JP2006259149A - Evaluation method and evaluation apparatus for flow property of electrostatic charge image developing toner, electrostatic charge image developing toner obtained by using the same, cartridge container stored with the same, and development method using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new highly accurate evaluation method and evaluation apparatus for flow property free from individual differences, and to provide an electrostatic charge image developing toner specified in physical properties by using the evaluation method and the evaluation apparatus, and a development method using the same. <P>SOLUTION: The evaluation method and evaluation apparatus for flow property of the electrostatic charge image developing toner are provided which comprise: a container housing the toner; a compacting means for putting the toner in the container into a compacted state; and a torque detecting means for detecting the torque of the toner powder phase in the compacted state, and the development method using the same is also provided. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an electrostatic charge developing toner fluidity evaluation method, a fluidity evaluation apparatus, an electrostatic charge developing toner obtained by using the toner, a cartridge container containing the toner, and a developing method using the same.

The image quality of copiers and printers has been improved, and recently, the reproducibility of fine dots has become very important. The dot reproducibility is greatly influenced by the fluidity in addition to the charge amount of the toner and developer, and the uniform toner layer or developer layer can be stably supplied to the fine latent image portion and transported. Is needed. In particular, in the one-component developing system, it is necessary to always provide a very thin layer on the developing roller stably, and toner fluidity has become important.
Further, as the image quality is improved, the toner used in the toner is becoming smaller in particle size and higher in function. For this reason, the structure of the toner has become complicated, and finer control at the time of production has become necessary. In particular, since the fluidity of toner affects various image qualities in addition to dot reproducibility, there is a need for a highly accurate evaluation method with no individual differences in terms of evaluation.
In addition, when the toner production method changes from the pulverization method to another method such as a polymerization method, the change in the flow characteristics with respect to the manufacturing conditions is large. Evaluation is required.
In addition, the toner is becoming low-temperature fixing and the oil-less fixing is progressed, and the toner base composition and structure become complicated, which affects the fluidity of the toner. For this reason, it is necessary to control the structure with higher precision than before, and accordingly, a highly sensitive fluidity evaluation method is required. Such fluidity evaluation methods include the following.

Patent Document 1 discloses a method for accurately evaluating the fluidity of a developer in an electrophotographic developing machine by measuring the time required for the toner to pass through and fall through a funnel sandwiched by a magnetic field. ing.
Patent Document 2 discloses a method for evaluating the fluidity of a developer by placing toner on a tiltable plate, gradually tilting the plate, and measuring the angle when the flow starts and ends. Are listed.
Furthermore, Patent Document 3 discloses that the amount of toner remaining in each sieve portion after a certain period of time is obtained by putting a plurality of sieves on top of each other and adding toner on the sieves to give horizontal and vertical vibrations to the sieve portion. A method of calculating by multiplying a preset coefficient is disclosed. However, with this method, there is a large variation in data, and there are differences depending on the measurer, and it has not been possible to evaluate the difference in fluidity between fine toners.

Japanese Patent Laid-Open No. 01-203941 Japanese Patent Laid-Open No. 04-116449 JP 2000-292967 A

  An object of the present invention is to provide a novel evaluation method and evaluation apparatus having high fluidity accuracy and no individual difference, and for use in electrostatic charge development whose physical properties are specified by using this evaluation method and evaluation apparatus. The object is to provide a toner and a developing method using the toner.

According to the first aspect of the present invention, the fluidity of a toner containing at least a resin and a pigment is determined by immersing a flat plate member in the toner powder phase, and the toner powder phase or the flat plate member in the longitudinal direction of the flat plate member. The present invention relates to a method for evaluating the fluidity of an electrostatic charge developing toner, characterized by measuring the force generated on a flat plate member.
According to the second aspect of the present invention, the toner powder phase is pressed in the direction perpendicular to the flat plate member by the compacting means in a state where the flat plate member is embedded in the toner powder phase, 2. The static body according to claim 1, wherein the body phase or the flat plate member is moved in a direction perpendicular to the consolidation direction and in the longitudinal direction of the flat plate member, and the force generated in the flat plate member is measured at this time. The present invention relates to a method for evaluating the fluidity of a charge developing toner.
A third aspect of the present invention relates to a method for evaluating the fluidity of an electrostatic charge developing toner according to claim 1 or 2, wherein the relative movement speed of the flat plate member is 0.1 to 10 mm / sec.
A fourth invention relates to a method of relative movement acceleration of the plate member is to evaluate the fluidity of the toner for developing an electrostatic image according to any one of claims 1 to 3, a 0.001~1mm / sec ^2.
The fifth aspect of the present invention is to evaluate the fluidity of the electrostatic charge developing toner according to any one of claims 1 to 4, wherein the plate-like member is reciprocated relatively 1 to 10 times relative to the toner powder phase. On how to do.
The sixth aspect of the present invention relates to the method for evaluating the fluidity of the electrostatic charge developing toner according to claim 1, wherein the relative movement amount of the flat plate member is 5 to 50 mm.
The seventh aspect of the present invention is the fluidity of the electrostatic charge developing toner according to any one of claims 1 to 6, which is measured such that the toner powder phase has a space ratio of 0.45 to 0.70. It relates to the method of evaluation.
According to an eighth aspect of the present invention, a flat plate member, a container containing toner, means for horizontally burying the flat plate member in the toner powder phase in the container, and compacting the toner powder phase downward from above the container Means for relatively moving the toner powder phase and the flat plate member in the longitudinal direction of the flat plate member in the toner powder phase, and means for detecting the force acting on the flat plate member at this time The present invention relates to a fluidity evaluation apparatus for toner for developing electrostatic charge.
A ninth aspect of the present invention relates to a fluidity evaluation apparatus for electrostatic charge developing toner, wherein the surface of the flat plate member has a regular uneven shape.
A tenth aspect of the present invention is for electrostatic charge development, wherein the cross-sectional shape of the flat plate member is a quadrangle having a thickness (length) t of 0.1 to 5 mm and an aspect ratio w / t of 3 to 10. The present invention relates to a toner fluidity evaluation apparatus.
In the eleventh aspect of the present invention, a compact member having a compaction pressure of 50 g / cm ² to the toner powder phase and a cross section in the moving direction of the flat plate member of 1 mm × 5 mm is used. / Sec, when the relative moving acceleration is 0.14 mm / sec ² , the value when the force acting on the flat plate member is measured with a load cell is 0.05 to 0.4 N, and at least electrostatic development including a resin and a pigment The present invention relates to a toner.
The twelfth aspect of the present invention relates to the electrostatic charge developing toner according to claim 11, wherein the toner has a weight average particle diameter of 4 to 8 μm.
The thirteenth aspect of the present invention relates to the electrostatic charge developing toner according to claim 11 or 12, wherein the toner has an average circularity of 0.9 to 0.99.
A fourteenth aspect of the present invention relates to a cartridge container selected from the group consisting of a toner cartridge and a process cartridge, which contains the electrostatic charge developing toner according to any one of claims 11 to 13.
The fifteenth aspect of the present invention relates to a developing method using the electrostatic charge developing toner according to any one of claims 11 to 13.
The sixteenth aspect of the present invention relates to the developing method according to claim 15, wherein the developing is performed by applying an AC bias voltage component.
The seventeenth aspect of the present invention relates to a one-component developing method, wherein contact or non-contact development is performed using the electrostatic charge developing toner according to any one of claims 11 to 13.
The eighteenth aspect of the present invention relates to the one-component developing method according to claim 17, wherein a doctor roller and / or a supply roller are used.
A nineteenth aspect of the present invention relates to a two-component developing method, wherein the development is performed using the electrostatic charge developing toner according to any one of claims 11 to 13 and a carrier having an average particle diameter of 20 to 70 μm.

