic solvent to prepare a toner solution, and then the toner solution is dispersed in an aqueous medium to prepare a dispersion liquid. And reacting the active hydrogen group-containing compound with the modified polyester resin, which is a polymer capable of reacting with the active hydrogen group-containing compound, to form an adhesive substrate in the form of particles, and removing the organic solvent. The toner obtained is preferably mentioned.

-Toner solution-
The toner solution is prepared by dissolving the toner material in the organic solvent.

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

-Dispersion-
The dispersion is prepared by dispersing the toner solution in an aqueous medium.
When the toner solution is dispersed in the aqueous medium, a dispersion (oil droplets) made of the toner solution is formed in the aqueous medium.

--- Aqueous medium--
The aqueous medium is not particularly limited and may be appropriately selected from known ones. Examples thereof include water, solvents miscible with water, and mixtures thereof. Among these, Is particularly preferred.
The solvent miscible with water is not particularly limited as long as it is miscible with water, and examples thereof include alcohol, dimethylformamide, tetrahydrofuran, cellosolves, and lower ketones.
Examples of the alcohol include methanol, isopropanol, ethylene glycol and the like. Examples of the lower ketones include acetone and methyl ethyl ketone. These may be used individually by 1 type and may use 2 or more types together.

The toner solution is preferably dispersed in the aqueous medium with stirring.
The dispersion method is not particularly limited and can be appropriately selected using a known disperser. Examples of the disperser include a low-speed shear disperser, a high-speed shear disperser, and a friction disperser. High pressure jet disperser, ultrasonic disperser, and the like. Among these, a high-speed shearing disperser is preferable in that the particle diameter of the dispersion (oil droplets) can be controlled to 2 μm to 20 μm.
When the high-speed shearing disperser is used, conditions such as the rotation speed, dispersion time, and dispersion temperature are not particularly limited and can be appropriately selected according to the purpose. For example, the rotation speed is 1 5,000 rpm to 30,000 rpm is preferable, 5,000 rpm to 20,000 rpm is more preferable, and the dispersion time is preferably 0.1 to 5 minutes in the case of a batch method, and the dispersion temperature is under pressure. 0 degreeC-150 degreeC is preferable, and 40 degreeC-98 degreeC is more preferable. The dispersion temperature is generally easier when the temperature is higher.

As an example of the method for producing the toner, a method for producing the toner by forming the adhesive base material in the form of particles will be described below.
In the method of granulating the toner by forming the adhesive substrate into particles, for example, preparation of an aqueous medium phase, preparation of the toner solution, preparation of the dispersion, addition of the aqueous medium, etc. Synthesis of the modified polyester resin (prepolymer), which is a polymer that can react with the active hydrogen group-containing compound, synthesis of the active hydrogen group-containing compound, and the like are performed.

The aqueous medium phase can be prepared, for example, by dispersing the resin fine particles in the aqueous medium. There is no restriction | limiting in particular as the addition amount in this aqueous medium of this resin fine particle, According to the objective, it can select suitably, For example, 0.5 mass%-10 mass% are preferable.
The toner solution is prepared by mixing, in the organic solvent, the active hydrogen group-containing compound, the modified polyester resin that is a polymer that can react with the active hydrogen group-containing compound, the colorant, the release agent, and the charging agent. It can be carried out by dissolving or dispersing toner materials such as a control agent and the ethyl acetate-soluble polyester component.
In the toner material, components other than the modified polyester resin (prepolymer), which is a polymer capable of reacting with the active hydrogen group-containing compound, are used in the aqueous medium phase preparation, and the resin fine particles are used as the aqueous medium. When dispersed in the aqueous medium, it may be added and mixed in the aqueous medium, or when the toner solution is added to the aqueous medium phase, it may be added to the aqueous medium phase together with the toner solution.

The dispersion can be prepared by emulsifying and dispersing the previously prepared toner solution in the previously prepared aqueous medium phase. In the emulsification / dispersion, when the active hydrogen group-containing compound and the modified polyester resin, which is a polymer that can react with the active hydrogen group-containing compound, are subjected to an extension reaction or a cross-linking reaction, the adhesive base material becomes Generate.
The adhesive substrate (for example, the urea-modified polyester resin) is, for example, (1) the modified polyester resin (for example, the isocyanate group-containing polyester prepolymer (a) that is a polymer that can react with the active hydrogen group-containing compound. The toner solution containing A)) is emulsified and dispersed in the aqueous medium phase together with the active hydrogen group-containing compound (for example, the amines (B)) to form a dispersion, and in the aqueous medium phase (2) The toner solution is emulsified and dispersed in the aqueous medium to which the active hydrogen group-containing compound has been added in advance to form a dispersion. Or may be produced by subjecting both to an extension reaction or a crosslinking reaction in the aqueous medium phase, or (3) adding and mixing the toner solution into the aqueous medium. After allowed, adding the active hydrogen group-containing compound, to form a dispersion, it may be generated by elongation reaction or crosslinking reaction from particle interfaces in the aqueous medium phase. In the case of (3), a modified polyester resin is preferentially produced on the surface of the toner to be produced, and a concentration gradient can be provided in the toner particles.

  Reaction conditions for producing the adhesive substrate by the emulsification / dispersion are not particularly limited, and the modified polyester resin that is a polymer that can react with the active hydrogen group-containing compound and the active hydrogen group-containing The reaction time can be suitably selected according to the combination with the compound, the reaction time is preferably 10 minutes to 40 hours, more preferably 2 hours to 24 hours, and the reaction temperature is preferably 0 ° C. to 150 ° C. C. to 98.degree. C. is more preferable.

  A method of stably forming the dispersion containing the modified polyester resin (for example, the isocyanate group-containing polyester prepolymer (A)) which is a polymer capable of reacting with the active hydrogen group-containing compound in the aqueous medium phase. For example, in the aqueous medium phase, the modified polyester resin (for example, the isocyanate group-containing polyester prepolymer (A)), which is a polymer that can react with the active hydrogen group-containing compound, the colorant, The toner solution prepared by dissolving or dispersing the toner material such as a release resin, the charge control agent, and a binder resin different from the polymer having a site capable of reacting with the active hydrogen group-containing compound in the organic solvent. And a method of adding and dispersing by shearing force. The details of the dispersion method are as described above.

In the preparation of the dispersion, if necessary, a dispersant is used from the viewpoint of stabilizing the dispersion (oil droplets composed of the toner solution) and sharpening the particle size distribution while obtaining a desired shape. Is preferred.
There is no restriction | limiting in particular as said dispersing agent, According to the objective, it can select suitably, For example, surfactant, a slightly water-soluble inorganic compound dispersing agent, a polymeric protective colloid, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, surfactants are preferable.

Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.
Examples of the anionic surfactant include alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters and the like, and those having a fluoroalkyl group are preferable. Examples of the anionic surfactant having a fluoroalkyl group include a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, disodium perfluorooctanesulfonylglutamate, 3- [omega-fluoroalkyl (6 carbon atoms). -11) Oxy] -1-alkyl (carbon number 3-4) sodium sulfonate, 3- [omega-fluoroalkanoyl (carbon number 6-8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (Carbon number 11-20) carboxylic acid or its metal salt, perfluoroalkyl carboxylic acid (carbon number 7-13) or its metal salt, perfluoroalkyl (carbon number 4-12) sulfonic acid or its metal salt, perfluoro Octanesulfonic acid diethanolamide, N-propyl-N- (2-hydroxy Ethyl) perfluorooctanesulfonamide, perfluoroalkyl (carbon number 6-10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (carbon number 6-10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (carbon number) 6-16) Ethyl phosphate and the like. Examples of commercially available surfactants having a fluoroalkyl group include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.); Florad FC-93, FC-95, FC-98, FC -129 (manufactured by Sumitomo 3M Co., Ltd.); Unidyne DS-101, DS-102 (manufactured by Daikin Industries, Ltd.); Megafac F-110, F-120, F-113, F-191, F-812, F- 833 (manufactured by Dainippon Ink & Chemicals, Inc.); Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products); 100, F150 (manufactured by Neos) and the like.

Examples of the cationic surfactant include amine salt type surfactants, quaternary ammonium salt type cationic surfactants, and cationic surfactants having a fluoroalkyl group. Examples of the amine salt type surfactant include alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazolines, and the like. Examples of the quaternary ammonium salt type cationic surfactant include alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride, and the like. . Examples of the cationic surfactant having a fluoroalkyl group include aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, perfluoroalkyl (6 to 10 carbon atoms) sulfonamidopropyltrimethylammonium salt, and the like. Aliphatic quaternary ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, and the like.
Commercially available cationic surfactants include, for example, Surflon S-121 (Asahi Glass Co., Ltd.); Florad FC-135 (Sumitomo 3M Co., Ltd.); Unidyne DS-202 (Daikin Industries Co., Ltd.), Mega Facks F-150, F-824 (manufactured by Dainippon Ink & Chemicals, Inc.); Xtop EF-132 (manufactured by Tochem Products);

Examples of the nonionic surfactant include fatty acid amide derivatives and polyhydric alcohol derivatives.
Examples of the amphoteric surfactant include alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine, N-alkyl-N, N-dimethylammonium betaine, and the like.

