JP5473353B2 - Toner container for electrophotography and image forming method - Google Patents

Description

  The present invention relates to a toner container used in electrophotography and an image forming method using the toner container.

  In conventional image forming apparatuses such as copiers and laser beam printers, in order to prevent toner from leaking from a container such as a toner replenishing container or a toner cartridge, a plurality of toners are formed between the frames constituting the cartridge or inside the container. Sealing is performed by using a sealing member. As an example of the toner sealing member, an elastic body such as urethane foam, soft rubber, or elastomer resin is used. And the said sealing member is provided in the junction part between frames and a container, and the method of compressing and deforming and sealing with a predetermined amount of crushing is generally used.

  On the other hand, since the accuracy of attaching the sealing member becomes more important in order to securely press the convex portion, it is necessary to perform the attaching operation with high accuracy by manual work.

  In order to improve such work, there is a configuration in which a predetermined space is provided between the sealing members, and an adhesive or hot melt is injected into the predetermined space as a filler to seal the sealing members. (For example, refer to Patent Document 1). Therefore, it has been considered that the above-mentioned concerns can be reduced by adopting a sealing configuration in which a sealing member and a filler such as an adhesive or hot melt are integrated. With such a seal configuration, not only can it be completely sealed so as to fill the gaps in the container, but the work is easy and the work man-hours can be reduced, so there is an advantage that the cost can be reduced, It becomes a very useful sealing material. In this case, a method of injecting and filling the integrated sealing member into a predetermined space can be adopted, but for that purpose, a device for reducing the hardness of the sealing member to some extent and improving the handling property of the sealing member injection is required. is there. For example, the hardness of the sealing member can be controlled by adjusting the material configuration and physical properties of the sealing member. Specifically, when the molecular weight of the sealing member is reduced or the plasticizer is used, the hardness of the sealing member can be reduced by increasing the amount of the plasticizer, and the handling property of sealing member injection can be improved.

  However, the above-mentioned sealing member has no problem in normal use, but the low molecular weight component attacks the toner due to continuous use at a high temperature for a long time, and the toner blocks, thereby contaminating the developing member that becomes particularly high in temperature. In addition, various problems such as streak-like image defects may occur. Therefore, in order to use it as a toner sealing member of an electrophotographic toner container, it is necessary to further devise the low molecular weight component of the thermoplastic elastomer, the toner structure, and a combination thereof.

JP 2004-126003 A

  An object of the present invention is to provide an electrophotographic toner container capable of obtaining a stable developable image free from streak-like image defects caused by contamination of a developing member, even by copying or printing a large number of continuous sheets in a high temperature and high humidity environment. And providing an image forming method using the toner container.

  The present invention for solving the above problems is as follows.

<1> In an electrophotographic toner container containing toner,
The electrophotographic toner container has a toner sealing member,
The said toner sealing member, and a thermoplastic elastomer plasticizer is added is used,
The plasticizer is paraffin oil;
In the molecular weight distribution chart of the molecular weight measured by gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble content of the thermoplastic elastomer to which the plasticizer is added , the area ratio of the total component having a molecular weight of 800 or less Is 0.05% or more and 30.00% or less,
The toner has a binder resin, toner particles having containing a colorant and a wax component, and an inorganic fine powder,
After the toner particles were allowed to stand in an environment of 20 ° C. for 5 hours, the methanol concentration (%) at 50% transmission in a methanol wettability test was D20 , and the toner particles were left to stand in an environment of 40 ° C. for 5 hours. When methanol concentration (%) at the time of 50% transmission by the methanol wettability test is D40,
10.0 ≦ D20 ≦ 40.0
0 ≦ (D40−D20) ≦ 2.0
An electrophotographic toner container characterized by satisfying the relationship:

<2> In the molecular weight distribution chart of the molecular weight measured by gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble part of the thermoplastic elastomer to which the plasticizer is added , the whole of the components having a molecular weight of 800 or less <1> The toner container for electrophotography according to <1>, wherein the area ratio of the toner is 0.05% or more and 15.00% or less.

<3> the D20 and the D40 is,
0 ≦ (D40−D20) ≦ 1.0
Satisfying the relationship <1> or electrophotographic toner container according to <2>.

<4> The D20 is,
15.0 ≦ D20 ≦ 25.0
To satisfy the relationship <1> to electrophotographic toner container of any crab description of the <3>.

<5> The toner container for electrophotography according to any one of <1> to <4>, wherein the toner has a viscosity at 100 ° C. of 3,000 Pa · s to 60,000 Pa · s.

<6> The toner particles Oh Ru toner particles obtained I by the turbidimetric polymerization suspension <1> ~ electrophotographic toner container any crab description of <5>.

<7> charging step of charging by the charging means the electrostatic latent image bearing member, exposure to form an electrostatic latent image on the latent electrostatic image bearing member by exposing the electrostatic latent image bearing member is a static- step, a developing step of forming by developing the electrostatic latent image with the toner accommodated in the electrophotographic toner container of the toner image on the latent electrostatic image bearing member, an intermediate transfer member the toner image in the image forming method having a transfer step of transferring to a transfer medium without passing through the through effort other,
The electrophotographic toner container has a toner sealing member,
The said toner sealing member, and a thermoplastic elastomer plasticizer is added is used,
In the molecular weight distribution chart of the molecular weight measured by gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble content of the thermoplastic elastomer to which the plasticizer is added , the area ratio of the total component having a molecular weight of 800 or less Is 0.05% or more and 30.00% or less,
The toner has a binder resin, toner particles having containing a colorant and a wax component, and an inorganic fine powder,
Methanol concentration (%) at the time of 50% permeation by methanol wettability test after leaving the toner particles in an environment of 20 ° C. for 5 hours and methanol after standing in an environment of D20 and 40 ° C. for 5 hours When the methanol concentration (%) at 50% permeation by the wettability test is D40,
10.0 ≦ D20 ≦ 40.0
0 ≦ (D40−D20) ≦ 2.0
An image forming method characterized by satisfying the relationship:
<8> In the molecular weight distribution chart of the molecular weight measured by gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble part of the thermoplastic elastomer to which the plasticizer is added, the whole of the components having a molecular weight of 800 or less The image forming method according to <7>, wherein the area ratio is 0.05% or more and 15.00% or less.
<9> The D20 and the D40 are
0 ≦ (D40−D20) ≦ 1.0
<7> or <8> The image forming method according to <8> satisfying the above relationship.
<10> The D20 is
15.0 ≦ D20 ≦ 25.0
The image forming method according to any one of <7> to <9>, wherein the relationship is satisfied.
<11> The image forming method according to any one of <7> to <10>, wherein the toner has a viscosity at 100 ° C. of 3,000 Pa · s to 60,000 Pa · s.
<12> The image forming method according to any one of <7> to <11>, wherein the toner particles are toner particles obtained by a suspension polymerization method.

  According to the present invention, by appropriately adjusting the amount of low molecular weight components of a thermoplastic elastomer used as a toner sealing member and methanol wettability of toner particles, a large number of continuous copies or prints, particularly under high temperature and high humidity. Can also contain toner that suppresses adhesion and fusion of the toner and inorganic fine powder added to the toner to the toner regulating member and the toner carrying member, and can provide a stable developable image without streak-like image defects. A toner container and an image forming method using the toner container can be provided.