  In this evaluation method, a long flat plate-like member is provided in the powder phase, the toner powder phase or the flat plate member is moved in the longitudinal direction, the force applied to the flat plate member at that time is measured, and the value of the force is determined. It evaluates fluidity. The surface shape of the flat plate member may be anything, and the surface may be uneven or may not be uneven. However, in the case of a flat plate-like member having an uneven surface, it is necessary to have a regular uneven shape so as not to depend on the moving direction of the flat plate member. The material of the flat plate member may be hard or soft. For example, a flat plate made of a flat plate with a groove, Cu, Fe, SUS or the like may be used. A flat plate member having a cross-sectional shape of a rectangle having a thickness (length) t of 0.1 to 5 mm and an aspect ratio w / t of 3 to 10 is suitable. If the thickness of the flat plate member is smaller than 0.1 mm, the contact area between the flat plate member and the toner powder phase at the time of driving is not stabilized, so the variation in force applied to the flat plate member becomes large and there is a small difference in fluidity. Cannot be evaluated. On the contrary, when the thickness of the flat plate member is larger than 5 mm, it is strongly influenced by the side of the flat plate having a different compaction state, and it is difficult to accurately measure the force acting on the flat plate member, and the toner fluidity. It is not suitable for evaluation. In addition, when the aspect ratio w / t of the cross section of the flat plate member is smaller than 3, the contribution of the thickness of the flat plate becomes large, so that the flat plate member is strongly influenced by the side of the flat plate having a different consolidated state. When the force acting on the flat plate member is difficult to measure accurately and the aspect ratio w / t is larger than 10, the distribution of the contact state between the flat plate member and the toner powder phase becomes large. Is not suitable for evaluation of toner fluidity.

  The length of the flat plate member needs to be long enough so that the flat plate member continuously exists in the toner powder phase even if the toner powder phase or the flat plate member moves. Further, when a groove is cut on the surface of the flat plate member, the friction component between the material surface of the flat plate member and the toner particles is not measured, but the friction component between the toner particles and the toner particles can be measured. It becomes possible. For this purpose, when the flat plate member moves relatively in the toner powder phase, the toner particles enter the groove cut on the surface of the flat plate member, and the toner particles and the surrounding toner are included. It is necessary to measure the friction state with the particles. The shape of the groove is not limited, but it is necessary to devise so that the contact between the material surface of the flat plate member and the toner particles becomes small.

  An example is shown in FIG. This is formed by cutting grooves on the upper and lower surfaces of the flat plate member, and the grooves have a sawtooth shape in which the cross section of the grooves is triangular irregularities. In this case, the contact between the flat member material surface and the toner particles is only at the tip of the triangular groove crest. Most of the contact is between the toner particles that have entered the groove and the surrounding toner particles. Any material may be used for the flat plate-like member, but a material that is easy to process, has a hard surface, and does not deteriorate is preferable. A material that is not charged is suitable. Examples of this are SUS, Al, Cu, Au, Ag, brass, and the like.

The force characteristics of the toner powder change depending on the relative movement speed of the flat plate member and the relative movement acceleration of the flat plate member. In this measurement, in order to increase the accuracy of the measurement, the measurement is performed by lowering the moving speed and moving acceleration of the flat plate member so that the delicate contact state between the toner particles can be measured. Therefore, the measurement conditions were as follows.
-Relative moving speed of flat plate member: 0.1 to 10 mm / sec
-Relative movement acceleration of flat plate member: 0.001 to 1 mm / sec ²
If the relative movement speed of the flat plate member is slower than 0.1 mm / sec, it is easily affected by the delicate state of the toner powder phase, which causes a problem of force measurement variation and is not suitable for measurement. When it is faster than 10 mm / sec, toner scattering, jetting, etc. occur, and it is not suitable because it cannot be measured stably.
When the relative movement acceleration of the flat plate member is slower than 0.001 mm / sec ² , it is easily affected by the delicate state of the toner powder phase, and a measurement variation problem occurs, which is not suitable for measurement. When the speed is faster than 1 mm / sec ^2, toner splattering and jetting occur, and the contact state between the toner particles and the flat plate member changes, which is not suitable for fluidity evaluation.

Examples of the configuration of the apparatus include those shown in FIGS. A plate-like member is used as a detection member, which is provided in the toner powder phase, and its tip is connected to a load cell which is a force detector. Specifically, the case where the flat plate-shaped detection member is flexible and the case where it is a rigid body are different.
When the flat plate-shaped detection member is flexible, a weight is attached to the end of the guide pulley using a guide pulley as shown in FIG. To. At that time, the flat plate-shaped detection member is set so as to pass through the central portion of the toner powder phase. The flat plate detection member may be arranged in any direction in the toner powder phase, but the flat plate detection member may be arranged in a direction (a direction parallel to or perpendicular to the surface of the toner powder phase) that applies a uniform tension or compressive force. Is suitable.
On the other hand, when the flat plate-shaped detection member is a rigid body, a guide pulley is provided on both sides of the sample container, and a detection rod is placed thereon. Also at this time, the flat plate detection member (detection rod) is set so as to pass through the central portion of the toner powder phase. Naturally, the flat plate-shaped detection member optimizes the position through holes formed at appropriate positions on both sides of the side surface of the sample container. The hole on the side surface of the sample container needs to be a hole that matches the size of the flat plate-shaped detection member so as not to leak toner. However, when the tolerance of the size of the hole is small, a contact state is likely to occur between the flat plate detection member and the hole, which is not good because it is reflected in the force characteristics as a friction component. Therefore, an appropriate gap is required between the flat plate detection member and the hole.
The sample container is placed on the sample stage, and the sample stage is driven by the drive unit in parallel with the arrangement direction of the flat plate detection members. The force acting on the flat plate detection member at that time is detected by the load cell. The amount of movement of the sample stage is measured with a position detector, and the relationship between the amount of movement and the force is obtained as measurement data on a PC or the like.
At the time of measuring the toner, the toner is put in a sample container, and a load is applied to the toner powder phase using a piston so that the toner powder phase is pre-consolidated, and the sample stage is driven to perform measurement. At that time, the sample stage is moved in the direction perpendicular to the compaction direction of the toner powder phase. This configuration is merely an example, and other configurations such as fixing a sample container containing toner, moving the flat plate detection member itself, and measuring the force applied to the flat plate detection member may be used. In other words, since the friction component generated between the toner powder phase and the flat plate member is measured, the flat plate member may be fixed and the toner powder phase may be moved. The flat plate member may be moved while fixing the phase.