Examples of the poorly water-soluble inorganic compound dispersant include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.
Examples of the polymeric protective colloid include acids, (meth) acrylic monomers containing a hydroxyl group, vinyl alcohol or ethers of vinyl alcohol, esters of vinyl alcohol and a compound containing a carboxyl group, amides Examples thereof include homopolymers or copolymers of compounds or their methylol compounds, chlorides, those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylenes, celluloses, and the like.
Examples of the acids include acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, and the like. Examples of the (meth) acrylic monomer containing a hydroxyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, and γ-acrylate. -Hydroxypropyl, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate Glycerin monomethacrylate, N-methylol acrylamide, N-methylol methacrylamide and the like. Examples of the vinyl alcohol or ethers with vinyl alcohol include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, and the like. Examples of the esters of vinyl alcohol and a compound containing a carboxyl group include vinyl acetate, vinyl propionate, and vinyl butyrate. Examples of the amide compound or these methylol compounds include acrylamide, methacrylamide, diacetone acrylamide acid, or these methylol compounds. Examples of the chlorides include acrylic acid chloride and methacrylic acid chloride. Examples of the homopolymer or copolymer such as those having a nitrogen atom or a heterocyclic ring thereof include vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, and ethylene imine. Examples of the polyoxyethylene are polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene Examples thereof include oxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, and polyoxyethylene nonyl phenyl ester. Examples of the celluloses include methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.

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

  In the preparation of the dispersion, a catalyst for the extension reaction or the crosslinking reaction can be used. Examples of the catalyst include dibutyltin laurate and dioctyltin laurate.

  The organic solvent is removed from the obtained dispersion (emulsified slurry). The organic solvent is removed by (1) a method of gradually raising the temperature of the entire reaction system to completely evaporate and remove the organic solvent in the oil droplets, and (2) spraying the emulsified dispersion in a dry atmosphere. And a method of completely removing the water-insoluble organic solvent in the oil droplets to form toner fine particles and evaporating and removing the aqueous dispersant together.

  When the organic solvent is removed, toner particles are formed. The toner particles can be washed, dried, etc., and then classified as desired. The classification can be performed, for example, by removing fine particle portions in a liquid by a cyclone, a decanter, centrifugation, or the like, and the classification operation may be performed after obtaining a powder after drying.

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

  The toner has the following weight average particle diameter (Dw), weight average particle diameter (Dw) / number average particle diameter (Dn), glass transition temperature (Tg), glass transition temperature, and the like. It is preferable.

The weight average particle diameter of the toner is, for example, preferably 3 μm to 8 μm, more preferably 4 μm to 7 μm, and still more preferably 5 μm to 6 μm.
When the weight 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 unit, and the charging ability of the carrier may be reduced. In the developer, toner filming on the developing roller and toner fusion to a member such as a blade are likely to occur because the toner is thinned. When the thickness exceeds 8 μm, the resolution is high and high. It becomes difficult to obtain an image of an image quality, and when the balance of the toner in the developer is performed, the variation in the particle diameter of the toner may increase.

The ratio (Dw / Dn) of the weight average particle diameter (Dw) to the number average particle diameter (Dn) in the toner is preferably 1.25 or less, more preferably 1.05 to 1.25.
In general, it is said that the smaller the particle size of the toner, the more advantageous it is to obtain a high-resolution and high-quality image, but it is disadvantageous for transferability and cleaning properties. is there. In addition, when the weight average particle diameter is smaller than the range of the present invention, in the case of a two-component developer, the toner is fused to the surface of the carrier during a long period of stirring in the developing device, leading to a decrease in the charging ability of the carrier, When used as a developer, toner filming on the developing roller and toner fusion to a member such as a blade for thinning the toner are likely to occur. Further, these phenomena are the same for the toner having a fine powder content larger than the range of the present invention. On the contrary, when the particle diameter of the toner is larger than the range of the present invention, it becomes difficult to obtain a high resolution and high quality image, and when the balance of the toner in the developer is performed, In many cases, the variation of the particle size becomes large. It was also clarified that the same was true when the weight average particle diameter / number average particle diameter was larger than 1.25.
On the other hand, when the weight average particle diameter / number average particle diameter is smaller than 1.05, there are some aspects that are preferable in terms of stabilizing the behavior of the toner and uniformizing the charge amount, but the toner is insufficiently charged. In some cases, it was also found that the cleaning property may be deteriorated.

  The weight average particle diameter (Dw) and number average particle diameter (Dn) of the toner were measured with a particle size measuring device (“Multisizer III”, manufactured by Beckman Coulter, Inc.) at an aperture diameter of 100 μm, and analyzed software (Beckman Coulter). Analysis was performed using 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 beaker made of glass, and 0.5 g of each toner is added. 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 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.

The glass transition temperature of the toner is preferably 40 ° C to 70 ° C. If the glass transition temperature is less than 40 ° C, the heat-resistant storage stability may be insufficient, and if it exceeds 70 ° C, the low-temperature fixability may be adversely affected.
Here, the glass transition temperature (Tg) is specifically determined by the following procedure. Using Shimadzu TA-60WS and DSC-60 as measuring devices, the measurement was performed under the following measurement conditions.
〔Measurement condition〕
・ Sample container: Aluminum sample pan (with lid)
-Sample amount: 5mg
Reference: Aluminum sample pan (alumina 10 mg)
・ Atmosphere: Nitrogen (flow rate 50ml / min)
・ Temperature conditions ・ Starting temperature: 20 ℃
・ Raising rate: 10 ° C / min
・ End temperature: 150 ℃
-Holding time: None-Temperature drop: 10 ° C / min
・ End temperature: 20 ℃
-Holding time: None-Temperature rising rate: 10 ° C / min
・ End temperature: 150 ℃
The measurement results were analyzed using the data analysis software (TA-60, version 1.52) manufactured by Shimadzu Corporation. The analysis method is to specify a range of ± 5 ° C centering on the point showing the maximum peak on the lowest temperature side of the DrDSC curve, which is the DSC differential curve of the second temperature rise, and use the peak analysis function of the analysis software to determine the peak temperature. Ask. Next, the maximum endothermic temperature of the DSC curve is obtained using the peak analysis function of the analysis software in the range of the peak temperature + 5 ° C. and −5 ° C. in the DSC curve. The temperature shown here corresponds to the glass transition temperature (Tg) of the toner.

  The coloration of the toner is not particularly limited and may be appropriately selected according to the purpose, and may be at least one selected from black toner, cyan toner, magenta toner, and yellow toner. Can be obtained by appropriately selecting the type of the colorant, and is preferably a color toner.

(Developer)
The developer of the present invention contains at least the toner of the present invention, and other components such as a carrier selected appropriately. 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 of the present invention, even if the balance of the toner is performed, there is little fluctuation in the particle diameter of the toner, and the filming of the toner on the developing roller or the toner is made thin. Therefore, the toner is not fused to a member such as a blade, and good and stable developability and images can be obtained even when the developing device is used (stirred) for a long time. Further, in the case of the two-component developer using the toner of the present invention, even if the balance of the toner over a long period of time is performed, the fluctuation of the toner particle diameter in the developer is small, and even in the long-term stirring in the developer, Good and stable developability can be obtained.

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

  There is no restriction | limiting in particular as a material of the said core material, It can select suitably from well-known things, For example, 50-90 emu / g manganese-strontium (Mn-Sr) type material, manganese-magnesium (Mn-) Mg) -based materials and the like are preferable, and highly magnetized materials such as iron powder (100 emu / g or more) and magnetite (75 to 120 emu / g) are preferable in terms of securing image density. In addition, a weakly magnetized material such as a copper-zinc (Cu—Zn) -based (30 to 80 emu / g) is advantageous in that it can weaken the contact with the photoconductor in which the toner is in a spiked state and is advantageous in improving the image quality. Is preferred. These may be used alone or in combination of two or more.