6 is a graph showing the transmittance with respect to the methanol concentration after the toner particles of Example 1 of the present invention were allowed to stand at 20 ° C. and 55% for 5 hours.

The toner container for electrophotography of the present invention is an electrophotographic toner container containing toner,
The toner container uses a thermoplastic elastomer as a toner sealing member,
In the molecular weight distribution chart of the molecular weight measured by gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble part of the thermoplastic elastomer, the area ratio of the whole component having a molecular weight of 800 or less is 0.05% or more and 30 0.000% or less,
The toner has toner particles containing at least a binder resin, a colorant, and a wax component, and an inorganic fine powder,
When the methanol concentration (%) at 50% transmission by the methanol wettability test after leaving the toner particles in an environment of 20 ° C. and 40 ° C. for 5 hours is D20 and D40, respectively.
10.0 ≦ D20 ≦ 40.0
0 ≦ D40−D20 ≦ 2.0
It is characterized by satisfying the relationship.

  In general, during continuous printing under high temperature and high humidity, it is considered that the low molecular weight component contained in the toner sealing member is eluted and bleeds into the toner, so that toner blocking is likely to occur. In addition, the wax component in the toner precipitates on the surface at a high temperature, which promotes toner fusion to the developing member such as the toner regulating member and the toner carrier during development, and causes streak-like image defects, so-called development streaks. Such image defects are likely to occur.

  As a result of intensive studies by the present inventors, the low molecular weight component in the toner sealing member and the surface wettability of the toner particles are largely involved in the suppression of toner fusion to the developing member under high temperature and high humidity. It was revealed.

  A low molecular weight component in the thermoplastic elastomer used for the toner sealing member, in the present invention, a component having a molecular weight of 800 or less elutes at a high temperature. In the present invention, since the low molecular weight component of the toner sealing member is in the optimum range, the amount of adhesion to the toner surface is controlled to an appropriate amount, so that the release of the external additive from the toner surface can be suppressed. As a result, it is possible to suppress contamination of free external additives, deterioration of toner durability, and deterioration of chargeability under high temperature and high humidity, and image quality due to fog even when copied or printed for a long period of time and left for a long period of time. It is possible to obtain an image having a stable developability without deterioration. Here, the external additive refers to a material that is added by a dry mixing method after the toner particles are formed for the purpose of improving the fluidity of the toner and stabilizing the charging performance, most of which are silica fine particles. Inorganic fine powders such as titanium oxide fine particles and alumina fine particles.

  Also in the toner, in order to suppress the fusion to the toner regulating member, it is necessary that the wax is included, and the wax does not exist on the toner surface at the time of development. On the other hand, if the toner surface is too hydrophilic, moisture is adsorbed on the toner surface under high humidity and fogging occurs. Accordingly, the wettability of the toner particles to methanol, that is, the degree of hydrophobicity of the toner particle surface is in the optimum range, so that it is possible to continue providing a stable image over a long period of time.

  The toner container for electrophotography of the present invention uses a thermoplastic elastomer as a toner sealing member, and has a molecular weight measured by gel permeation chromatography (GPC) soluble in tetrahydrofuran (THF) of the thermoplastic elastomer. In the molecular weight distribution chart, the area ratio occupied by components having a molecular weight of 800 or less is 0.05% or more and 30.00% or less. When the proportion of components having a molecular weight of 800 or less is less than 0.05%, the amount of adhesion to the toner surface is extremely small even at high temperatures, and the suppression of liberation of external additives from the toner surface is insufficient. Accordingly, in continuous use at high temperatures, the developing member is contaminated by the free external additive, and streak-like image defects occur. Further, since the fluidity of the toner deteriorates due to the liberation of the external additive, the uniform coating of the toner on the developing member becomes insufficient, and density unevenness occurs. On the other hand, when the proportion of the component having a molecular weight of 800 or less is larger than 30.00%, the amount of adhesion to the toner surface becomes too high at high temperature, and the blocking property of the toner is deteriorated. As a preferable range, the proportion of components having a molecular weight of 800 or less is 0.05% or more and 15.00% or less. Even in a low-temperature fixing-compatible toner such as the present invention, the toner and external additives under high temperature and high humidity are used. Contamination of parts can be greatly suppressed. Furthermore, it is preferable that a very stable image with low development quality without deterioration of image quality due to development streaks and density unevenness can be obtained even by copying or printing for a long time and leaving for a long time.

  By the way, the low molecular weight component of the thermoplastic elastomer used for the toner sealing member of the present invention, particularly the component having a molecular weight of 800 or less, is mostly added as a plasticizer. That is, the amount of the component having a molecular weight of 800 or less of the thermoplastic elastomer used in the toner sealing member of the present invention is controlled by the addition amount and the molecular weight of the plasticizer, and has good sealing properties and handling as a toner sealing member. It becomes possible to express sex.

  The plasticizer component in the thermoplastic elastomer used for the toner sealing member is not particularly limited as long as it satisfies the physical property range of the present invention, but nonpolar paraffin oil may be used. preferable.

  Furthermore, examples of the thermoplastic elastomer used for the toner sealing member include styrene, polyester, and olefin.

  The molecular weight distribution and the molecular weight measurement method by gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble part of the thermoplastic elastomer in the present invention are shown below.

First, the thermoplastic elastomer was dissolved in tetrahydrofuran (THF) at room temperature over 24 hours. The obtained solution is filtered through a solvent-resistant membrane filter “Maescho Disc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is about 0.8% by mass. Using this sample solution, measurement was performed under the following conditions.
Column: Tosoh TSK guard column Super H-H x 1 + TSK gel HM-M x 2 + TSK gel Super H 2000 x 1 Eluent: Tetrahydrofuran (THF)
Detector: differential refractometer (RI), UV-visible detector (UV: 254 nm)
Oven temperature: 40.0 ° C
Sample injection volume: 50 μl

  In calculating the molecular weight of the sample, standard polystyrene resin (for example, trade name “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F— 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 "manufactured by Tosoh Corporation) were used.

The toner used in the electrophotographic toner container of the present invention has toner particles containing at least a binder resin, a colorant, and a wax component, and inorganic fine powder. When the methanol concentration (%) at the time of 50% permeation by the methanol wettability test after standing in an environment of 40 ° C. for 5 hours is D20 and D40, respectively.
10.0 ≦ D20 ≦ 40.0 [Formula 1]
0 ≦ D40−D20 ≦ 2.0 [Formula 2]
It is characterized by satisfying the relationship.

  The wettability with respect to methanol represents the degree of hydrophobicity of the toner particle surface. That is, the toner particles having the above characteristics have a moderate polarity on the surface at room temperature. Furthermore, [Expression 2] represents that the surface precipitation of the wax is suppressed during development at high temperature and high humidity. Therefore, the toner fusion to the toner carrier and the toner regulating member is suppressed even in the durability under high temperature and high humidity, and stable developability can be maintained over a long period of time.

  The low molecular weight component in the thermoplastic elastomer used for the toner sealing member is not particularly limited as long as it satisfies the physical property range of the present invention. For example, hydrophobic paraffin oil should be used. Is preferred. This is preferable because it causes an interaction with the hydrophobic part of the toner particles so that it easily adheres to the surface of the toner, and it is easy to suppress member contamination due to liberation of the external additive.