  As the shape of the flat plate member, as described above, a cross-sectional shape having a thickness (length) t of 0.1 to 5 mm and an aspect ratio w / t of 3 to 10 is suitable. The length of the flat plate member needs to be long enough so that the flat plate member continuously exists in the toner powder phase even when the flat plate member moves. The shape of the groove may be any shape, but it is necessary to have a regular uneven shape so as not to depend on the moving direction of the flat plate member. Further, the groove shape of the flat plate member should have a simple uneven shape so that the same flat plate member can be formed any number of times. An example of this is shown in FIG. 3 (the shape seen from the side). There are a sawtooth shape having triangular irregularities, an irregular shape in which a coil is wound around a core wire, and a surface having no irregularities. . The material of the container is not limited, but a conductive material is suitable so as not to be affected by charging with the powder. In addition, since the measurement is performed while changing the powder, it is preferable that the surface is close to a mirror surface in order to reduce dirt. The size of the container is important, and in order to increase the uniformity of compaction when the toner powder phase is compacted, it is necessary to select a size that increases the diameter of the toner container relative to the thickness of the toner powder phase.

  A load cell with a wide load range and high resolution is suitable. The position detector includes a linear scale, a displacement sensor using light, etc., but a specification of 0.01 mm or less is suitable for accuracy. The drive unit is preferably one that can be driven with high accuracy using a servo motor or a stepping motor. In order to move the sample stage in parallel with the flat columnar member, a guide rail is provided, and the sample stage is moved along the guide rail. Since the sample stage not only moves in a certain direction but also reciprocates back and forth, the level of the sample stage must be adjusted accurately using a level or the like. .

  The means for compacting the toner powder phase, for example, the piston, is made of Cu, Al, SUS, brass, or the like, and the surface and side surfaces need to have a smooth surface close to a mirror surface with no irregularities on the surface. Since the powder is compacted many times, a hard material that does not easily scratch is suitable.

  The sample container is also preferably made of a hard material that is not easily deformed, but Cu, Al, SUS, brass or the like is used in terms of workability. Since the sample is changed and used many times, the inner surface of the container may be surface-treated so as to be hard so as not to be damaged.

  In the measurement, the sample container is previously placed on the sample stage, and the flat plate-shaped detection member is set through the hole on the side surface of the sample container. A fixed amount of toner is put into the sample container, and the toner powder phase is consolidated by a piston. Thereafter, the piston is mounted and the sample stage is moved under a predetermined driving condition in a state where the piston is kept compact, and the flat plate member is relatively moved in the toner powder phase. At that time, the force acting on the flat plate member is measured by the load cell. Force measurement is performed under the specified speed and acceleration conditions. It is also necessary to determine the driving direction of the sample stage and the number of reciprocations.

  Of course, it is possible to measure only in a certain direction, but it is better to perform reciprocal measurement when looking at the dependency of the moving direction. In that case, the number of reciprocations is preferably 1 to 10 times. Even if the reciprocating measurement is performed more than 10 times, there is almost no change and the measurement is meaningless. The moving distance is basically arbitrary, and it is preferable to move to a position where data is stable. However, a moving amount of 5 to 50 mm is suitable from the relationship of measurement time and the like. If it is smaller than 5 mm, there arises a problem that the data is not stable in a region where the force characteristic is greatly changed. If it is larger than 50 mm, the force characteristic is stabilized, but there is a problem that the measurement time becomes long.

The measurement mode can be performed under any conditions, but examples include the following measurement mode.
(A) Place the container on the sample stage.
(B) The flat plate member is set through the hole on the side surface of the sample container.
(C) Put a certain amount of toner in the sample container.
(D) The toner powder phase is pressurized by a piston to create a compacted state.
(E) The sample stage is driven in a consolidated state, and the force at that time is measured.
(F) When moving to a preset distance, the moving operation is stopped.
(G) The sample stage is returned to the start position (first home position).
Measurement is performed by repeating the above operations (a) to (g). The change in force may be measured by reciprocating a certain distance without stopping the movement of the sample stage.

  As another measurement method, after the toner powder phase is consolidated by the piston, the sample stage is moved and stopped for a fixed distance, and then the fixed distance is further moved and stopped (a single operation may be performed). ) Measure the force change at that time.

  In this measurement method, the space ratio of the toner powder phase becomes important, but this space ratio indicates the degree of compaction due to pressing, and our experimental results show that the space ratio is stable when the space ratio is 0.45 or more. Measurement was possible. If it is less than 0.45, the subtle difference in the consolidated state has an effect on the force characteristics, and stable measurement is difficult. The range of the space ratio of the toner powder phase was 0.45 to 0.70 including various measurement methods. When it is larger than 0.70, the contact state between the toner powder phase and the flat plate member is not constant, and is not suitable for stable measurement. However, the measurement system and measurement conditions are not limited to this. Of course, this evaluation method can also be used to evaluate powders other than toner.

  The toner measured by this evaluation method preferably has a weight average particle diameter of 4 to 8 μm, more preferably 5 to 7 μm, in order to realize a high-quality image. If the weight average particle diameter is less than 4 μm, problems such as contamination in the machine due to toner scattering during long-term use, image density reduction in a low-humidity environment, and poor photoconductor cleaning are likely to occur, and there is a concern about the effect on the human body. When the weight average particle size exceeds 8 μm, the resolution of minute spots of 100 μm or less is not sufficient, and the image quality tends to be inferior due to many scattering to non-image areas.

  The developer using this toner needs to have an average particle diameter of the carrier of 20 to 70 μm in order to realize a high quality image. When the average particle diameter of the carrier is in the range of 20 to 70 μm, the charge amount of the toner can be made more uniform when the toner concentration in the developing machine is in the range of 2 to 10% by weight. When it is smaller than 20 μm, carrier particles are likely to adhere to the photoreceptor, and the stirring efficiency with the toner is deteriorated, so that it is difficult to obtain a uniform charge amount of the toner. On the other hand, when the average particle diameter of the carrier exceeds 70 μm, fine image reproducibility deteriorates and high image quality cannot be obtained.

  The components of the toner of the present invention will be described below.

  The resin used in the toner of the present invention is preferably a polyester resin or / and a polyol resin conventionally used in color toners. This is because polyester resins and polyol resins are superior in low-temperature fixability and relatively good in heat-resistant storage stability, compared to styrene-acrylic resins that have been widely used in the past. However, polyester resin and polyol resin have poor dispersibility of the release agent compared to styrene-acrylic resin, and therefore, the pulverization stress tends to concentrate on the interface between the resin and the wax during pulverization. It is easy to pulverize at the interface, and the surface of the pulverized toner is exposed to more than the ratio of the added release agent, and there is a surface that deteriorates the stability of the toner. It is preferable to do. Examples of resins that can be used in the present invention include polystyrene resins, epoxy resins, polyester resins, polyamide resins, styrene-acrylic resins, styrene methacrylate resins, polyurethane resins, vinyl resins, polyolefin resins, styrene butadiene resins, phenol resins, butyral resins, Examples include terpene resins and polyol resins.