The particle diameter of the core material is preferably an average particle diameter (weight average particle diameter (D ₅₀ )) of 10 μm to 200 μm, and more preferably 40 μm to 100 μm.
When the average particle size (weight average particle size (D ₅₀ )) is less than 10 μm, the distribution of carrier particles may increase the number of fine powders and lower the magnetization per particle and cause carrier scattering. If the thickness exceeds 200 μm, the specific surface area may decrease and toner scattering may occur. In the case of a full color having a large solid portion, the reproduction of the solid portion may be deteriorated.

  The material of the resin layer is not particularly limited and can be appropriately selected from known resins according to the purpose. For example, amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, Polyester resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, fluorine And a copolymer of vinylidene fluoride and vinyl fluoride, a fluoroterpolymer such as a terpolymer of tetrafluoroethylene, vinylidene fluoride and a non-fluorinated monomer, and a silicone resin. These may be used individually by 1 type and may use 2 or more types together.

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

  The resin layer may contain conductive powder or the like as necessary. Examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. The average particle diameter of these conductive powders is preferably 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control electric resistance.

For example, the resin layer is prepared by dissolving the silicone resin or the like in a solvent to prepare a coating solution, and then uniformly coating the coating solution on the surface of the core material by a known coating method, drying, and baking. It can be formed by doing. Examples of the coating method include a dipping method, a spray method, and a brush coating method.
There is no restriction | limiting in particular as said solvent, Although it can select suitably according to the objective, For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cellosolve, butyl acetate, etc. are mentioned.
The baking is not particularly limited, and may be an external heating method or an internal heating method. For example, a stationary electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, etc. The method of using, the method of using a microwave, etc. are mentioned.

  The amount of the resin layer in the carrier is preferably 0.01% by mass to 5.0% by mass. When the amount is less than 0.01% by mass, the uniform resin layer may not be formed on the surface of the core material. When the amount exceeds 5.0% by mass, the resin layer becomes thick. In some cases, granulation of carriers occurs, and uniform carrier particles may not be obtained.

When the developer is the two-component developer, the content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 90% by mass to 98% % By mass is preferable, and 93% by mass to 97% by mass is more preferable.
The mixing ratio of the toner and the carrier of the two-component developer is generally 1 part by mass to 10.0 parts by mass of the toner with respect to 100 parts by mass of the carrier.

Since the developer of the present invention contains the toner of the present invention, it is possible to achieve both excellent low-temperature fixability and anti-offset performance and form a good high-definition image.
The developer of the present invention can be suitably used for image formation by various known electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method. It can be particularly suitably used for containers, process cartridges, image forming apparatuses and image forming methods.

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

(Process cartridge)
The process cartridge of the present invention develops an electrostatic latent image carrier carrying an electrostatic latent image and the electrostatic latent image carried on the electrostatic latent image carrier using toner to produce a visible image. And at least developing means to be formed, and other means appropriately selected as necessary.
The developing means includes a developer container that contains the toner or developer of the present invention, and a developer carrier that carries and transports the toner or developer contained in the developer container. And a layer thickness regulating member for regulating the thickness of the toner layer to be carried.
The process cartridge of the present invention can be detachably mounted on various electrophotographic apparatuses, and is preferably detachably mounted on the electrophotographic apparatus of the present invention described later.

Here, as shown in FIG. 1, the process cartridge includes a photosensitive member 101, and at least one of a charging unit 102, a developing unit 104, a transfer unit 108, a cleaning unit 107, and a charge eliminating unit (not shown). And an apparatus (part) that can be attached to and detached from the image forming apparatus main body.
Here, the image forming process using the process cartridge shown in FIG. 1 will be described. The photosensitive member 101 is exposed to the surface by rotating by the charging unit 102 and exposing 103 by the exposing unit (not shown) while rotating in the direction of the arrow. An electrostatic latent image corresponding to the image is formed. The electrostatic latent image is developed with toner by the developing unit 104, and the toner development is transferred to the recording medium 105 by the transfer unit 108 and printed out. Next, the surface of the photoconductor after the image transfer is cleaned by the cleaning unit 107 and further neutralized by a neutralizing unit (not shown), and the above operation is repeated again.

(Image forming apparatus and image forming method)
The image forming apparatus of 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 further appropriately selected as necessary. It has other means, for example, static elimination means, cleaning means, recycling means, control means and the like.
The image forming method of the present invention includes at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step, and other steps appropriately selected as necessary, for example, a static elimination step, a cleaning step. , Including recycling process, control process, etc.

  The image forming method of the present invention can be preferably carried out by the image forming apparatus of the present invention, the electrostatic latent image forming step can be performed by the electrostatic latent image forming means, and the developing step is the developing The transfer step can be performed by the transfer unit, the fixing step can be performed by the fixing unit, and the other steps can be performed by the other unit.

-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.
The electrostatic latent image bearing member (sometimes referred to as “photoconductive insulator”, “electrophotographic photosensitive member”, “photosensitive member”) is particularly about the material, shape, structure, size, etc. There is no limitation, and it can be appropriately selected from known ones, but as its shape, a drum shape is preferably mentioned, and as its material, for example, an inorganic photoreceptor such as amorphous silicon, selenium, polysilane, phthalopolymethine, etc. Organic photoreceptors, and the like. Among these, amorphous silicon or the like is preferable in terms of long life.

  As the amorphous silicon photoreceptor, for example, a support is heated to 50 to 400 ° C., and a vacuum deposition method, a sputtering method, an ion plating method, a thermal CVD method, a photo CVD method, a plasma CVD method, or the like is applied on the support. A photoconductor having a photoconductive layer made of a-Si (hereinafter sometimes referred to as “a-Si-based photoconductor”) can be used. Among these, a plasma CVD method, that is, a method in which a source gas is decomposed by direct current, high frequency or microwave glow discharge to form an a-Si deposited film on a support is preferable.

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

The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charger.
The charger is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charging device including a conductive or semiconductive roller, brush, film, rubber blade, etc. And non-contact chargers using corona discharge such as corotrons and corotrons.

The shape of the charging member may take any form such as a magnetic brush or a fur brush in addition to the roller, and can be selected according to the specifications and form of the electrophotographic apparatus. In the case of using a magnetic brush, the magnetic brush is composed of various ferrite particles such as Zn—Cu ferrite as a charging member, a non-magnetic conductive sleeve for supporting it, and a magnet roll included therein. Or, when using a brush, for example, as a material of the fur brush, a fur treated with carbon, copper sulfide, metal or metal oxide is used, and this is wound or attached to a metal or other conductive core. To make a charger.
The charger is not limited to the contact charger as described above. However, since an image forming apparatus in which ozone generated from the charger is reduced is obtained, a contact charger is used. preferable.

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

-Development process and development means-
The developing step is a step of developing the electrostatic latent image using the toner or the developer of the present invention to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image using the toner or the developer of the present invention, and can be performed by the developing unit.
The developing unit is not particularly limited as long as it can be developed using, for example, the toner or the developer of the present invention, and can be appropriately selected from known ones. For example, the toner of the present invention Preferred examples include a developer containing at least a developer, and at least a developing device capable of contacting or non-contacting the toner or the developer with the electrostatic latent image. More preferred is a developing device.

  The developing unit may be a dry developing type, a wet developing type, a single color developing unit, or a multi-color developing unit. For example, a toner having a stirrer for charging the toner or the developer by frictional stirring and a rotatable magnet roller is preferable.

  In the developing device, for example, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier (photoconductor), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted. It moves to the surface of the electrostatic latent image carrier (photoconductor) by force. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier (photoconductor).

  The developer accommodated in the developing device is a developer containing the toner of the present invention, but the developer may be a one-component developer or a two-component developer. The toner contained in the developer is the toner of the present invention.

-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 intermediate transfer member preferably has a static friction coefficient of 0.1 to 0.6, and more preferably 0.3 to 0.5. The volume resistance of the intermediate transfer member is preferably from several Ωcm to 10 ³ Ωcm. By setting the volume resistance to several Ωcm or more and 10 ³ Ωcm or less, the intermediate transfer member itself is prevented from being charged, and the charge imparted by the charge imparting means is less likely to remain on the intermediate transfer member. Transfer unevenness can be prevented. Further, it is possible to easily apply a transfer bias at the time of secondary transfer.