  In [Formula 1], a more preferable range is 15.0 ≦ D20 ≦ 25.0. If D20 is less than 10.0, the toner particles have high hydrophilicity, and the amount of moisture adsorbed on the toner increases in a high-temperature and high-humidity environment, resulting in a decrease in the charge amount of the toner. Fusing to the member. If D20 is greater than 40.0, a large amount of wax is deposited on the surface, the developing member is contaminated by rubbing against the toner regulating member, and the toner is fused.

  In [Formula 2], a more preferable range is 0 ≦ D40−D20 ≦ 1.0. During continuous printing at a high temperature of 30 ° C. or higher, the developing portion reaches 40 ° C. or higher due to frictional heat generated by the friction between the toner carrier and the toner regulating member and the toner. When D40-D20 is larger than 2.0, the toner becomes a high temperature of 40 ° C. or higher during continuous development under high temperature and high humidity, and the wax is deposited on the surface. Fusion occurs.

  The methanol wettability test in the present invention is performed as follows.

  First, 60 ml of water is put into a cylindrical glass container having a diameter of 5 cm and a thickness of 1.75 mm, and dispersed for 5 minutes with an ultrasonic disperser in order to remove bubbles and the like in the measurement sample.

Next, the toner particles are shaken with a mesh having an opening of 150 μm, 0.1 g of the toner particles passing through the mesh are precisely weighed, and added to the container containing the water to prepare a sample solution for measurement. As the toner particles, toner particles after standing for 5 hours in an environment of 20 ° C. and toner particles after standing for 5 hours in an environment of 40 ° C. were used, respectively.

  Then, the measurement sample solution is set in a powder wettability tester “WET-100P” (manufactured by Reska). The sample liquid for measurement is stirred at a speed of 300 rpm using a magnetic stirrer. As the rotor of the magnetic stirrer, a spindle type rotor having a length of 25 mm and a maximum barrel diameter of 8 mm coated with a fluororesin is used.

  Next, the transmittance is measured with light having a wavelength of 780 nm while continuously adding methanol into the sample solution for measurement through the above apparatus at a dropping rate of 0.8 ml / min, and a methanol dropping transmittance curve is prepared. To do. A methanol dropping transmittance curve of the toner particles of Example 1 of the present invention is shown in FIG. From this curve, the methanol concentration when the transmittance was 50% was used as an index of the degree of hydrophobicity.

  The above physical properties relating to methanol wettability can be satisfied by adjusting the manufacturing method and manufacturing conditions of the toner particles, the wax component, the physical properties of the binder resin, and the like.

  The toner used in the present invention preferably has a viscosity at 100 ° C. of 3,000 Pa · s or more and 60,000 Pa · s or less. This range is preferable because the toner has moderate softness and can suppress the release of the external additive due to durability deterioration. Furthermore, since a small amount of the low molecular weight component of the plasticizer in the toner sealing member adheres to the toner, liberation of the external additive can be further suppressed. When the viscosity at 100 ° C. is less than 3,000 Pa · s, the toner is soft, and it is not preferable because it is easily fused to the member due to damage caused by rubbing between the toner carrier and the toner regulating member during development. On the other hand, if the viscosity at 100 ° C. is larger than 60,000 Pa · s, the toner is too hard, and the liberation of the external additive due to durability deterioration is promoted. Unevenness is likely to occur, which is not preferable. Furthermore, it is difficult to obtain low-temperature fixability.

  The viscosity of the toner at 100 ° C. is measured using a constant-load extrusion type capillary rheometer “Flow Characteristic Evaluation Apparatus Flow Tester CFT-500D” (manufactured by Shimadzu Corporation) according to the manual attached to the apparatus. In this device, while applying a constant load from the top of the measurement sample by the piston, the measurement sample filled in the cylinder is heated and melted, and the molten measurement sample is extruded from the die at the bottom of the cylinder, and the temperature at this time And measure the relationship between the amount of piston descent.

  In the present invention, measurement is performed from 50 ° C. to 200 ° C., and the apparent viscosity calculated at 100 ° C. is defined as the viscosity (Pa · s) of the toner at 100 ° C.

The apparent viscosity η (Pa · s) at 100 ° C. is calculated as follows. First, the flow rate Q (cm ³ / s) is calculated from the following equation (1). In the formula, the cross-sectional area of the piston is A (cm ² ), and the time required for the piston to descend between 0.10 mm above and below the position of the piston at 100 ° C. (interval 0.20 mm) is Δt (Seconds).
Q = (0.20 × A) / (10 × Δt) (1)

And the apparent viscosity (eta) in 100 degreeC is computed from the following formula (2) using the obtained flow rate Q. In the formula, the piston load is P (Pa), the diameter of the hole of the die is B (mm), and the length of the die is L (mm).
η = (π × B4 × P) / (128000 × L × Q) (2)

As a measurement sample, about 1.0 g of toner is compression-molded at about 10 MPa using a tablet molding compressor (for example, NT-100H, manufactured by NPA System) in an environment of 25 ° C. for about 60 seconds. A cylindrical shape having a diameter of about 8 mm is used. The measurement conditions of CFT-500D are as follows.
Test mode: Temperature rising start temperature: 50 ° C
Achieving temperature: 200 ° C
Measurement interval: 1.0 ° C
Temperature increase rate: 4.0 ° C./min
Piston cross-sectional area: 1.000 cm ²
Test load (piston load): 10.0 kgf (0.9807 MPa)
Preheating time: 300 seconds Die hole diameter: 1.0 mm
Die length: 1.0mm

  The toner particles used in the present invention may be produced by any method, but a production method of granulating in an aqueous medium such as a suspension polymerization method, an emulsion polymerization method, or a suspension granulation method. It is preferable that it is manufactured by. In the case of toner particles produced by a general pulverization method, it is very difficult to add a large amount of the wax component. In the production method of granulating toner particles in an aqueous medium, even if a large amount of a wax component is added to the toner particles, the wax component is hardly present on the surface of the toner particles and can be encapsulated. Among these production methods, the suspension polymerization method is one of the most preferred production methods from the viewpoint of long-term development stability due to the inclusion of the wax component in the toner particles and the production cost such that no solvent is used. That is, the toner particles are obtained by dispersing a polymerizable monomer composition containing at least a polymerizable monomer, a colorant and a wax component in an aqueous medium, granulating the polymerized monomer. The toner particles obtained by the above are preferable.

  Hereinafter, the most suitable suspension polymerization method for obtaining the toner particles used in the present invention will be exemplified and the production method of the toner particles will be described. A polymerizable monomer, a colorant, a wax component and other additives as necessary are uniformly dissolved or dispersed by a disperser such as a homogenizer, a ball mill, a colloid mill, or an ultrasonic disperser, and polymerized therein. An initiator is dissolved to prepare a polymerizable monomer composition. Next, toner particles are produced by dispersing the polymerizable monomer composition in an aqueous medium containing a dispersion stabilizer, granulating, and polymerizing the polymerizable monomer. The polymerization initiator may be added simultaneously with the addition of other additives to the polymerizable monomer, or may be mixed immediately before being suspended in the aqueous medium. Also, a polymerization initiator dissolved in a polymerizable monomer or solvent can be added immediately after granulation and before starting the polymerization reaction.