  Examples of vinyl resins such as styrene-acrylic resins include homopolymers of styrene such as polystyrene, poly-p-chlorostyrene, polyvinyltoluene, and the like: styrene-p-chlorostyrene copolymers, styrene- Propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, 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 Polymer, styrene-vinyl methyl ether Polymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer Styrene copolymers such as coalescence and styrene-maleic acid ester copolymer: polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate and the like. These resins may be used alone or in combination.

The polyester resin is composed of a dihydric alcohol as shown in the following group A and a dibasic acid salt as shown in the group B, and further a trivalent or higher alcohol as shown in the group C or Carboxylic acid may be added as a third component.
Group A: ethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,4-bis (hydroxymethyl) ) Cyclohexane, bisphenol A, hydrogenated bisphenol A, polyoxyethylenated bisphenol A, polyoxypropylene (2,2) -2,2'-bis (4-hydroxyphenyl) propane, polyoxypropylene (3,3)- 2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2,0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2,0) -2,2'-bis (4-hydroxyphenyl) propane and the like.
Group B: maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, succinic acid, adipic acid, sebacic acid, malonic acid, linolenic acid, or These acid anhydrides or esters of lower alcohols.
Group C: Trivalent or higher alcohols such as glycerin, trimethylolpropane and pentaerythritol, and trivalent or higher carboxylic acids such as trimellitic acid and pyromellitic acid. As the polyol resin, an alkylene oxide adduct of an epoxy resin and a dihydric phenol, or a compound having one active hydrogen in the molecule that reacts with the glycidyl ether and the epoxy group, and an active hydrogen that reacts with the epoxy resin in the molecule. There are those obtained by reacting two or more compounds.

There is no restriction | limiting in particular as a pigment used by this invention, For example, the following can be used.
Examples of black pigments include azine dyes such as carbon black, oil furnace black, channel black, lamp black, acetylene black and aniline black, metal salt azo dyes, metal oxides, and composite metal oxides.
Examples of yellow pigments include cadmium yellow, mineral fast yellow, nickel titanium yellow, navel yellow, naphthol yellow S, Hansa Yellow G, Hansa Yellow 10G, Benzidine Yellow GR, Quinoline Yellow Lake, Permanent Yellow NCG and Tartrazine Lake. Can be mentioned.
Examples of orange pigments include molybdenum orange, permanent orange GTR, pyrazolone orange, vulcan orange, indanthrene brilliant orange RK, benzidine orange G, and indanthrene brilliant orange GK.
Examples of red pigments include Bengala, Cadmium Red, Permanent Red 4R, Resol Red, Pyrazolone Red, Watching Red Calcium Salt, Lake Red D, Brilliant Carmine 6B, Eosin Lake, Rhodamine Lake B, Alizarin Lake, Brilliant Carmine 3B. It is done.
Examples of purple pigments include fast violet B and methyl violet lake.
Examples of blue pigments include cobalt blue, alkali blue, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partially chlorinated, first sky blue, and indanthrene blue BC.
Examples of green pigments include chrome green, chromium oxide, pigment green B, and malachite green lake.
These can use 1 type (s) or 2 or more types.
Especially in color toners, uniform dispersion of good pigments is essential. Instead of putting pigments directly into a large amount of resin, a master batch in which pigments are once dispersed at a high concentration is prepared and diluted. The method of throwing in is used. In this case, a solvent is generally used to help dispersibility. However, there is a problem of environment and the like, and in the present invention, water is used without using a solvent. When water is used, temperature control is important so that residual moisture in the masterbatch does not become a problem.

In the toner of the present invention, a charge control agent may be blended (internally added) inside the toner particles, but in some cases, it may be used by mixing (externally adding) with the toner particles. The charge control agent makes it possible to control the optimum charge amount according to the development system. In particular, in the present invention, the balance between the particle size distribution and the charge amount can be further stabilized.
For controlling the toner to be positively charged, nigrosine and quaternary ammonium salts, triphenylmethane dyes, imidazole metal complexes and salts can be used alone or in combination of two or more. Further, salicylic acid metal complexes, salts, organic boron salts, calixarene compounds, and the like are used for controlling the toner to be negatively charged.

In the toner according to the present invention, a release agent is internally added to prevent offset at the time of fixing.
Examples of the release agent include natural waxes such as candelilla wax, carnauba wax, and rice wax, montan wax, paraffin wax, sazol wax, low molecular weight polyethylene, low molecular weight polypropylene, and alkyl phosphate ester.
The melting point of these release agents is preferably 65 to 90 ° C. When the temperature is lower than this range, blocking during storage of the toner tends to occur, and when the temperature is higher than this range, an offset is likely to occur in a region where the fixing roller temperature is low.

  For the purpose of improving the dispersibility of the release agent or the like, an additive for dispersing the release agent may be further added. Examples of the release agent dispersing additive include styrene acrylic resin, polyethylene resin, polystyrene resin, epoxy resin, polyester resin, polyamide resin, styrene methacrylate resin, polyurethane resin, vinyl resin, polyolefin resin, styrene butadiene resin, phenol resin, butyral There are resins, terpene resins, polyol resins, etc., and a mixture of two or more of these resins may be used.

    Examples of the method for producing the toner according to the present invention include a pulverization method and a polymerization method (suspension polymerization, emulsion polymerization dispersion polymerization, emulsion aggregation, emulsion association, etc.), but are not limited to these production methods.

  As an example of the pulverization method, first, the above-mentioned resin, pigment or dye as a colorant, charge control agent, release agent, other additives, etc. are sufficiently mixed by a mixer such as a Henschel mixer, and then batch type. The constituent materials are well kneaded using a two-roll, Banbury mixer, continuous twin-screw extruder, continuous single-screw kneader, or the like, and cut after rolling and cooling. The toner kneaded product after cutting is crushed, coarsely pulverized using a hammer mill, etc., and further pulverized by a fine pulverizer or mechanical pulverizer using a jet stream, and a classifier or Coanda effect using a swirling airflow Is classified to a predetermined particle size by a classifier using Thereafter, an additive composed of inorganic particles or the like is adhered or fixed to the particle surface by a mixer. The toner particles after the mixing step are sampled, and the fluidity is evaluated using this evaluation method. On the other hand, the product that has undergone the mixing step is passed through a sieve of 250 mesh or more to remove coarse particles and agglomerated particles, thereby obtaining the toner of the present invention.

In this case, in the sampling (sampling) inspection, a sample is put in a sample container, and the sample container is directly placed on the sample stage of the evaluation apparatus shown in FIG. The relative movement speed of the flat plate member was 0.1 to 10 mm / sec, and the relative movement acceleration of the flat plate member was 0.001 to 1 mm / sec ² . In the measurement, the flat plate member is fixed, the sample stage is driven by a preset moving distance of 5 mm or more, and then returned to the original initial position. The force applied to the flat plate member at this time is measured to evaluate the fluidity of the toner.

When the toner fluidity is evaluated by this evaluation method, the measured value (force) and the toner fluidity have the following relationship.
If the force is small, the fluidity is good.
If the force is large, the fluidity is bad.