  The material of the intermediate transfer member is not particularly limited and can be appropriately selected from known materials according to the purpose. For example, (1) a material having a high Young's modulus (tensile elastic modulus) is used as a single-layer belt. PC (polycarbonate), PVDF (polyvinylidene fluoride), PAT (polyalkylene terephthalate), PC (polycarbonate) / PAT (polyalkylene terephthalate) blend material, ETFE (ethylene tetrafluoroethylene copolymer) / PC, ETFE / PAT, PC / PAT blend material, carbon black dispersed thermosetting polyimide, and the like. These single-layer belts having a high Young's modulus have the advantage that the amount of deformation with respect to stress during image formation is small, and registration is not likely to occur particularly during color image formation. (2) A belt having a two- to three-layer structure in which a belt having a high Young's modulus is used as a base layer and a surface layer or an intermediate layer is provided on the outer periphery of the belt. Therefore, the line image has a performance capable of preventing the line image from being lost. (3) Belts having a relatively low Young's modulus using rubber and elastomer, and these belts have an advantage that line images are hardly lost due to their softness. In addition, the belt width is made larger than that of the drive roll and the tension roll, and the elasticity of the belt ear protruding from the roll is used to prevent meandering, so that a low cost can be realized without the need for ribs or meandering prevention devices. .

Conventionally, fluorine-based resin, polycarbonate resin, polyimide resin, and the like have been used for the intermediate transfer belt. However, in recent years, an elastic belt using an entire belt layer or a part of the belt as an elastic member has been used. . The transfer of a color image using a resin belt has the following problems.
A color image is usually formed with four colored toners. On one color image, toner layers of 1 to 4 layers are formed. The toner layer receives pressure by passing through the primary transfer (transfer from the photoreceptor to the intermediate transfer belt) and the secondary transfer (transfer from the intermediate transfer belt to the sheet), and the cohesive force between the toners increases. When the cohesive force between the toners increases, the phenomenon of missing characters in the characters and missing edges in the solid portion image tends to occur. Since the resin belt has a high hardness and does not deform according to the toner layer, the toner layer is easily compressed, and the character dropout phenomenon is likely to occur.
Recently, there is an increasing demand for forming full-color images on various papers, for example, Japanese paper, intentionally irregularities, and forming images on paper. However, a paper with poor smoothness is liable to generate toner and voids at the time of transfer, and transfer loss is likely to occur. If the transfer pressure at the secondary transfer portion is increased to improve the adhesion, the condensing power of the toner layer is increased, and the above-described character void is generated.
The elastic belt is used for the following purposes. The elastic belt is deformed corresponding to the toner layer and the paper having poor smoothness at the transfer portion. In other words, since the elastic belt deforms following local irregularities, it is possible to obtain a good adhesion without excessively increasing the transfer pressure with respect to the toner layer, and a paper with poor flatness that has no void in characters. In contrast, a transfer image with excellent uniformity can be obtained.

  Examples of the resin for the elastic belt include polycarbonate, fluororesin (ETFE, PVDF), polystyrene, chloropolystyrene, poly-α-methylstyrene, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, styrene- Vinyl acetate copolymer, styrene-maleic acid copolymer, styrene-acrylic acid ester copolymer (for example, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer) Styrene-octyl acrylate copolymer and styrene-phenyl acrylate copolymer), styrene-methacrylic acid ester copolymer (for example, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer) , Styrene-phenyl methacrylate copolymer Styrene-resin (monopolymer or copolymer containing styrene or a styrene-substituted product), methacrylic acid, such as styrene-α-chloroacrylic acid methyl copolymer, styrene-acrylonitrile-acrylic acid ester copolymer Methyl resin, butyl methacrylate resin, ethyl acrylate resin, butyl acrylate resin, modified acrylic resin (for example, silicone-modified acrylic resin, vinyl chloride resin-modified acrylic resin, acrylic / urethane resin, etc.), vinyl chloride resin, styrene-acetic acid Vinyl copolymer, vinyl chloride-vinyl acetate copolymer, rosin-modified maleic acid resin, phenol resin, epoxy resin, polyester resin, polyester polyurethane resin, polyethylene, polypropylene, polybutadiene, polyvinylidene chloride, ionomer resin, polyureta It is possible to use one or a combination of two or more selected from the group consisting of resins, silicone resins, ketone resins, ethylene-ethyl acrylate copolymers, xylene resins and polyvinyl butyral resins, polyamide resins, modified polyphenylene oxide resins, etc. it can. However, it is a matter of course that the material is not limited to the above materials.

  The elastic rubber or elastomer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, butyl rubber, fluorine rubber, acrylic rubber, EPDM, NBR, acrylonitrile-butadiene-styrene rubber natural rubber, isoprene Rubber, styrene-butadiene rubber, butadiene rubber, ethylene-propylene rubber, ethylene-propylene terpolymer, chloroprene rubber, chlorosulfonated polyethylene, chlorinated polyethylene, urethane rubber, syndiotactic 1,2-polybutadiene, epichlorohydrin series Rubber, Ricone rubber, Fluoro rubber, Polysulfide rubber, Polynorbornene rubber, Hydrogenated nitrile rubber, Thermoplastic elastomer (eg polystyrene, polyolefin, polyvinyl chloride, polyurethane, polyamide) , It can be used polyurea, polyester, one kind or two kinds or more combinations selected from the group consisting of fluorocarbon resin) or the like.

The conductive material for adjusting the resistance value is not particularly limited and can be appropriately selected depending on the purpose. For example, carbon black, graphite, metal powder such as aluminum or nickel, tin oxide, titanium oxide, antimony oxide, oxidation Conductive metal oxides such as indium, potassium titanate, antimony oxide-tin oxide composite oxide (ATO), indium oxide-tin oxide composite oxide (ITO), and the conductive metal oxides are barium sulfate and magnesium silicate. Further, it may be coated with insulating fine particles such as calcium carbonate. Of course, the conductive agent is not limited thereto.
Surface layer materials and surface layers are required to prevent contamination of the photoreceptor with elastic materials, reduce surface friction resistance to the surface of the transfer belt, reduce toner adhesion, and improve cleaning and secondary transfer properties. . For example, materials that use one or a combination of two or more of polyurethane, polyester, epoxy resin, etc. to reduce surface energy and increase lubricity, such as fluorine resin, fluorine compound, fluorocarbon, titanium dioxide, silicon carbide, etc. These powders and particles can be used by dispersing one type or two or more types or a combination of particles having different particle sizes. Further, it is also possible to use a material having a reduced surface energy by forming a fluorine-rich layer on the surface by heat treatment, such as a fluorine-based rubber material.
The manufacturing method of the belt is not limited. For example, a centrifugal molding method in which a material is poured into a rotating cylindrical mold to form a belt, a spray coating method in which a liquid paint is sprayed to form a film, a cylindrical mold is used. Examples include, but are not limited to, a dipping method in which the material is dipped in a solution of the material, a casting method in which it is injected into the inner mold and the outer mold, a method in which a compound is wound around a cylindrical mold and vulcanized and polished In general, a belt is manufactured by combining a plurality of manufacturing methods.

As a method for preventing elongation as an elastic belt, there are a method of forming a rubber layer in a core resin layer with little elongation, a method of putting a material for preventing elongation in a core layer, and the like, but the method is limited to a specific manufacturing method is not.
There is no restriction | limiting in particular as a material which comprises a core layer which prevents elongation, According to the objective, it can select suitably, For example, natural fibers, such as cotton and silk; Polyester fiber, nylon fiber, acrylic fiber, Synthetic fibers such as polyolefin fibers, polyvinyl alcohol fibers, polyvinyl chloride fibers, polyvinylidene chloride fibers, polyurethane fibers, polyacetal fibers, polyfluoroethylene fibers, and phenol fibers; inorganic fibers such as carbon fibers, glass fibers, and boron fibers; iron fibers In addition, a woven fabric or a thread-like material using a metal fiber such as copper fiber is also used.
The yarn may be twisted in any manner, such as one or a plurality of filaments twisted, one-twisted yarn, various twisted yarns, double yarn, or the like. Further, for example, fibers of a material selected from the above material group may be blended. Further, the yarn can be used after an appropriate conductive treatment. On the other hand, as the woven fabric, any woven fabric such as knitted fabric can be used, and a woven fabric interwoven can also be used, and naturally conductive treatment can be performed.
The production method for providing the core layer is not particularly limited and can be appropriately selected depending on the purpose.For example, a method of providing a coating layer on a woven fabric woven in a cylindrical shape on a mold or the like, A method of providing a coating layer on one or both sides of a core layer by immersing a woven fabric woven in a cylindrical shape into a liquid rubber or the like, winding a thread spirally around a mold at an arbitrary pitch, and coating a coating layer thereon The method of providing etc. can be mentioned.
The thickness of the elastic layer depends on the hardness of the elastic layer, but if it is too thick, the surface expands and contracts and cracks are likely to occur in the surface layer. Also, it is not preferable that the thickness is too large (about 1 mm or more) because the amount of expansion and contraction becomes large and the image is stretched.