  Examples of the binder resin constituting the toner include commonly used styrene-acrylic copolymers, styrene-methacrylic copolymers, epoxy resins, styrene-butadiene copolymers, and the like. Therefore, as the polymerizable monomer, a vinyl polymerizable monomer capable of radical polymerization can be used. As the vinyl polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used.

  Examples of the polymerizable monomer include the following. Styrene monomers such as styrene, o- (m-, p-) methylstyrene, m- (p-) ethylstyrene; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, Propyl methacrylate, butyl acrylate, butyl methacrylate, octyl acrylate, octyl methacrylate, dodecyl acrylate, dodecyl methacrylate, stearyl acrylate, stearyl methacrylate, behenyl acrylate, behenyl methacrylate, 2-ethylhexyl acrylate, Acrylic acid ester monomers such as 2-ethylhexyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate and diethylaminoethyl methacrylate, Ether-based monomers; butadiene, isoprene, cyclohexene, acrylonitrile, methacrylonitrile, acrylic acid amide, such as ene-based monomers methacrylamide.

  These polymerizable monomers are used alone or in general, and the theoretical glass transition temperature (Tg) described in the publication polymer handbook 2nd edition III-p139-192 (John Wiley & Sons) is 35 ° C. or higher. A polymerizable monomer is appropriately mixed and used so as to exhibit 75 ° C. or lower. When the theoretical glass transition temperature is less than 35 ° C., problems are likely to occur from the viewpoint of storage stability and durability stability of the toner, whereas when it exceeds 75 ° C., the fixability is lowered.

  In the case of producing toner particles for use in the toner of the present invention, a low molecular weight polymer may be added. The low molecular weight polymer can be added to the polymerizable monomer composition when toner particles are produced by suspension polymerization. As the low molecular weight polymer, the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) is in the range of 2,000 to 5,000, and Mw / Mn is less than 4.5, preferably Is preferably less than 3.0.

  Examples of the low molecular weight polymer include low molecular weight polystyrene, low molecular weight styrene-acrylic acid ester copolymer, and low molecular weight styrene-acrylic copolymer.

  A preferable addition amount of the low molecular weight polymer is 1 part by mass or more and 50 parts by mass or less, and more preferably 5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the binder resin.

  In the present invention, a polar resin having a carboxyl group such as a polyester resin or a polycarbonate resin can be used in combination with the above-described binder resin.

  For example, in the case of directly producing toner particles by a suspension polymerization method, when a polar resin is added during the polymerization reaction from the dispersion step to the polymerization step, a polymerizable monomer composition that becomes toner particles and an aqueous dispersion medium are exhibited. Depending on the polarity balance, the presence state of the polar resin can be controlled so that the added polar resin forms a thin layer on the surface of the toner particles or exists with a gradient from the toner particle surface toward the center. .

  A preferable addition amount of the polar resin is 0.5 part by mass or more and 25 parts by mass or less, and more preferably 0.5 part by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the binder resin. If the amount is less than 0.5 parts by mass, the presence state of the polar resin in the toner particles tends to be non-uniform. On the other hand, if the amount exceeds 25 parts by mass, the polar resin layer formed on the surface of the toner particles becomes thick. Absent.

  Examples of the polar resin used in the present invention include polyester resins, epoxy resins, styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, and styrene-maleic acid copolymers. In particular, as a polar resin, a polyester resin having a molecular weight of 3,000 to 10,000 and having a main peak molecular weight is preferable because the fluidity and negative triboelectric charging characteristics of toner particles can be improved.

  In the present invention, a crosslinking agent may be used when the binder resin is synthesized in order to increase the mechanical strength of the toner particles.

  Examples of the bifunctional crosslinking agent include the following. Divinylbenzene, bis (4-acryloxypolyethoxyphenyl) propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 -Hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200, # 400, # 600 diacrylate, dipropylene glycol diacrylate, polypropylene Glycol diacrylate, polyester-type diacrylate (MANDA Nippon Kayaku), and diacrylate above instead of diacrylate Thing.

  The following are mentioned as a polyfunctional crosslinking agent. Pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate and its methacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, diallyl phthalate, tri Allyl cyanurate, triallyl isocyanurate and triallyl trimellitate. The addition amount of these crosslinking agents is preferably 0.05 parts by mass or more and 10 parts by mass or less, more preferably 0.1 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer.

  The following are mentioned as a polymerization initiator used for the toner of the present invention. 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis Azo or diazo polymerization initiators such as -4-methoxy-2,4-dimethylvaleronitrile and azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl Peroxide-based polymerization initiators such as peroxide, lauroyl peroxide, tert-butyl-peroxypivalate.

  Although the usage-amount of these polymerization initiators changes with the target degree of polymerization, generally they are 3 mass parts or more and 20 mass parts or less with respect to 100 mass parts of polymerizable vinylic monomers. The kind of the polymerization initiator varies slightly depending on the polymerization method, but is used alone or in combination with reference to the 10-hour half-life temperature.

  The toner of the present invention contains a colorant as an essential component in order to impart coloring power. Examples of the colorant preferably used in the present invention include the following organic pigments, organic dyes, and inorganic pigments.

  Examples of organic pigments or organic dyes as cyan colorants include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, and basic dye lake compounds. Specific examples include the following. C. I. Pigment blue 1, C.I. I. Pigment blue 7, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 60, C.I. I. Pigment blue 62, C.I. I. Pigment blue.

  Examples of the organic pigment or organic dye as the magenta colorant include the following. Condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds. Specific examples include the following. C. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment violet 19, C.I. I. Pigment red 23, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 48: 4, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 144, C.I. I. Pigment red 146, C.I. I. Pigment red 150, C.I. I. Pigment red 166, C.I. I. Pigment red 169, C.I. I. Pigment red 177, C.I. I. Pigment red 184, C.I. I. Pigment red 185, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment Red 254.

  Examples of the organic pigment or organic dye as the yellow colorant include compounds typified by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specific examples include the following. C. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 62, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 111, C.I. I. Pigment yellow 120, C.I. I. Pigment yellow 127, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 174, C.I. I. Pigment yellow 175, C.I. I. Pigment yellow 176, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 181, C.I. I. Pigment yellow 191, C.I. I. Pigment Yellow 194.

  Examples of the black colorant include carbon black and those prepared by using the above yellow colorant / magenta colorant / cyan colorant to black.

  These colorants can be used alone or in combination and further in the form of a solid solution. The colorant used in the toner of the present invention is selected from the viewpoints of hue angle, saturation, brightness, light resistance, OHP transparency, and dispersibility in the toner.

  The colorant is preferably used by adding 1 part by mass or more and 20 parts by mass or less to 100 parts by mass of the polymerizable monomer or binder resin.

  In the present invention, when toner particles are obtained using a polymerization method, it is necessary to pay attention to the polymerization inhibitory property and water phase migration property of the colorant, and preferably, a hydrophobic treatment with a substance that does not inhibit polymerization is performed. It is better to apply it to the colorant. In particular, since dye-based colorants and carbon black have many polymerization-inhibiting properties, care must be taken when using them.