The characteristics of the present evaluation method using the flat plate-shaped detection member are as follows. Since the sample sample can be measured quickly and easily as it is, it is possible to perform highly accurate measurement without individual differences.
(I) Non-destructive inspection.
(Ii) The sample can be measured as it is.
(Iii) It can be measured in a short time.
(Iv) Anyone can easily measure.

  Therefore, measurement on the production line is also possible, and it can be installed between each process in the production process to evaluate the quality during the process. For example, after passing through the mixing process, a sample extraction / measurement zone is provided in the middle of transporting the powder sample to the next process, and a valve is opened and closed at a certain timing to transport a certain amount of sample to the measurement unit. The tip of the measurement part is a container made of SUS or the like, and is directly measured by this evaluation method. Alternatively, the container is taken to the evaluation apparatus in another nearby location, placed on the sample stage, and measured by the evaluation method. After the measurement, the toner is returned to the original sample. As a result of the evaluation, if the numerical value is out of the predetermined setting range, the sample is not sent to the filling process, but is sent to the toner reprocessing process. These mechanisms can be applied to the inspection after the pulverization / classification process, which is the process before the mixing process, the inspection after the air sieving process after the mixing process, the inspection before filling, and the like. (See Figure 5.)

  It is also possible to independently use a toner evaluation apparatus having these functions as an evaluation apparatus in the development stage.

In the case of toner, as described above, the measurement value of force in this evaluation method indicates fluidity, and quantitative evaluation is possible. The conventional evaluation method can evaluate the difference between toners, but there is a problem that it cannot be evaluated on the same soil if the toner types are different. However, the value measured by this evaluation method is a force value as a powder characteristic, and is a value that can be evaluated on the same earth regardless of the type of toner and the particle size. become.
The force characteristics at the time of movement of the flat plate member in the toner powder phase are closely related to the fluidity of the powder. When the fluidity of the powder is good, it is between the individual powder particles. Since the adhesive force is small, it is easy to move, and even if the flat plate member is moved in the powder phase, the force is small. However, when the flowability of the powder is poor, it is difficult to move because the adhesion between the powder particles is large, and when the flat plate member is moved within the powder phase, the flat plate The force applied to the shaped member increases.
Therefore, in the evaluation method of the present invention, the fluidity can be evaluated according to the following relationship.
When fluidity is good → The force when moving in the powder phase is small.
When the fluidity is poor → The force when moving in the powder phase is large.

The fluidity of the toner is almost determined by the mixing process in the toner preparation process. That is, the fluidity of the toner particles varies greatly depending on the state in which the additive composed of inorganic particles adheres to or adheres to the surface of the toner particles.
The mixing state of the toner varies depending on the mixing conditions (amount charged, the number of rotations, a mixing time, etc.) in the mixing step. Therefore, the mixing conditions play an important role in the fluidity, and the evaluation of the fluidity after the mixing process is important.

  In order to achieve high image quality in printers and copiers, it is necessary to improve the reproducibility of extremely minute dots. In order to realize this, toner development that is faithful to a very small latent image is required. In order to enable this faithful development, it is necessary to supply a uniform toner brush to the development area. For this purpose, it is necessary that the toner charge amount is in an appropriate condition. However, the toner is easy to move and transport so that a uniform toner brush can be constantly supplied to the development area. It becomes important. That is, in order to improve the fine dot reproducibility, it is necessary to increase the fluidity of the toner.

  In order to realize high image quality, it is necessary to improve the cleaning property so that past images are not affected even if different images are created many times. For this purpose, it is necessary to have fluidity so that the toner particles can be neatly removed by a cleaning member such as a blade. If the fluidity of the toner particles is too good, the toner particles easily pass through the blade, resulting in poor cleaning. On the contrary, when the fluidity of the toner particles is poor, the toner particles are fixed to the photoreceptor or the like, resulting in poor cleaning. Therefore, it is necessary to optimize the fluidity of the toner particles.

  Therefore, as a result of evaluating the fluidity of the toner by this method using a flat member and investigating the relationship between the dot reproducibility and the cleaning property, a very strong correlation exists, and the flat member (thickness: 1 mm, When the aspect ratio: 5) moves relatively in the powder phase, “the value of the force generated in the flat plate member is 0.05 to 0.4 N, preferably 0.1 to 0.35 N” It was found that dot reproducibility and cleanability improved when exhibiting such force characteristics. If the force value is less than 0.05 N, the fluidity of the toner is too good, so that the toner can pass under the blade, resulting in poor cleaning and a reduction in image quality. When it was larger than 0.4N, the fluidity was lowered, the dot reproducibility and the cleaning property were also deteriorated, and the image quality was lowered.

  As a method for producing the toner according to the present invention, methods other than the pulverization method are conceivable. As an example of the polymerization method, a monomer composition in which a colorant, a charge control agent and the like are added to a monomer is suspended in an aqueous medium. Toner particles are obtained by turbidity and polymerization. The granulation method is not particularly limited.

For example, an oil dispersion is prepared by adding a polyester-based prepolymer containing at least an isocyanate group, a pigment-based colorant, and a release agent in an organic solvent, and this oil-based dispersion is added to the presence of inorganic particles and / or polymer particles. This is then dispersed in an aqueous medium, and then the prepolymer is reacted with a polyamine and / or a monoamine having an active hydrogen-containing group to form a urea-modified polyester resin having a urea group. The toner of the present invention can be obtained by removing the liquid medium contained in the dispersion containing the polyester resin.
This urea-modified polyester resin has a Tg of 40 to 65 ° C., preferably 45 to 60 ° C., a number average molecular weight (Mn) of 2500 to 50000, preferably 2500 to 30000, and a weight average molecular weight (Mw) of 10,000 to 500,000, preferably 30,000 to 100,000.
This toner contains, as a binder resin, a urea-modified polyester resin having a urea bond that has been increased in molecular weight by the reaction between the prepolymer and the amine, and a colorant is highly dispersed in the binder resin. is there.

  Even in the case of these methods, inspection after granulation, inspection after treatment of charge control agent, inspection after mixing process of additive, inspection after air sieving process after mixing process, inspection before filling, etc. Either is applicable.

  In addition, although the fluidity is affected by the toner shape, in the case of a very spherical toner having an average circularity of 0.9 to 0.99, the fluidity is excellent, and dot reproducibility and cleaning properties are improved. Excellent image quality can be achieved.

  Further, when used as a two-component developer, a two-component developer is obtained by mixing with a magnetic carrier described later at a predetermined mixing ratio.

  This toner is used as a one-component developer used in a contact or non-contact development system. As the contact or non-contact development method, various known methods are used. For example, there are a contact development method using an aluminum sleeve, a contact development method using a conductive rubber belt, and a non-contact development method using a development sleeve in which a conductive resin layer containing carbon black or the like is formed on the surface of an aluminum base tube. .

  In addition, when an AC bias voltage component is applied during development using the present toner, development efficiency is improved and image characteristics are improved.