The transfer means (the primary transfer means and the secondary transfer means) is a transfer for peeling and charging the visible image formed on the electrostatic latent image carrier (photoconductor) to the recording medium side. It is preferable to have at least a vessel. There may be one transfer means or two or more transfer means. Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is typically plain paper, but is not particularly limited as long as it can transfer an unfixed image after development, and can be appropriately selected according to the purpose. PET for OHP A base or the like can also be used.

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

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

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

The recycling step is a step of recycling the electrophotographic 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.

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 sequencers and computers.

  Next, one mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. The image forming apparatus 100 shown in FIG. 2 includes a photosensitive drum 10 as the electrostatic latent image carrier (hereinafter also referred to as “photosensitive member 10”), a charging roller 20 as the charging unit, and the exposure. An exposure device 30 as a means, a developing device 40 as the developing means, an intermediate transfer member 50, a cleaning device 60 as the cleaning means having a cleaning blade, and a static elimination lamp 70 as the static elimination means.

  The intermediate transfer member 50 is an endless belt, and is designed to be movable in the direction of an arrow by three rollers 51 that are arranged inside and stretched. Part of the three rollers 51 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. The intermediate transfer body 50 is provided with a cleaning device 90 having a cleaning blade in the vicinity thereof, and for transferring (secondary transfer) a developed image (toner image) onto a transfer sheet 95 as a final recording medium. A transfer roller 80 serving as a transfer unit to which a transfer bias can be applied is disposed to face the transfer roller 80. Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the toner image on the intermediate transfer member 50 is arranged between the photosensitive member 10 and the intermediate transfer member 50 in the rotation direction of the intermediate transfer member 50. It is disposed between the contact portion and the contact portion between the intermediate transfer member 50 and the transfer paper 95.

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

  In the image forming apparatus 100 shown in FIG. 2, for example, the charging roller 20 charges the photosensitive drum 10 uniformly. The exposure device 30 performs imagewise exposure on the photosensitive drum 10 to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum 10 is developed by supplying toner from the developing device 40 to form a toner image. The toner image is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied from the roller 51 and further transferred (secondary transfer) onto the transfer paper 95. As a result, a transfer image is formed on the transfer paper 95. The residual toner on the photoconductor 10 is removed by the cleaning device 60, and the charge on the photoconductor 10 is temporarily removed by the charge eliminating lamp 70.

  Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. The image forming apparatus 100 shown in FIG. 3 does not include the developing belt 41 in the image forming apparatus 100 shown in FIG. 2, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and Except for the fact that the cyan developing unit 45C is arranged directly opposite, it has the same configuration as the image forming apparatus 100 shown in FIG. In FIG. 3, the same components as those in FIG. 2 are denoted by the same reference numerals.

In the tandem type electrophotographic apparatus in which the image forming method of the present invention is carried out by the image forming apparatus of the present invention, the image on each photoconductor 1 is transferred by the transfer device 2 by the sheet conveying belt 3 as shown in FIG. As shown in FIG. 5, the image on each photoconductor 1 is sequentially transferred to the intermediate transfer body 4 by the primary transfer device 2 as shown in FIG. There is an indirect transfer type in which an image on the transfer body 4 is collectively transferred to a sheet s by a secondary transfer device 5. The transfer device 5 is a transfer conveyance belt, but may be a roller shape.
Comparing the direct transfer type and the indirect transfer type, the former arranges the sheet feeding device 6 on the upstream side of the tandem image forming apparatus T on which the photoconductors 1 are arranged, and the fixing device 7 on the downstream side. There is a drawback in that the size increases in the sheet conveying direction. On the other hand, the latter can set the secondary transfer position relatively freely. The sheet feeding device 6 and the fixing device 7 can be arranged so as to overlap with the tandem image forming apparatus T, and there is an advantage that downsizing is possible.
In the former, in order not to increase the size in the sheet conveying direction, the fixing device 7 is disposed close to the tandem type image forming apparatus T. For this reason, the fixing device 7 cannot be disposed with a sufficient margin that allows the sheet s to bend, and an impact when the leading edge of the sheet s enters the fixing device 7 (particularly with a thick sheet) or fixing. Due to the difference in speed between the sheet conveyance speed when passing through the apparatus 7 and the sheet conveyance speed by the transfer conveyance belt, there is a drawback that the fixing device 7 tends to affect image formation on the upstream side. On the other hand, in the latter case, the fixing device 7 can be disposed with a sufficient margin that the sheet s can be bent, so that the fixing device 7 hardly affects the image formation.
In view of the above, recently, an indirect transfer type of tandem type electrophotographic apparatus has attracted attention.
In this type of color electrophotographic apparatus, as shown in FIG. 5, the transfer residual toner remaining on the photoreceptor 1 after the primary transfer is removed by the photoreceptor cleaning device 8 to clean the surface of the photoreceptor 1. In preparation for another image formation. Further, the transfer residual toner remaining on the intermediate transfer body 4 after the secondary transfer is removed by the intermediate transfer body cleaning device 9 to clean the surface of the intermediate transfer body 4 to prepare for image formation again.

A tandem image forming apparatus 100 shown in FIG. 6 is a tandem color image forming apparatus. The tandem image forming apparatus 120 includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.
The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16, and can be rotated clockwise in FIG. 6. An intermediate transfer member cleaning device 17 for removing residual toner on the intermediate transfer member 50 is disposed in the vicinity of the support roller 15. The intermediate transfer member 50 stretched between the support roller 14 and the support roller 15 is a tandem type in which four image forming units 18 of yellow, cyan, magenta, and black are arranged to face each other along the conveyance direction. A developing device 120 is disposed. An exposure device 21 is disposed in the vicinity of the tandem developing device 120. A secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed. In the secondary transfer device 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the transfer paper conveyed on the secondary transfer belt 24 and the intermediate transfer body 50 are in contact with each other. Is possible. A fixing device 25 is disposed in the vicinity of the secondary transfer device 22. The fixing device 25 includes a fixing belt 26 that is an endless belt, and a pressure roller 27 that is pressed against the fixing belt 26.
In the tandem image forming apparatus, a sheet reversing device 28 for reversing the transfer paper for image formation on both sides of the transfer paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25. .

  Next, formation of a full-color image (color copy) using the tandem developing device 120 will be described. That is, first, a document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and the document is set on the contact glass 32 of the scanner 300. 400 is closed.

  When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the contact glass 32. Immediately after that, the scanner 300 is driven, and the first traveling body 33 and the second traveling body 34 travel. At this time, light from the light source is irradiated by the first traveling body 33 and reflected light from the document surface is reflected by the mirror in the second traveling body 34 and is received by the reading sensor 36 through the imaging lens 35 to be color. An original (color image) is read and used as black, yellow, magenta, and cyan image information.

  Each image information of black, yellow, magenta, and cyan is stored in each image forming unit 18 (black image forming unit, yellow image forming unit, magenta image forming unit, and cyan image) in the tandem developing device 120. Each of the image forming units forms black, yellow, magenta, and cyan toner images. That is, each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem type developing device 120 is a static image as shown in FIG. An electrostatic latent image carrier 10 (black electrostatic latent image carrier 10K, yellow electrostatic latent image carrier 10Y, magenta electrostatic latent image carrier 10M, and cyan electrostatic latent image carrier 10C); The electrostatic latent image carrier 10 is uniformly charged, and the electrostatic latent image carrier is exposed (L in FIG. 7) for each color image corresponding to each color image information. An exposure device that forms an electrostatic latent image corresponding to each color image on the electrostatic latent image carrier, and each color toner (black toner, yellow toner, magenta toner, and cyan toner) Develop with A developing device 61 for forming a toner image with each color toner, a transfer charger 62 for transferring the toner image onto the intermediate transfer member 50, a cleaning device 63, and a static eliminator 64 are provided. Each single color image (black image, yellow image, magenta image, and cyan image) can be formed based on the color image information. The black image, the yellow image, the magenta image, and the cyan image formed in this way are respectively transferred to the black electrostatic latent image carrier 10K on the intermediate transfer member 50 that is rotationally moved by the support rollers 14, 15, and 16. Black image formed on top, yellow image formed on electrostatic latent image carrier 10Y for yellow, magenta image formed on electrostatic latent image carrier 10M for magenta, and electrostatic latent image carrier for cyan The cyan image formed on 10C is sequentially transferred (primary transfer). Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

  On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed out a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143. Each sheet 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 and stopped. Alternatively, the sheet feed roller 142 is rotated to feed out sheets (recording paper) on the manual feed tray 54, separated one by one by the separation roller 145, put into the manual feed path 53, and abutted against the registration roller 49 and stopped. . The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet. Then, the registration roller 49 is rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 50, and a sheet (recording paper) is interposed between the intermediate transfer member 50 and the secondary transfer device 22. The secondary color transfer device 22 transfers the composite color image (color transfer image) onto the sheet (recording paper), thereby transferring the color image onto the sheet (recording paper). Is formed. The residual toner on the intermediate transfer member 50 after image transfer is cleaned by the intermediate transfer member cleaning device 17.