  In addition, as a method for suppressing the polymerization inhibitory property of the dye-based colorant, a method of polymerizing a polymerizable monomer in the presence of these dyes in advance can be mentioned, and the obtained colored polymer is composed of a polymerizable monomer composition. Add to product.

  Moreover, about carbon black, you may process with the substance (for example, polyorganosiloxane etc.) which reacts with the surface functional group of carbon black besides the process similar to the said dye.

  The toner used in the present invention essentially contains a wax component. The content of the wax component is preferably 4.0% by mass or more and 25% by mass or less with respect to the total amount of the binder resin. More preferably, it is 5.0 mass% or more and 20 mass% or less, More preferably, it is 5.0 mass% or more and 15 mass% or less. When the content of the wax component is less than 4.0% by mass, the releasability effect at the time of fixing cannot be sufficiently exhibited, and the transfer paper is likely to be wound when the fixing body is at a low temperature. On the other hand, if it is greater than 25% by mass, the wax component tends to be unevenly distributed on the surface of the toner particles when subjected to mechanical stress such as excessive friction in the developing device, and problems such as fusing and fogging are likely to occur.

  Further, the wax component preferably has a maximum endothermic peak temperature in the range of 60 ° C. or more and 120 ° C. or less in the DSC curve at the time of temperature rise measured by a differential scanning calorimetry (DSC) apparatus, more preferably It is 62 degreeC or more and 110 degrees C or less, More preferably, they are 65 degreeC or more and 90 degrees C or less. When the maximum endothermic peak temperature is less than 60 ° C., the storage stability and developability of the toner deteriorate. On the other hand, when the maximum endothermic peak temperature exceeds 120 ° C., the plasticizing effect on the toner is small and the low-temperature fixability is lowered.

  The wax component used in the present invention preferably includes a nonpolar hydrocarbon wax. Other wax components include the following. Amide waxes, higher fatty acids, long chain alcohols, ketone waxes, ester waxes, and derivatives such as these graft compounds and block compounds. If necessary, two or more wax components may be used in combination.

  Examples of the hydrocarbon wax used in the present invention include the following. Petroleum wax such as paraffin wax, microcrystalline wax, petrolatum and derivatives thereof; Fischer-Tropsch wax and derivatives thereof according to Fischer-Tropsch method; polyolefin wax such as polyethylene wax and polypropylene wax and derivatives thereof. Derivatives include oxides, block copolymers with vinyl monomers, and graft modified products. Further examples include hydrogenated castor oil and derivatives thereof, vegetable waxes and animal waxes. These wax components may be used alone or in combination of two or more.

  Among these, when the hydrocarbon wax by the Fischer-Tropsch method is used, the high temperature offset resistance can be maintained well while maintaining the developability particularly in the contact development over a long period of time. These hydrocarbon waxes may contain an antioxidant within a range that does not affect the chargeability of the toner.

  As the dispersion stabilizer used when preparing the aqueous medium, known inorganic and organic dispersion stabilizers can be used.

  Specifically, the following are mentioned as an example of an inorganic dispersion stabilizer. Tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina .

  Examples of the organic dispersant include the following. Polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, carboxymethyl cellulose sodium salt, starch.

  Commercially available nonionic, anionic and cationic surfactants can also be used. Examples of such surfactants include the following. Sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, calcium oleate.

  As the dispersion stabilizer, an inorganic poorly water-soluble dispersion stabilizer is preferable, and a poorly water-soluble inorganic dispersion stabilizer that is soluble in an acid is preferably used.

  In the present invention, when preparing an aqueous medium using a hardly water-soluble inorganic dispersion stabilizer, the amount of these dispersion stabilizers used is 0.2 mass relative to 100 parts by mass of the polymerizable monomer. It is preferable that it is at least 2.0 parts by mass. Moreover, in this invention, it is preferable to prepare an aqueous medium using 300 to 3000 mass parts of water with respect to 100 mass parts of polymerizable monomer compositions.

  In the present invention, when preparing an aqueous medium in which the above poorly water-soluble inorganic dispersion stabilizer is dispersed, a commercially available dispersion stabilizer may be used as it is. In order to obtain particles of a dispersion stabilizer having a fine uniform particle size, an aqueous medium may be prepared by generating a poorly water-soluble inorganic dispersion stabilizer in a liquid medium such as water under high-speed stirring. For example, when tricalcium phosphate is used as a dispersion stabilizer, a preferred dispersion stabilizer can be obtained by mixing sodium phosphate aqueous solution and calcium chloride aqueous solution under high speed stirring to form fine particles of tricalcium phosphate. Can do.

  In the toner of the present invention, a charge control agent can be mixed with toner particles and used as necessary. By adding a charge control agent, the charge characteristics can be stabilized, and the optimum triboelectric charge amount can be controlled according to the development system.

  As the charge control agent, a known one can be used, and a charge control agent that has a high charging speed and can stably maintain a constant charge amount is particularly preferable. Further, when the toner particles are produced by a direct polymerization method, a charge control agent having a low polymerization inhibition property and substantially free from a solubilized product in an aqueous medium is particularly preferable.

  Examples of the charge control agent that control the toner to be negatively charged include the following. Organic metal compounds and chelate compounds are effective, and monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids, and dicarboxylic acid-based metal compounds. Other examples include aromatic oxycarboxylic acids, aromatic mono- and polycarboxylic acids and metal salts thereof, anhydrides, esters, and phenol derivatives such as bisphenol. Further examples include urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, boron compounds, quaternary ammonium salts, calixarene, and resin charge control agents.

  Examples of the charge control agent that controls the toner to be positively charged include the following. Nigrosine-modified products such as nigrosine and fatty acid metal salts; guanidine compounds; imidazole compounds; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and the like Onium salts such as phosphonium salts and lake pigments thereof; triphenylmethane dyes and lake pigments thereof. Gallic acid, ferricyanide, ferrocyanide, etc.); metal salt of higher fatty acid; resin charge control agent.

  The toner of the present invention can contain these charge control agents alone or in combination of two or more.

  Among these charge control agents, a salicylic acid-based compound containing a metal is preferable in order to fully exhibit the effects of the present invention, and the metal is particularly preferably aluminum or zirconium. The most preferred charge control agent is an aluminum 3,5-di-tert-butylsalicylate compound.

  A preferable blending amount of the charge control agent is 0.01 parts by mass or more and 20 parts by mass or less, more preferably 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer or the binder resin. . However, it is not essential to add a charge control agent to the toner of the present invention, and the toner does not necessarily contain a charge control agent by actively utilizing frictional charging with the toner layer thickness regulating member or the toner carrier. There is no need to let it.

  An inorganic fine powder can be added to the toner particles of the present invention as a fluidity improver.

  Examples of the inorganic fine powder to be added to the toner particles of the present invention include fine powder such as silica fine powder, titanium oxide fine powder, alumina fine powder, or double oxide fine powder thereof. Among the inorganic fine powders, silica fine powder and titanium oxide fine powder are preferable.