In the one-component development method, the present toner is preferably used in a development method in which a roller blade for making the toner layer uniform and a supply roller for supplying toner are provided at the outlet of the toner supply unit. In the case of such a system, not only filming on the photoconductor but also filming on the doctor roller and the supply roller occurs. For this reason, the toner layer cannot be formed uniformly, the toner charge becomes non-uniform, and the toner charge amount becomes small. For this reason, poor development occurs.
However, when the toner of the present invention is used, filming on the doctor roller and the supply roller does not occur, stable development is performed, and the system has excellent durability characteristics. (See Figure 6.)

  Since the present toner has excellent fluidity, it can be stored in a cartridge container and is suitable for an apparatus configured to convey toner from the cartridge container to the developing unit. The present toner can also be used in a process cartridge or the like that integrally supports a toner cartridge filled with electrostatic charge developing toner and a developing unit, and is detachable from the main body of the image forming apparatus.

  Further, when the magnetic toner is used, magnetic particles may be internally added to the toner particles. Examples of the magnetic material include ferromagnetic materials such as ferrite, magnetite, iron, nickel, cobalt, and alloys thereof. The average particle size of the magnetic material is preferably 0.1 to 1 μm. The content of the magnetic material is preferably 10 to 70 parts by weight with respect to 100 parts by weight of the toner.

  As the carrier used in the two-component developer, known carriers can be used. For example, magnetic particles such as iron powder, ferrite powder, nickel powder, magnetite powder, or the surface of these magnetic particles are made of fluorine resin or vinyl resin. And those treated with a silicone-based resin or the like, or magnetic particle-dispersed resin particles in which magnetic particles are dispersed in the resin. The average particle size of these magnetic carriers is preferably 20 to 70 μm.

As described above, the one-component or two-component developer of the present invention can be used by adding inorganic fine powder to the toner as a fluidity improver.
As the inorganic fine powder of the present invention, Si, Ti, Al, Mg, Ca, Sr, Ba, In, Ga, Ni, Mn, W, Fe, Co, Zn, Cr, Mo, Cu, Ag, V, Zr, etc. And oxides and composite oxides. Of these, fine particles of silicon dioxide (silica), titanium dioxide (titania), and alumina are preferably used.

Furthermore, it is effective to perform surface modification treatment with a hydrophobizing agent or the like. Typical examples of the hydrophobizing agent include the following.
Dimethyldichlorosilane, trimethylchlorosilane, methyltrichlorosilane, allyldimethyldichlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, p-chloroethyltrichlorosilane, Chloromethyldimethylchlorosilane, chloromethyltrichlorosilane, hexaphenyldisilazane, hexatolyldisilazane, etc.

  The inorganic fine powder is preferably used in an amount of 0.1 to 2% by weight based on the toner. If it is less than 0.1% by weight, the effect of improving toner aggregation is poor, and if it exceeds 2% by weight, problems such as toner scattering between fine wires, contamination in the machine, scratches and abrasion of the photoreceptor tend to occur. is there.

  Further, the developer of the present invention may further contain other additives, for example, a lubricant powder such as Teflon (registered trademark) powder, zinc stearate powder, and polyvinylidene fluoride powder; Abrasives such as cerium powder, silicon carbide powder, and strontium titanate powder; or a conductivity-imparting agent such as carbon black powder, zinc oxide powder, and tin oxide powder can be used in small amounts as a developability improver.

(1) With the evaluation method and evaluation apparatus of the present invention, it is possible to accurately evaluate the difference in fluidity between fine toners.
(2) The measured value obtained by the evaluation method of the present invention is a titer as a powder characteristic, and is a value that can be evaluated on the same soil regardless of the type of toner or the particle size. This is a very general evaluation value.
(3) The data obtained by the evaluation method and evaluation apparatus of the present invention has no individual difference and is highly accurate.
(4) When the toner of the present invention is used, the cleaning property is good and filming to the doctor roller and the supply roller does not occur.

Hereinafter, although an Example is described, this does not limit this invention at all. This time, toners with different mixing conditions were prepared, the toner fluidity was evaluated using this evaluation method, the cleaning property was evaluated by the image density on the photoconductor after passing through the blade, and the dot reproducibility was evaluated. It was rated on a five-point scale. The fluidity of the toner was measured under the following conditions, and the force when the flat plate member moved relatively in the toner powder phase (in the table, indicated as pulling force) was measured.
Flat plate member: Brass (thickness: 1 mm, aspect ratio: 5)
-Relative moving speed of flat plate member: 1.40 mm / sec
-Relative movement acceleration of flat plate member: 0.14 mm / sec ²
・ Consolidation pressure by piston: 50 g / cm ²
In addition, all the parts in the following mixing | blending are a weight part.

Example 1
Resin Polyester resin 100 parts Colorant Magenta pigment (CI Pigment Red 57) 4 parts Charge control agent Zinc salicylate 5 parts The above raw materials are thoroughly mixed with a mixer and then kneaded at a barrel temperature of 100 ° C with a twin screw extruder. Melt kneading was performed at a machine rotation speed of 110 rpm. The kneaded product was rolled and cooled, coarsely pulverized by a cutter mill, pulverized by a fine pulverizer using a jet stream, and then classified into a particle size distribution having a weight average particle size of 6.5 μm using a swirling air classifier.
To 100 parts of the base colored particles thus obtained, an additive was mixed under the following mixing conditions to prepare a toner.
Additive Silica fine powder 1.0 part
Titanium oxide fine powder 0.3 part Mixing rotation speed 1000rpm
Mixing time 120sec
Mixer Supermixer After the toner was prepared, the fluidity was measured by this evaluation method.
The obtained toner was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation, cleaning experiments, and running experiments were performed. The results are shown in Table 1.

Example 2
Kneading, pulverization, and classification were carried out using the same raw materials and production methods as in Example 1, and classified into a particle size distribution with a weight average particle size of 6.5 μm.
To 100 parts of the base colored particles thus obtained, an additive was mixed under the following mixing conditions to prepare a toner.
Additives Silica fine powder 1.2 parts
Titanium oxide fine powder 0.3 part Mixing rotation speed 1000rpm
Mixing time 120sec
Mixer Supermixer After the toner was prepared, the fluidity was measured by this evaluation method.
The obtained toner was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation, cleaning experiments, and running experiments were performed. The results are shown in Table 1.

Example 3
Kneading, pulverization, and classification were carried out using the same raw materials and production methods as in Example 1, and classified into a particle size distribution with a weight average particle size of 6.5 μm.
To 100 parts of the base colored particles thus obtained, an additive was mixed under the following mixing conditions to prepare a toner.
Additive silica fine powder 1.5 parts
Titanium oxide fine powder 0.3 part Mixing rotation speed 1000rpm
Mixing time 120sec
Mixer Supermixer After the toner was prepared, the fluidity was measured by this evaluation method.
The obtained toner was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation, cleaning experiments, and running experiments were performed. The results are shown in Table 1.

Example 4
Kneading, pulverization, and classification were carried out using the same raw materials and production methods as in Example 1, and classified into a particle size distribution with a weight average particle size of 6.5 μm.
To 100 parts of the base colored particles thus obtained, an additive was mixed under the following mixing conditions to prepare a toner.
Additive Silica fine powder 1.8 parts
Titanium oxide fine powder 0.3 part Mixing rotation speed 1000rpm
Mixing time 120sec
Mixer Supermixer After the toner was prepared, the fluidity was measured by this evaluation method.
The obtained toner was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation, cleaning experiments, and running experiments were performed. The results are shown in Table 1.