  The sheet (recording paper) on which the color image has been transferred is conveyed by the secondary transfer device 22 and sent to the fixing device 25, where the combined color image (color) is generated by heat and pressure. (Transfer image) is fixed on the sheet (recording paper). Thereafter, the sheet (recording paper) is switched by the switching claw 55 and discharged by the discharge roller 56 and stacked on the discharge tray 57, or switched by the switching claw 55 and reversed by the sheet reversing device 28 and transferred again. After being guided to the position and recording an image on the back surface, the image is discharged by the discharge roller 56 and stacked on the discharge tray 57.

  In the image forming method and the image forming apparatus of the present invention, since the toner of the present invention that can achieve both excellent low-temperature fixability and offset resistance performance is used, high-quality images can be efficiently formed.

Examples of the present invention will be described below, but the present invention is not limited to these examples. In the following examples, “part” and “%” are based on mass unless otherwise specified.
In the following examples and comparative examples, “toner weight average particle size (Dw) and particle size distribution (Dw / Dn)”, “isocyanate group content (NCO%)”, “acid value and hydroxyl value”, “ The measurement of “glass transition temperature (Tg)” and “content of Ti, Bi, and Sn” was performed as follows.

<Weight average particle size (Dw) and particle size distribution (Dw / Dn)>
The weight average particle diameter (Dw) and number average particle diameter (Dn) of the toner are measured with a particle size measuring device (“Multisizer III”, manufactured by Beckman Coulter, Inc.) with an aperture diameter of 100 μm, and analysis software (Beckman Coulter Multisizer) is used. 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 beaker made of glass, and 0.5 g of each toner is added. 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 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.

<Measurement of free isocyanate group content (NCO%)>
The free isocyanate group content (NCO%) was measured by a method based on JIS K1603.

<Method for measuring acid value and hydroxyl value>
-Method of measuring acid value-
The acid value is measured under the following conditions based on the measurement method described in JIS K0070-1992.
Sample preparation: 0.5 g of toner (0.3 g for ethyl acetate-soluble component) is added to 120 ml of toluene and dissolved by stirring for about 10 hours at room temperature (23 ° C.). Furthermore, 30 ml of ethanol is added to prepare a sample solution.
The measurement can be calculated by the apparatus described above, but specifically, the calculation is performed as follows. Titrated with a standardized N / 10 caustic potassium alcohol solution in advance, and the acid value is determined from the consumption of the alcohol potassium solution by the following formula.
Acid value = KOH (ml) x N x 56.1 / sample mass (where N is a factor of N / 10 KOH)
-Measurement method of hydroxyl value-
Weigh accurately 0.5 g of sample into a 100 ml volumetric flask and add 5 ml of acetylating reagent correctly. Then, it is immersed in a bath at 100 ° C. ± 5 ° C. and heated. After 1-2 hours, the flask is removed from the bath, allowed to cool, water is added and shaken to decompose acetic anhydride. Next, in order to complete the decomposition, the flask is again heated in a bath for 10 minutes or more and allowed to cool, and then the wall of the flask is thoroughly washed with an organic solvent. This solution is subjected to potentiometric titration with an N / 2 potassium hydroxide ethyl alcohol solution using the electrode to determine the OH value (according to JIS K0070-1966).

<Glass transition temperature (Tg)>
The glass transition temperature (Tg) is specifically determined by the following procedure. Shimadzu TA-60WS and DSC-60 were used as measurement devices, and the measurement was performed under the following measurement conditions.
〔Measurement condition〕
・ Sample container: Aluminum sample pan (with lid)
-Sample amount: 5mg
Reference: Aluminum sample pan (alumina 10 mg)
・ Atmosphere: Nitrogen (flow rate 50ml / min)
・ Temperature conditions ・ Starting temperature: 20 ℃
・ Raising rate: 10 ° C / min
・ End temperature: 150 ℃
-Holding time: None-Temperature drop: 10 ° C / min
・ End temperature: 20 ℃
-Holding time: None-Temperature rising rate: 10 ° C / min
・ End temperature: 150 ℃
The measurement results were analyzed using the data analysis software (TA-60, version 1.52) manufactured by Shimadzu Corporation. The analysis method is to specify a range of ± 5 ° C centering on the point showing the maximum peak on the lowest temperature side of the DrDSC curve, which is the DSC differential curve of the second temperature rise, and use the peak analysis function of the analysis software to determine the peak temperature. Ask. Next, the maximum endothermic temperature of the DSC curve is obtained using the peak analysis function of the analysis software in the range of the peak temperature + 5 ° C. and −5 ° C. in the DSC curve. The temperature shown here corresponds to the glass transition temperature (Tg) of the toner.

<Measurement of Ti, Bi, and Sn Content in Toner>
The contents of Ti, Bi, and Sn in the toner were quantified with a fluorescent X-ray measuring apparatus (manufactured by RIGAKU, ZSX-100E).

Example 1
-Synthesis of organic fine particle emulsion-
In a reaction vessel equipped with a stirring bar and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries, Ltd.), 83 parts of styrene, methacrylic acid When 83 parts of acid, 110 parts of butyl acrylate and 1 part of ammonium persulfate were charged and stirred for 15 minutes at 400 rpm, a white emulsion was obtained. This was heated to raise the temperature in the system to 75 ° C. and reacted for 5 hours. Next, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours to give a vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). An aqueous dispersion was obtained. This is designated as [fine particle dispersion 1].
The weight average particle diameter of the fine particles contained in the obtained [fine particle dispersion 1] was measured with a particle size distribution measuring apparatus (“LA-920”, manufactured by Horiba, Ltd.) using a laser light scattering method. there were. Further, a part of [Fine Particle Dispersion 1] was dried to isolate the resin component. The glass transition temperature (Tg) of the resin was 59 ° C., and the weight average molecular weight (Mw) was 150,000.

-Preparation of aqueous phase-
990 parts of water, 83 parts of [fine particle dispersion 1], 37 parts of 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries, Ltd.) and 90 parts of ethyl acetate are mixed and stirred. A milky white liquid was obtained. This is designated as [Aqueous Phase 1].

-Synthesis of low molecular weight polyester-
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 229 parts of bisphenol A ethylene oxide 2 mol adduct, 529 parts of bisphenol A propylene oxide 3 mol adduct, 208 parts terephthalic acid, 46 parts adipic acid, and 2 parts of dibutyltin oxide was charged and reacted at 230 ° C. under normal pressure for 8 hours. Subsequently, after reacting under reduced pressure of 10 to 15 mmHg for 5 hours, 44 parts of trimellitic anhydride was put in a reaction vessel and reacted at 180 ° C. and normal pressure for 2 hours to obtain [Low molecular weight polyester 1].
The obtained [low molecular weight polyester 1] had a glass transition temperature (Tg) of 43 ° C., a weight average molecular weight (Mw) of 6,700, a number average molecular weight of 2,500, and an acid value of 25 mgKOH / g.

-Synthesis of Prepolymer 1-
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 463 parts of propylene glycol, 657 parts of terephthalic acid, 96 parts of trimellitic anhydride, and 2 parts of titanium tetrabutoxide are placed at 230 ° C. under normal pressure. Then, the reaction was carried out at a reduced pressure of 10 to 15 mmHg for 5 hours to obtain [Intermediate Polyester 1].
The obtained [Intermediate polyester 1] had a weight average molecular weight of 28,000, a glass transition temperature (Tg) of 36 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 16.5 mgKOH / g.
Next, 250 parts of the [intermediate polyester 1], 18 parts of isophorone diisocyanate, 250 parts of ethyl acetate, and a Bi-based catalyst (Neostan U-600) were placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe. 2 parts), and reacted at 100 ° C. for 15 hours to obtain [Prepolymer 1].
The isocyanate mass% of the obtained [Prepolymer 1] was 0.61%.

-Synthesis of ketimine-
In a reaction vessel equipped with a stir bar and a thermometer, 170 parts of isophoronediamine and 150 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to synthesize [ketimine 1]. The amine value of the obtained [ketimine 1] was 416.

-Synthesis of MB-
Add 1200 parts of water, 540 parts of carbon black (Printex 35, manufactured by Dexa) [DBP oil absorption = 42 ml / 100 mg, pH = 9.5], 1200 parts of polyester resin, and mix with a Henschel mixer (Mitsui Mining Co., Ltd.). The mixture was kneaded at 150 ° C. for 30 minutes using two rolls, and then cooled and pulverized with a pulverizer to prepare [Masterbatch 1].