Examples of the silica fine powder include dry silica or fumed silica produced by vapor phase oxidation of silicon halide, and wet silica produced from water glass. As the inorganic fine powder, dry silica having less silanol groups on the surface and inside the silica fine powder and less Na ₂ O and SO ₃ ²⁻ is preferable. The dry silica may be a composite fine powder of silica and another metal oxide produced by using a metal halogen compound such as aluminum chloride or titanium chloride together with a silicon halogen compound in the production process.

  The inorganic fine powder is preferably externally added to the toner particles in order to improve the fluidity of the toner and make the toner particles uniformly charged. By hydrophobizing the inorganic fine powder, it is possible to adjust the charge amount of the toner, improve the environmental stability, and improve the characteristics in a high-humidity environment. More preferably, it is used. When the inorganic fine powder added to the toner absorbs moisture, the charge amount as the toner is reduced, and the developability and transferability are easily lowered.

  As treatment agents for the hydrophobic treatment of inorganic fine powder, unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organosilicon compounds, organotitanium Compounds. These treatment agents may be used alone or in combination.

  Among these, inorganic fine powder treated with silicone oil is preferable. More preferably, the hydrophobicity-treated inorganic fine powder treated with silicone oil treated with silicone oil simultaneously or after the hydrophobic treatment of the inorganic fine powder with a coupling agent increases the charge amount of the toner particles even in a high humidity environment. It is good for maintaining high and reducing selective developability.

  The amount of the inorganic fine powder added is preferably 0.1 parts by mass or more and 4.0 parts by mass or less, more preferably 0.2 parts by mass or more and 3.5 parts by mass with respect to 100 parts by mass of the toner particles. It is as follows. If the amount is less than 0.1 parts by mass, the improvement in toner fluidity and the uniform charging of the toner particles cannot be fully achieved, which is not preferable. When the amount is more than 4.0 parts by mass, excessive inorganic fine powder contaminates various members and induces image defects, which is not preferable.

The toner used in the present invention preferably has a weight average particle diameter D ₄ of 3.0 μm or more and 8.0 μm. More preferably, it is 5.0 μm or more and 7.5 μm. When the weight average particle diameter D _{4 of the} toner is less than 3.0 μm, the fog is deteriorated, and when it is more than 8.0 μm, the character reproducibility is remarkably deteriorated.

  The toner and toner container according to the present invention include a charging step of charging the electrostatic latent image carrier with a charging unit, an exposure step of exposing the charged electrostatic latent image carrier to form an electrostatic latent image, A developing step of developing the electrostatic latent image with toner to form a toner image on the electrostatic latent image carrier; and a transferring step of transferring the toner image to a transfer material with or without an intermediate transfer member. It is suitably used for an image forming method.

  Hereinafter, the present invention will be specifically described with reference to production examples and examples, but this does not limit the present invention in any way.

[Example 1]
<Manufacture of toner particles A>
With respect to 100 parts by mass of the styrene monomer, C.I. I. 16.5 parts by mass of Pigment Blue 15: 3 and 3.0 parts by mass of an aluminum 3,5-di-tert-butylsalicylate compound [Bontron E88 (manufactured by Orient Chemical Co., Ltd.)] were prepared. These were introduced into an attritor (manufactured by Mitsui Mining Co., Ltd.) and stirred at 200 rpm at 25 ° C. for 180 minutes using zirconia beads (140 parts by mass) with a radius of 1.25 mm to prepare a master batch dispersion 1. .

On the other hand, after adding 450 parts by mass of 0.1 M Na ₃ PO ₄ aqueous solution to 710 parts by mass of ion-exchanged water and heating to 60 ° C., 67.7 parts by mass of 1.0 M CaCl ₂ aqueous solution was gradually added. An aqueous medium containing a calcium phosphate compound was obtained.
Master batch dispersion 1 40 parts by mass Styrene monomer 28 parts by mass n-butyl acrylate monomer 18 parts by mass Low molecular weight polystyrene 20 parts by mass (Mw = 3,000, Mn = 1,050, Tg = 55 ° C)
Hydrocarbon wax 9 parts by mass (Fischer-Tropsch wax, maximum endothermic peak = 78 ° C., Mw = 750)
Charge control resin (details will be described later) 0.3 parts by mass Polyester resin 5 parts by mass (terephthalic acid: isophthalic acid: propylene oxide modified bisphenol A (2 mol adduct): ethylene oxide modified bisphenol A (2 mol adduct) = 30: 30: 30: 10 polycondensate, acid number 11, Tg = 74 ° C., Mw = 11,000, Mn = 4,000)
The above material was heated to 65 ° C., and uniformly dissolved and dispersed at 5,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). In this, 7.1 mass part of 70% toluene solution of polymerization initiator 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate was dissolved to prepare a polymerizable monomer composition.

The polymerizable monomer composition is charged into the aqueous medium, and stirred at 10,000 rpm for 10 minutes with a TK homomixer in a N ₂ atmosphere at a temperature of 65 ° C. to prepare a polymerizable monomer composition. Grained. Thereafter, the temperature was raised to 67 ° C. while stirring with a paddle stirring blade. When the polymerization conversion rate of the polymerizable vinyl monomer reached 90%, a 0.1 mol / liter sodium hydroxide aqueous solution was added. The pH of the aqueous dispersion medium was adjusted to 9. Furthermore, it heated up at 80 degreeC with the temperature increase rate of 40 degreeC / h, and was made to react for 4 hours. After completion of the polymerization reaction, the residual monomer in the toner particles was distilled off under reduced pressure. After cooling the aqueous medium, hydrochloric acid was added to adjust the pH to 1.4, and the mixture was stirred for 6 hours to dissolve the calcium phosphate salt. The toner particles were separated by filtration, washed with water, and then dried at a temperature of 40 ° C. for 48 hours to obtain cyan toner particles A.

  Table 1 shows the value of the methanol concentration (%) at the time of 50% transmission according to the methanol wettability test after the toner particles A were allowed to stand at 20 ° C. and 40 ° C. for 5 hours.

(Manufacture of charge control resin)
In a pressurizable reaction vessel equipped with a reflux tube, a stirrer, a thermometer, a nitrogen introduction tube, a dropping device and a decompression device, 250 parts by mass of methanol as a solvent, 150 parts by mass of 2-butanone and 100 parts by mass of 2-propanol, As a monomer, 77 parts by mass of styrene, 15 parts by mass of 2-ethylhexyl acrylate, and 8 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid were added and heated to reflux temperature while stirring. A solution obtained by diluting 1 part by mass of t-butylperoxy-2-ethylhexanoate as a polymerization initiator with 20 parts by mass of 2-butanone was added dropwise over 30 minutes, and stirring was continued for 5 hours. Further, t-butylperoxy was further added. A solution prepared by diluting 1 part by mass of 2-ethylhexanoate with 20 parts by mass of 2-butanone was added dropwise over 30 minutes, and the mixture was further stirred for 5 hours to complete the polymerization. Furthermore, 500 parts by mass of deionized water was added while maintaining the temperature, and the mixture was stirred for 2 hours at 80 to 100 revolutions per minute so as not to disturb the interface between the organic layer and the aqueous layer, and then allowed to stand for 30 minutes for separation. Later, the aqueous layer was discarded, and anhydrous sodium sulfate was added to the organic layer for dehydration.