Example 5
Kneading, pulverization, and classification were carried out using the same raw materials and production methods as in Example 1, and classified into a particle size distribution with a weight average particle size of 6.5 μm.
To 100 parts of the base colored particles thus obtained, an additive was mixed under the following mixing conditions to prepare a toner.
Additive Silica fine powder 1.8 parts
Titanium oxide fine powder 0.3 part Mixing rotation speed 1200rpm
Mixing time 120sec
Mixer Supermixer After the toner was prepared, the fluidity was measured by this evaluation method.
The obtained toner was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation, cleaning experiments, and running experiments were performed. The results are shown in Table 1.

Comparative Example 1
Kneading, pulverization, and classification were carried out using the same raw materials and production methods as in Example 1, and classified into a particle size distribution with a weight average particle size of 6.5 μm.
To 100 parts of the base colored particles thus obtained, an additive was mixed under the following mixing conditions to prepare a toner.
Additive Silica fine powder 1.0 part
Titanium oxide fine powder 0.3 part Mixing rotation speed 700rpm
Mixing time 120sec
Mixer Supermixer After the toner was prepared, the fluidity was measured by this evaluation method. The drawing force was 0.51 N, which was outside the scope of the present invention.
The obtained toner was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation, cleaning experiments, and running experiments were performed. The results are shown in Table 1.

Example 6
(1) Synthesis of toner binder 724 parts of bisphenol A ethylene oxide 2-mole adduct, 276 parts of isophthalic acid, and 2 parts of dibutyltin oxide are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe. The mixture was reacted at 230 ° C. for 8 hours, further reacted at a reduced pressure of 10 to 15 mmHg for 5 hours, cooled to 160 ° C., 32 parts of phthalic anhydride was added thereto, and reacted for 2 hours. Subsequently, it cooled to 80 degreeC and reacted with 188 parts of isophorone diisocyanate in ethyl acetate for 2 hours, and the isocyanate containing prepolymer I was obtained. Next, 267 parts of prepolymer I and 14 parts of isophoronediamine were reacted at 50 ° C. for 2 hours to obtain urea-modified polyester I having a weight average molecular weight of 64,000. In the same manner as above, 724 parts of bisphenol A ethylene oxide 2-mole adduct and 276 parts of terephthalic acid were polycondensed at 230 ° C. for 8 hours under normal pressure, and then reacted for 5 hours at a reduced pressure of 10 to 15 mmHg. Polyester A was obtained. 200 parts of urea-modified polyester I and 800 parts of unmodified polyester A were dissolved and mixed in 2000 parts of an ethyl acetate / MEK (1/1) mixed solvent to obtain an ethyl acetate / MEK solution of toner binder I. Part of the mixture was dried under reduced pressure to isolate toner binder I. As a result of analysis, Tg was 62 ° C.
(2) Preparation of toner Toner binder I in ethyl acetate / MEK solution 240 parts Pentaerythritol tetrabehenate (melt viscosity 25 cps) 20 parts Copper phthalocyanine blue pigment (CI Pigment Blue 15: 3) 5 parts In a beaker, the mixture was stirred at 12000 rpm with a TK homomixer at 60 ° C., and uniformly dissolved and dispersed to prepare a toner material solution.
706 parts of ion exchange water 10% suspension of hydroxyapatite (Superpatite 10 manufactured by Nippon Chemical Industry Co., Ltd.)
294 parts Sodium dodecylbenzenesulfonate 0.2 part The above raw materials were put in a beaker and dissolved uniformly. Thereafter, the temperature was raised to 60 ° C., and the toner material solution was added and stirred for 10 minutes while stirring at 12000 rpm with a TK homomixer. The mixture was then transferred to a flask equipped with a stir bar and a thermometer, the solvent was removed under reduced pressure at 30 ° C., filtered, washed and dried, and then air classified to obtain toner particles. The weight average particle diameter was 6.0 μm. An additive was mixed with 100 parts of the toner particles under the following mixing conditions to obtain base colored particles.
To 100 parts of the base colored particles thus obtained, an additive was mixed under the following mixing conditions to prepare a toner.
Additive Silica fine powder 1.0 part
Titanium oxide fine powder 0.3 part Mixing rotation speed 1200rpm
Mixing time 120sec
Mixer Q mixer After the toner was prepared, the fluidity was measured by this evaluation method.
Two-component developer was prepared by mixing 2.5 parts of toner obtained by the above preparation method and 97.5 parts of carrier.
The obtained developer was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation, cleaning experiments, and running experiments were performed. The results are shown in Table 1.

Example 7
Toner was prepared using the same raw materials and preparation method as in Example 6, and classified into a particle size distribution having a weight average particle size of 6.0 μm.
To 100 parts of the base colored particles thus obtained, an additive was mixed under the following mixing conditions to prepare a toner.
Additives Silica fine powder 1.2 parts
Titanium oxide fine powder 0.3 part Mixing rotation speed 1200rpm
Mixing time 120sec
Mixer Q mixer After the toner was prepared, the fluidity was measured by this evaluation method.
Two-component developer was prepared by mixing 2.5 parts of the toner obtained by the above preparation method and 97.5 parts of the carrier.
The obtained developer was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation, cleaning experiments, and running experiments were performed. The results are shown in Table 1.

Example 8
Toner was prepared using the same raw materials and preparation method as in Example 6, and classified into a particle size distribution having a weight average particle size of 6.0 μm.
To 100 parts of the base colored particles thus obtained, an additive was mixed under the following mixing conditions to prepare a toner.
Additive silica fine powder 1.5 parts
Titanium oxide fine powder 0.3 part Mixing rotation speed 1200rpm
Mixing time 120sec
Mixer Q mixer After the toner was prepared, the fluidity was measured by this evaluation method.
Two-component developer was prepared by mixing 2.5 parts of the toner obtained by the above preparation method and 97.5 parts of the carrier.
The obtained developer was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation, cleaning experiments, and running experiments were performed. The results are shown in Table 1.

Example 9
Toner was prepared using the same raw materials and preparation method as in Example 6, and classified into a particle size distribution having a weight average particle size of 6.0 μm.
To 100 parts of the base colored particles thus obtained, an additive was mixed under the following mixing conditions to prepare a toner.
Additive Silica fine powder 1.8 parts
Titanium oxide fine powder 0.3 part Mixing rotation speed 1200rpm
Mixing time 120sec
Mixer Q mixer After the toner was prepared, the fluidity was measured by this evaluation method.
Two-component developer was prepared by mixing 2.5 parts of the toner obtained by the above preparation method and 97.5 parts of the carrier.
The obtained developer was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation, cleaning experiments, and running experiments were performed. The results are shown in Table 1.