-Preparation of oil phase-
In a container equipped with a stir bar and a thermometer, 378 parts of [Low molecular polyester 1], 110 parts of carnauba wax, 22 parts of charge control agent (CCA) (salicylic acid metal complex E-84, manufactured by Orient Chemical Industries, Ltd.) , And 947 parts of ethyl acetate were added, the temperature was raised to 80 ° C. with stirring, the temperature was kept at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged into the reaction vessel and mixed for 1 hour to obtain a dissolved product. This is referred to as [Raw material solution 1].
Next, 1324 parts of [Raw Material Solution 1] was transferred into the reaction vessel, and using a bead mill (Ultra Visco Mill, manufactured by IMEX), liquid feeding speed: 1 kg / hr, disk peripheral speed: 6 m / second, 0. Carbon black and wax were dispersed under the conditions of 5 mm zirconia bead filling amount: 80% by volume and number of passes: 3 times.
Next, 1324 parts of a 65% by weight ethyl acetate solution of [low molecular weight polyester 1] was added, and a dispersion was obtained by using a bead mill under the same conditions as described above, with a pass number of one time. This is designated as [Pigment and Wax Dispersion 1].
The obtained [Pigment and Wax Dispersion 1] had a solid content concentration (130 ° C., 30 minutes) of 50% by mass.

-Emulsification-
[Pigment and Wax Dispersion 1] 749 parts, [Prepolymer 1] 115 parts, and “Ketimine 1” 2.5 parts are put in a container, and TK homomixer (manufactured by Tokushu Kika Co., Ltd.) Mix for 1 minute at 000 rpm. Thereafter, 1,200 parts of [Aqueous Phase 1] was added to the reaction vessel, and mixed with a TK homomixer at a rotational speed of 13,000 rpm for 20 minutes to obtain an aqueous medium dispersion. This is designated as [Emulsified slurry 1].

-Deorganic solvent-
[Emulsion slurry 1] is put into a reaction vessel equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging is performed at 45 ° C. for 4 hours, and the organic solvent is distilled off. A dispersion was obtained. This is designated as [Dispersion Slurry 1].
The obtained [Dispersion Slurry 1] had a weight average particle diameter of 5.21 μm and a number average particle diameter of 4.54 μm as measured with Multisizer II (manufactured by Coulter Inc.).

-Cleaning and drying-
[Dispersion Slurry 1] 100 parts were filtered under reduced pressure, and then washed and dried as follows.
(1) 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed: 12000 rpm for 10 minutes), and then filtered.
(2) 100 parts of distilled water was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(3) 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (rotation speed: 12000 rpm for 10 minutes), and then filtered.
(4) 300 parts of ion-exchanged water was added to the filter cake of (3) and mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes) and then filtered twice to obtain a filter cake. The obtained filter cake was dried at 45 ° C. for 48 hours with a circulating drier and sieved with a mesh of 75 μm to obtain a toner. This is referred to as [Toner 1].

(Example 2)
-Production of Toner 2-
In Example 1, instead of [Prepolymer 1], [Prepolymer 2] synthesized as follows was used, except that 2.5 parts of “ketimine 1” was changed to 2.9 parts. [Toner 2] was produced in the same manner as described above.

-Synthesis of Prepolymer 2-
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 463 parts of propylene glycol, 657 parts of terephthalic acid, 96 parts of trimellitic anhydride, and 2 parts of titanium tetrabutoxide are placed at 230 ° C. under normal pressure. Then, the reaction was carried out at a reduced pressure of 10 to 15 mmHg for 3 hours to obtain [Intermediate Polyester 2].
The obtained [Intermediate polyester 2] had a weight average molecular weight of 19,000, a glass transition temperature (Tg) of 34 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 19.2 mgKOH / g.
Next, 250 parts of the [intermediate polyester 2], 21 parts of isophorone diisocyanate, 250 parts of ethyl acetate, and a Bi-based catalyst (Neostan U-600) were placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe. 2 parts), and reacted at 100 ° C. for 15 hours to obtain [Prepolymer 2].
The isocyanate mass% of the obtained [Prepolymer 2] was 0.72%.

(Example 3)
-Production of Toner 3-
In Example 1, instead of [Prepolymer 1], [Prepolymer 3] synthesized as follows was used, except that 2.5 parts of “ketimine 1” was changed to 3.4 parts. In the same manner, [Toner 3] was produced.

-Synthesis of Prepolymer 3-
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 463 parts of propylene glycol, 657 parts of terephthalic acid, 96 parts of trimellitic anhydride, and 2 parts of titanium tetrabutoxide are placed at 230 ° C. under normal pressure. For 5 hours, and then for 3 hours under reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester 3].
The obtained [Intermediate polyester 3] had a weight average molecular weight of 11,000, a glass transition temperature (Tg) of 33 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 22.1 mgKOH / g.
Next, 250 parts of the [intermediate polyester 3], 25 parts of isophorone diisocyanate, 250 parts of ethyl acetate, and a Bi-based catalyst (Neostan U-600) were placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe. 2 parts), and reacted at 100 ° C. for 15 hours to obtain [Prepolymer 3].
The isocyanate mass% of the obtained [Prepolymer 3] was 0.84%.

Example 4
-Production of Toner 4-
[Toner 4] was produced in the same manner as in Example 1 except that [Low Molecular Polyester 1] synthesized in the following manner was used instead of [Low Molecular Polyester 1].

-Synthesis of low molecular weight polyester 2-
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 3-mole adduct, 208 parts terephthalic acid, 46 parts adipic acid, and 1 part of dibutyltin oxide was charged and reacted at 230 ° C. for 8 hours under normal pressure. Subsequently, after reacting under reduced pressure of 10 to 15 mmHg for 5 hours, 44 parts of trimellitic anhydride was put in a reaction vessel and reacted at 180 ° C. and normal pressure for 2 hours to obtain [Low molecular weight polyester 2].
The obtained [low molecular weight polyester 1] had a glass transition temperature (Tg) of 43 ° C., a weight average molecular weight (Mw) of 6,700, a number average molecular weight of 2,500, and an acid value of 25 mgKOH / g.

(Example 5)
-Production of Toner 5-
In Example 4, instead of [Prepolymer 1], [Prepolymer 2] synthesized in Example 2 above was used, except that 2.5 parts of “ketimine 1” was changed to 2.9 parts. [Toner 5] was produced in the same manner as described above.

(Example 6)
-Production of Toner 6-
In Example 4, instead of [Prepolymer 1], [Prepolymer 3] synthesized in Example 3 above was used, except that 2.5 parts of “ketimine 1” was changed to 3.4 parts. [Toner 6] was produced in the same manner as described above.

(Comparative Example 1)
-Production of Toner 7-
In Example 1, instead of [Prepolymer 1], [Prepolymer 4] synthesized as follows was used, except that 2.5 parts of “ketimine 1” was changed to 2.6 parts. [Toner 7] was produced in the same manner as described above.

-Synthesis of Prepolymer 4-
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 463 parts of propylene glycol, 657 parts of terephthalic acid, 96 parts of trimellitic anhydride, and 2 parts of titanium tetrabutoxide are placed at 230 ° C. under normal pressure. And then reacted for 3 hours at a reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester 4].
The obtained [Intermediate Polyester 4] had a weight average molecular weight of 19,000, a glass transition temperature (Tg) of 34 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 19.2 mgKOH / g.
Next, 250 parts of the [intermediate polyester 4], 19 parts of isophorone diisocyanate, and 250 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and the mixture is heated at 100 ° C. for 72 hours. Reaction was performed to obtain [Prepolymer 4].
The isocyanate mass% of the obtained [Prepolymer 4] was 0.64%.

(Comparative Example 2)
-Production of Toner 8-
In Example 1, instead of [Prepolymer 1], [Prepolymer 5] synthesized as follows was used, except that 2.5 parts of “ketimine 1” was changed to 2.9 parts. In the same manner, [Toner 8] was produced.

-Synthesis of Prepolymer 5-
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 463 parts of propylene glycol, 657 parts of terephthalic acid, 96 parts of trimellitic anhydride, and 2 parts of dibutyltin oxide are placed at 230 ° C. under normal pressure. For 6 hours, and then for 3 hours at a reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester 5].
The obtained [Intermediate polyester 5] had a weight average molecular weight of 20,000, a glass transition temperature (Tg) of 34 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 19.1 mgKOH / g.
Next, 250 parts of the [intermediate polyester 5], 21 parts of isophorone diisocyanate, and 250 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and are heated at 100 ° C. for 15 hours. The reaction was performed to obtain [Prepolymer 5].
The isocyanate mass% of the obtained [Prepolymer 5] was 0.71%.