  Next, the polymer obtained after the polymerization solvent was distilled off under reduced pressure was coarsely pulverized to 100 μm or less using a cutter mill equipped with a 150 mesh screen. The obtained charge control resin having a sulfur atom had Tg = 58 ° C., Mp = 13,000, and Mw = 30,000.

[Production of Toner A]
With respect to 100 parts by mass of the toner particles A, 1.8 parts by mass of hydrophobic silica fine powder surface-treated with hexamethyldilazan (number average primary particle diameter: 7 nm), 0.15 parts by mass of rutile titanium oxide fine powder, (Number average primary particle size: 30 nm) was dry mixed for 5 minutes with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) to obtain toner A of the present invention.

[Image evaluation]
Image evaluation was performed using a Canon printer LBP5300 remodeled machine. In the modified part, an SUS blade having a thickness of 8 μm is used as a toner regulating member, and a blade bias can be applied to the toner regulating member at −200 V with respect to the developing bias, and in order to perform printing at high speed. These are two points that can be printed on A4 paper at 40 sheets / minute. The evaluation cartridge is an image output cartridge in which the seal member for bonding the toner regulating member and the cartridge container is replaced with the toner sealing member a shown in Table 2, and 160 g of the toner A is used as the toner. did. A styrene-based thermoplastic elastomer was used for the toner sealing member, and paraffin oil was added as a plasticizer. Image evaluation was carried out by mounting the above cartridge on the cyan station and mounting a dummy cartridge on the other.

<Development streak (longitudinal streaks due to fusion of toner and external additive to development member)> Image evaluation>
In the development streak image evaluation, an image having a printing rate of 1% was continuously output in a high temperature and high humidity environment of 30 ° C. and 80% RH and in a normal temperature and normal humidity environment of 23 ° C. and 55% RH. The presence or absence of development streaks was confirmed each time 1,000 sheets were output, and finally 15,000 sheets of images were output. The development streaks were evaluated by the following method. The evaluation results are shown in Table 3.

The presence or absence of development streaks was determined by outputting a solid image and a halftone image each time 1,000 sheets were printed and visually observing the image, and finally evaluated the durability up to 15,000 sheets. The slower the development streak generation number, the better the development streak characteristics. The relationship between the number of development streaks starting and the development streak level is shown below. Evaluations A, B, and C are levels that do not cause a problem in use, while D and E are levels that cause a problem in use.
A: Up to 15,000 sheets, no development streaks B: 14,001 to 15,000 sheets, development streaks C: 12,001 to 14,000 sheets, development streaks D: 10,001 to 12, Developed streak occurred at 10000 sheets E: Developed streak occurred before 10,000 sheets

<Fog evaluation>
For fog evaluation, 12,000 sheets of images with a printing rate of 1% were continuously output in a high temperature and high humidity environment of 30 ° C. and 80% RH and in a normal temperature and normal humidity environment of 23 ° C. and 55% RH. Thereafter, an image having a white background portion is output, and the whiteness (reflectance Ds (%)) of the white portion of the printout image measured by “REFLECTMETER MODEL TC-6DS” (manufactured by Tokyo Denshoku) and the whiteness of the transfer paper The fog density (%) (= Dr (%) − Ds (%)) was calculated from the difference in degree (average reflectance Dr (%)), and the image fog at the end of the durability evaluation was evaluated. An amberlite filter was used as the filter. The evaluation results are shown in Table 3. A, B, and C are levels that do not cause problems in use, while D and E are levels that cause problems in use.
A: Less than 0.5% B: 0.5% or more and less than 1.0% C: 1.0% or more and less than 1.5% D: 1.5% or more and less than 5.0% E: 5.0% or more

<Evaluation of density unevenness>
Density unevenness evaluation was performed by continuously outputting 12,000 images with a printing rate of 1% in a high-temperature and high-humidity environment at 30 ° C. and 80% RH, and subsequently outputting three solid images. Thereafter, the density unevenness on the image was visually determined as follows. The evaluation results are shown in Table 3.
A: There is no density unevenness in all three sheets.
B: The density unevenness slightly occurs on the third sheet, but this is not a problem.
C: Slight density unevenness occurs on the second sheet, but the third sheet can withstand some practical use.
D: Complete density unevenness occurs slightly on the first sheet from the second sheet. There are practical problems.
E: Complete density unevenness from the first sheet.

[Example 2]
The same procedure as in Example 1 was performed except that the toner sealing member a was changed to the toner sealing member b shown in Table 2. The evaluation results are shown in Table 3.

Example 3
The same procedure as in Example 1 was performed except that the toner B produced by changing the polyester resin in the production example of the toner A to 3 parts by mass was used. Table 1 shows the physical properties of the toner particles B, and Table 3 shows the evaluation results.

Example 4
The same procedure as in Example 1 was performed except that toner C produced by changing the polyester resin in the production example of toner A to 7 parts by mass was used. Table 1 shows the physical properties of the toner particles C, and Table 3 shows the evaluation results.

Example 5
The same procedure as in Example 1 was performed except that the toner D and toner sealing member a shown below were changed to the toner sealing member c shown in Table 2. The evaluation results are shown in Table 3.

<Manufacture of toner D>
In the production of the toner A, the styrene monomer other than that used in the master batch dispersion 1 is changed to 15 parts by mass, the n-butyl acrylate monomer is changed to 24 parts by mass, and the low molecular weight polystyrene is changed to 25 parts by mass. Except that the polymerization initiator 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate in 70% toluene solution is changed to 12 parts by mass and the reaction temperature during polymerization is changed from 67 ° C. to 75 ° C. Toner D was prepared in the same manner as toner A. Table 1 shows the physical properties of the toner particles D.

Example 6
The same procedure as in Example 1 was performed except that toner E shown below and toner sealing member c were used. The evaluation results are shown in Table 3.

<Manufacture of toner E>
In the production of the toner A, the styrene monomer other than that used in the master batch dispersion 1 is changed to 16 parts by mass, the n-butyl acrylate monomer is changed to 23 parts by mass, and the low molecular weight polystyrene is changed to 25 parts by mass. Furthermore, the polymerization initiator 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate in a 70% toluene solution was added in 12 parts by mass, and the reaction temperature during the first stage polymerization after granulation was 67 ° C. A toner E was produced in the same manner as in the production of the toner A except that the temperature was changed from 75 ° C. to 75 ° C. Table 1 shows the physical properties of Toner Particles E.

Example 7
The same procedure as in Example 1 was performed except that the toner E and the toner sealing member a were changed to the toner sealing member d shown in Table 2. The evaluation results are shown in Table 3.

Example 8
The same procedure as in Example 1 was performed except that the toner A and the toner sealing member c were used. The evaluation results are shown in Table 3.

Example 9
The same procedure as in Example 1 was performed except that the toner F produced by changing the low molecular weight polystyrene in the production example of the toner A to 0.5 parts by mass and the toner sealing member c were used. Table 1 shows the physical properties of the toner particles F, and Table 3 shows the evaluation results.

Example 10
The production of the toner A was performed in the same manner as in Example 1 except that the toner G produced without adding low molecular weight polystyrene and the toner sealing member c were used. Table 1 shows the physical properties of the toner particles G, and Table 3 shows the evaluation results.