(Comparative Example 3)
-Production of Toner 9-
In Example 4, Example 4 was used except that [Prepolymer 4] synthesized in Comparative Example 1 was used instead of [Prepolymer 1], and 2.5 parts of “ketimine 1” was changed to 2.6 parts. [Toner 9] was produced in the same manner as described above.

(Comparative Example 4)
-Production of Toner 10-
In Example 4, instead of [Prepolymer 1], [Prepolymer 5] synthesized in Comparative Example 2 above was used, except that 2.5 parts of “ketimine 1” was changed to 2.9 parts. [Toner 10] was produced in the same manner as described above.

  Next, with respect to the obtained toners of Examples 1 to 6 and Comparative Examples 1 to 4, the heat resistant storage stability, the fixability, and the charging characteristics were evaluated as follows. The results are shown in Table 2.

<Heat resistant storage stability>
Each toner was stored at 50 ° C. for 8 hours, and then sieved with a 42 mesh screen for 2 minutes. A toner having better heat-resistant storage stability has a lower residual ratio. The following four levels were evaluated.
〔Evaluation criteria〕
×: 30% or more △: 20% or more and less than 30% ○: 10% or more and less than 20% ◎: Less than 10%

<Fixability>
Using an image forming apparatus (Imagio Neo 450 manufactured by Ricoh Co., Ltd.), a solid image and a thick paper transfer paper (Ricoh Co., Ltd., type 6200, manufactured by NBS Ricoh Co., copy printing paper <135>) are solid images and 1 Adjustment is made so that each toner of 0.0 ± 0.1 mg / cm ² is developed, and adjustment is made so that the temperature of the fixing belt is variable, so that the temperature at which no offset occurs with plain paper is fixed with thick paper. The minimum temperature was measured. The minimum fixing temperature was determined as the fixing minimum temperature at which the remaining ratio of the image density after rubbing the obtained fixed image with a pad was 70% or more.

<Charging characteristics>
(1) Stirring for 15 seconds Q / M
100 parts by mass of a silicone resin-coated ferrite carrier (average particle size 50 μm) and 4 parts by mass of each toner were placed in a stainless steel pot up to 30% of the internal volume, stirred for 15 seconds at a stirring speed of 100 rpm, and determined by a blow-off method.
(2) 10 minutes stirring Q / M
The amount of charge when stirring for 10 minutes was determined in the same manner as in (1) above.

<Comprehensive evaluation>
The above evaluation results were comprehensively evaluated and evaluated according to the following criteria.
○: Good ×: Bad

  The toner of the present invention can achieve both excellent low-temperature fixability and anti-offset performance, and is suitably used for high-quality image formation. The developer, toner-containing container, process cartridge, image forming apparatus, and image forming method of the present invention using the toner of the present invention are suitably used for high-quality electrophotographic image formation.

FIG. 1 is a schematic configuration diagram showing an example of a process cartridge of the present invention. FIG. 2 is a schematic configuration diagram showing an example of the image forming apparatus of the present invention. FIG. 3 is a schematic configuration diagram showing another example of the image forming apparatus of the present invention. FIG. 4 is a schematic configuration diagram showing another example of the image forming apparatus of the present invention. FIG. 5 is a schematic configuration diagram showing another example of the image forming apparatus of the present invention. FIG. 6 is a schematic configuration diagram showing another example of the tandem type image forming apparatus of the present invention. FIG. 7 is a partially enlarged view of FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Photoconductor 2 Transfer device 3 Sheet conveyance belt 4 Intermediate transfer body 5 Secondary transfer device 6 Paper feed device 7 Fixing device 8 Photoconductor cleaning device 9 Intermediate transfer body cleaning device 10 Photoconductor (photoconductor drum)
10K black photoconductor 10Y yellow photoconductor 10M magenta photoconductor 10C cyan photoconductor 14 support roller 15 support roller 16 support roller 17 intermediate transfer cleaning device 18 image forming means 20 charging roller 21 exposure device 22 secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure roller 28 Sheet reversing device 30 Exposure device 32 Contact glass 33 First traveling member 34 Second traveling member 35 Imaging lens 36 Reading sensor 40 Developer 41 Developing belt 42K Developer container 42Y Developer container 42M Developer container 42C Developer container 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer supply roller 44K Developer roller 44Y Developer roller 44M Development roller Roller 44C Development roller 45K Black development unit 45Y Yellow development unit 45M Magenta development unit 45C Cyan development unit 49 Registration roller 50 Intermediate transfer member 51 Roller 52 Separation roller 53 Manual feed path 54 Manual feed tray 55 Switching claw 56 Ejection Roller 57 Discharge tray 58 Corona charger 60 Cleaning device 61 Developer 62 Transfer charger 63 Photoconductor cleaning device 64 Charger 70 Charger lamp 80 Transfer roller 90 Cleaning device 95 Transfer paper 100 Image forming device 101 Photoconductor 102 Charging means 103 Exposure Exposure by means 104 Developing means 105 Recording medium 107 Cleaning means 108 Transfer means 110 Belt-type image fixing device 120 Tandem type developing device 130 Document table 142 Feed roller 143 Paper bank 1 4 paper feeding cassette 145 separating roller 146 feed path 147 transport rollers 148 feed path 150 copier main body 200 feeder table 210 image fixing device 220 heating roller 230 pressing roller 300 Scanner 400 automatic document feeder (ADF)

Claims (16)

At least an active hydrogen group-containing compound, a polymer having a site capable of reacting with the active hydrogen group-containing compound, and a toner material containing a colorant are dissolved or dispersed in an organic solvent, and a solution or dispersion is emulsified in an aqueous medium. Or a toner obtained by dispersing and reacting the active hydrogen group-containing compound and the polymer with or after reacting, and then removing the organic solvent,
The polymer includes at least a modified polyester, and the modified polyester has a bond portion derived from an isocyanate group,
The content of Sn in the toner is 800 ppm or less, the content of Ti derived from the non-Sn polyesterification catalyst is 10 ppm to 200 ppm, and the content of Bi derived from the non-Sn isocyanate catalyst is 10 ppm to A toner characterized by being 200 ppm. The content of Sn in the toner is 0 ppm or more and 500 ppm or less, the content of Ti derived from the non-Sn polyesterification catalyst is 10 ppm to 200 ppm, and the content of Bi derived from the non-Sn isocyanate conversion catalyst is 10 ppm. The toner according to claim 1, wherein the toner is ˜200 ppm. The toner according to claim 1, wherein the bond portion derived from the isocyanate group is at least one of a urea bond and a urethane bond. The modified polyester contains an isocyanate terminal-modified polyester, and the isocyanate terminal-modified polyester is obtained by reacting an unmodified polyester with a diisocyanate compound in the presence of a non-Sn isocyanate catalyst. The toner described in 1. The toner according to claim 1, wherein the unmodified polyester is polymerized using a polyesterification catalyst that is non-Sn. The toner according to any one of claims 4 to 5, wherein the isocyanate terminal-modified polyester has a ratio (NCO / OH) of the OH number of the unmodified polyester and the NCO number of the diisocyanate compound of 2.0 to 2.5. The toner according to claim 1, comprising a crosslinkable polyester formed by a reaction between a modified polyester and an active hydrogen group-containing compound. The toner according to claim 1, wherein the toner contains at least a binder resin different from the polymer having a site capable of reacting with an active hydrogen group-containing compound, and the glass transition temperature of the binder resin is 30 ° C. to 50 ° C. The toner according to any one of the above. The toner according to claim 8, wherein the acid value of the binder resin is 1 mgKOH / g to 30 mgKOH / g. The toner according to claim 1, wherein the toner has a glass transition temperature of 40 ° C. to 70 ° C. The toner according to claim 1, wherein the toner has a weight average particle diameter of 3 μm to 8 μm, and the toner has a weight average particle diameter / number average particle diameter of 1.25 or less. A developer comprising the toner according to claim 1. A toner-filled container filled with the toner according to claim 1. An electrostatic latent image carrier and developing means for developing a latent image formed on the electrostatic latent image carrier using the toner according to claim 1 to form a visible image. A process cartridge having at least An electrostatic latent image carrier, an electrostatic latent image forming unit that forms an electrostatic latent image on the electrostatic latent image carrier, and the toner according to any one of claims 1 to 11 At least developing means for forming a visible image by developing the toner, 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. An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image with the toner according to claim 1 to form a visible image An image forming method comprising: a developing step for forming the image; a transfer step for transferring the visible image to a recording medium; and a fixing step for fixing the transferred image transferred to the recording medium.

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