Example 11
The same procedure as in Example 1 was performed except that the toner H shown below and the toner sealing member c were used. The evaluation results are shown in Table 3.

<Manufacture of toner H>
In the production of the toner A, 15 parts by mass of styrene monomer other than that used in the master batch dispersion 1, 24 parts by mass of n-butyl acrylate monomer, 25 parts by mass of low molecular weight polystyrene, hydrocarbons 10 parts by weight of the system wax and 2 parts by weight of the polyester resin, and further 12 parts by weight of a 70% toluene solution of a polymerization initiator 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate In addition, toner H was produced in the same manner as in the production of toner A, except that the reaction temperature during the first stage polymerization after granulation was changed from 67 ° C. to 75 ° C. Table 1 shows the physical properties of the toner particles H.

[Comparative Example 1]
The same procedure as in Example 1 was performed except that the toner sealing member a was changed to a comparative toner sealing member e shown in Table 2. The evaluation results are shown in Table 3.

[Comparative Example 2]
The same procedure as in Example 1 was performed except that the toner B and the toner sealing member a were changed to the comparative toner sealing member f shown in Table 2. The evaluation results are shown in Table 3.

[Comparative Example 3]
The same operation as in Example 1 was performed except that the following comparative toner I was used. The evaluation results are shown in Table 3.

<Production of Comparative Toner I>
In the production of toner A, the styrene monomer other than that used in the master batch dispersion 1 is 18 parts by mass, the n-butyl acrylate monomer is 21 parts by mass, and the low molecular weight polystyrene is 25 parts by mass. The wax was changed to 13 parts by mass and the polyester resin to 0.5 parts by mass. Further, a 70% toluene solution of a polymerization initiator 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate was added to 12 parts. Toner I was produced in the same manner as in the production of toner A except that the reaction temperature at the first stage of polymerization after granulation was changed from 67 ° C. to 75 ° C. in parts by mass. Table 1 shows the physical properties of the toner particles I.

[Comparative Example 4]
The same operation as in Example 1 was performed except that the following comparative toner J was used. The evaluation results are shown in Table 3.

<Manufacture of comparative toner J>
In the production of toner A, the styrene monomer other than that used in the master batch dispersion 1 is 18 parts by mass, the n-butyl acrylate monomer is 21 parts by mass, and the low molecular weight polystyrene is 25 parts by mass. 13 parts by weight of the system wax and 2 parts by weight of the polyester resin, and further 12 parts by weight of a 70% toluene solution of a polymerization initiator 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate In addition, Toner J was produced in the same manner as in the production of Toner A, except that the reaction temperature during the first stage polymerization after granulation was changed from 67 ° C. to 75 ° C. Table 1 shows the physical properties of the toner particles J.

[Comparative Example 5]
The same operation as in Example 1 was performed except that the following comparative toner K and the toner sealing member c were used. The evaluation results are shown in Table 3.

<Manufacture of comparative toner K>
In the production of the toner A, a toner K was produced in the same manner as in the production of the toner A, except that low molecular weight polystyrene was not added, the hydrocarbon wax was changed to 5 parts by mass, and the polyester resin was changed to 9 parts by mass. Table 1 shows the physical properties of the toner particles K.

Claims (12)

In an electrophotographic toner container containing toner,
The electrophotographic toner container has a toner sealing member,
The said toner sealing member, and a thermoplastic elastomer plasticizer is added is used,
The plasticizer is paraffin oil;
In the molecular weight distribution chart of the molecular weight measured by gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble content of the thermoplastic elastomer to which the plasticizer is added , the area ratio of the whole component having a molecular weight of 800 or less Is 0.05% or more and 30.00% or less,
The toner has a binder resin, toner particles having containing a colorant and a wax component, and an inorganic fine powder,
After the toner particles were allowed to stand in an environment of 20 ° C. for 5 hours, the methanol concentration (%) at 50% transmission in a methanol wettability test was D20 , and the toner particles were left to stand in an environment of 40 ° C. for 5 hours. When methanol concentration (%) at the time of 50% transmission by the methanol wettability test is D40,
10.0 ≦ D20 ≦ 40.0
0 ≦ (D40−D20) ≦ 2.0
An electrophotographic toner container characterized by satisfying the relationship: In the molecular weight distribution chart of the molecular weight measured by gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble portion of the thermoplastic elastomer to which the plasticizer is added , the area ratio of the whole component having a molecular weight of 800 or less The toner container for electrophotography according to claim 1, wherein the toner content is 0.05% or more and 15.00% or less. The D20 and the D40 is,
0 ≦ (D40−D20) ≦ 1.0
請 Motomeko satisfying the relation 1 or 2 electrophotographic toner container according to. The D20 is,
15.0 ≦ D20 ≦ 25.0
The electrophotographic toner container according to any one of 請 Motomeko 1-3 satisfying the relationship. The viscosity at 100 ° C. of the toner, the electrophotographic toner container according to any one of claims 1 to 4 or less 3,000 Pa · s or more 60,000 Pa · s. The electrophotographic toner container according to any one of the toner particles is ~ claim 1 Ru Ah in the toner particles obtained by suspension polymerization method 5. An exposure step of forming a charging step of charging an electrostatic latent image by exposing the latent electrostatic image bearing member which is a static-in latent electrostatic image bearing member by a charging means the electrostatic latent image bearing member, an electronic a developing step of forming by developing the electrostatic latent image with the toner accommodated in the toner container of the toner image on the latent electrostatic image bearing member, labor via an intermediate transfer member the toner image In an image forming method having a transfer step of transferring to a transfer material without intervention,
The electrophotographic toner container has a toner sealing member,
The said toner sealing member, and a thermoplastic elastomer plasticizer is added is used,
In the molecular weight distribution chart of the molecular weight measured by gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble content of the thermoplastic elastomer to which the plasticizer is added , the area ratio of the total component having a molecular weight of 800 or less Is 0.05% or more and 30.00% or less,
The toner has a binder resin, toner particles having containing a colorant and a wax component, and an inorganic fine powder,
Methanol concentration (%) at the time of 50% permeation by methanol wettability test after leaving the toner particles in an environment of 20 ° C. for 5 hours and methanol after standing in an environment of D20 and 40 ° C. for 5 hours When the methanol concentration (%) at 50% permeation by the wettability test is D40,
10.0 ≦ D20 ≦ 40.0
0 ≦ (D40−D20) ≦ 2.0
An image forming method characterized by satisfying the relationship: In the molecular weight distribution chart of the molecular weight measured by gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble portion of the thermoplastic elastomer to which the plasticizer is added, the area ratio of the whole component having a molecular weight of 800 or less The image forming method according to claim 7, wherein the ratio is 0.05% or more and 15.00% or less. D20 and D40 are
0 ≦ (D40−D20) ≦ 1.0
The image forming method according to claim 7 or 8, satisfying the relationship: D20 is
15.0 ≦ D20 ≦ 25.0
The image forming method according to claim 7, wherein the relationship is satisfied. The image forming method according to claim 7, wherein the toner has a viscosity at 100 ° C. of 3,000 Pa · s to 60,000 Pa · s. The image forming method according to claim 7, wherein the toner particles are toner particles obtained by a suspension polymerization method.

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