Example 10
Toner was prepared using the same raw materials and preparation method as in Example 6, and classified into a particle size distribution having a weight average particle size of 6.0 μm.
To 100 parts of the base colored particles thus obtained, an additive was mixed under the following mixing conditions to prepare a toner.
Additive Silica fine powder 1.8 parts
Titanium oxide fine powder 0.3 parts Mixing rotation speed 1400 rpm
Mixing time 120sec
Mixer Q mixer After the toner was prepared, the fluidity was measured by this evaluation method.
Two-component developer was prepared by mixing 2.5 parts of the toner obtained by the above preparation method and 97.5 parts of the carrier.
The obtained developer was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation, cleaning experiments, and running experiments were performed. The results are shown in Table 1.

Comparative Example 2
Toner was prepared using the same raw materials and preparation method as in Example 6, and classified into a particle size distribution having a weight average particle size of 6.0 μm.
To 100 parts of the base colored particles thus obtained, an additive was mixed under the following mixing conditions to prepare a toner.
Additive Silica fine powder 1.0 part
Titanium oxide fine powder 0.3 part Mixing rotation speed 700rpm
Mixing time 120sec
Mixer Supermixer After the toner was prepared, the fluidity was measured by this evaluation method. The drawing force was 0.03 N, which was outside the scope of the present invention.
Two-component developer was prepared by mixing 2.5 parts of toner obtained by the above preparation method and 97.5 parts of carrier.
The obtained developer was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation, cleaning experiments, and running experiments were performed. The results are shown in Table 1.

Example 11
Resin Polyester resin 100 parts Pigment Carbon black 10 parts Charge control agent Zinc salicylate 2 parts Mold release agent Rice wax 5 parts Additives Styrene acrylic resin 3 parts After mixing the above raw materials thoroughly with a mixer, the barrel is formed by a twin screw extruder. Melt kneading was performed at a temperature of 100 ° C. and a rotational speed of 120 rpm. The kneaded product was rolled and cooled, coarsely pulverized by a cutter mill, pulverized by a fine pulverizer using a jet stream, and then classified into a particle size distribution having a weight average particle size of 6 μm using a swirling air classifier.
To 100 parts of the base colored particles thus obtained, an additive was mixed under the following mixing conditions to prepare a toner.
Additives Silica fine powder 1.2 parts
Titanium oxide fine powder 0.3 part Mixing rotation speed 1200rpm
Mixing time 120sec
Mixer Q mixer After the toner was prepared, the fluidity was measured by this evaluation method.
Two-component developer was prepared by mixing 2.5 parts of the toner obtained by the above preparation method and 97.5 parts of the carrier.
The obtained developer was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation, cleaning experiments, and running experiments were performed. The results are shown in Table 1.

Example 12
The toner was prepared using the same raw materials and preparation method as in Example 11, and classified into a particle size distribution having a weight average particle size of 6.5 μm.
To 100 parts of the base colored particles thus obtained, an additive was mixed under the following mixing conditions to prepare a toner.
Additive silica fine powder 1.5 parts
Titanium oxide fine powder 0.3 part Mixing rotation speed 1200rpm
Mixing time 120sec
Mixer Q mixer After the toner was prepared, the fluidity was measured by this evaluation method.
Two-component developer was prepared by mixing 2.5 parts of the toner obtained by the above preparation method and 97.5 parts of the carrier.
The obtained developer was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation, cleaning experiments, and running experiments were performed. The results are shown in Table 1.

Example 13
The toner was prepared using the same raw materials and preparation method as in Example 11, and classified into a particle size distribution having a weight average particle size of 6.5 μm.
To 100 parts of the base colored particles thus obtained, an additive was mixed under the following mixing conditions to prepare a toner.
Additive Silica fine powder 1.8 parts
Titanium oxide fine powder 0.3 part Mixing rotation speed 1200rpm
Mixing time 120sec
Mixer Q mixer After the toner was prepared, the fluidity was measured by this evaluation method.
Two-component developer was prepared by mixing 2.5 parts of the toner obtained by the above preparation method and 97.5 parts of the carrier.
The obtained developer was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation, cleaning experiments, and running experiments were performed. The results are shown in Table 1.

Comparative Example 3
The toner was prepared using the same raw materials and preparation method as in Example 11, and classified into a particle size distribution having a weight average particle size of 6.5 μm.
To 100 parts of the base colored particles thus obtained, an additive was mixed under the following mixing conditions to prepare a toner.
Additive Silica fine powder 1.0 part
Titanium oxide fine powder 0.3 part Mixing rotation speed 700rpm
Mixing time 120sec
Mixer Supermixer After the toner was prepared, the fluidity was measured by this evaluation method. The drawing force was 0.52, which was outside the scope of the present invention.
Two-component developer was prepared by mixing 2.5 parts of the toner obtained by the above preparation method and 97.5 parts of the carrier.
The obtained developer was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation, cleaning experiments, and running experiments were performed. The results are shown in Table 1.

The measurement results of Examples 1 to 13 and Comparative Examples 1 to 3 are shown in Table 1.

As can be seen from the above results, there is a strong correlation between the fluidity evaluation value of the toner powder phase by this evaluation method and the cleaning property, and it can be seen that the cleaning property can be evaluated by this evaluation method. Table 1 also shows that there is a strong correlation between the fluidity evaluation value by this evaluation method and the dot reproducibility, and the dot reproducibility can be evaluated by this evaluation method.
From the results shown in FIG. 4 and Table 1, in order to obtain a toner with good fluidity necessary for obtaining high image quality with good dot reproducibility and cleaning property, a flat plate member (thickness: 1 mm, aspect ratio: 5) When moving relatively in the powder phase, it is necessary to satisfy the condition that “the value of the force generated in the flat plate member is 0.05 to 0.4 N”.

It is the schematic which shows one example of the fluidity evaluation apparatus of the electrostatic charge developing toner of this invention, and is an example in the case of using a flexible flat plate member (flat plate detection member). It is the schematic which shows one example of the fluidity | liquidity evaluation apparatus of the electrostatic charge developing toner of this invention, and is an example in the case of using the thing in which a flat plate member (flat plate detection member) is not flexible. Examples of various types of flat plate members according to the present invention are shown, wherein (a) has a sawtooth shape, (b) has an elliptical tooth shape, and (c) has no irregularities and is smooth. , Respectively. It is a graph which shows the relationship between the value (drawing force) when measured with the load cell which acts on the flat member in Examples 1-13 and Comparative Examples 1-3, and cleaning property. 1 is a schematic diagram illustrating an example of a toner manufacturing apparatus using a toner fluidity evaluation device for electrostatic charge development according to the present invention. It is the schematic which shows an example of the image development apparatus used by this invention.

Claims (19)

  The flowability of the toner containing at least a resin and a pigment is determined by embedding a flat plate member in the toner powder phase and moving the toner powder phase or the flat plate member in the longitudinal direction of the flat plate member. A method for evaluating the fluidity of an electrostatic charge developing toner, characterized by measuring a force generated in a member.   The toner powder phase or the flat member is pressed after the toner powder phase is pressed in a direction perpendicular to the flat member by the compacting means in a state where the flat member is buried in the toner powder phase. 2. The fluidity of an electrostatic charge developing toner according to claim 1, wherein the fluid is moved in a direction perpendicular to the consolidation direction and in the longitudinal direction of the flat plate member, and the force generated on the flat plate member is measured at this time. How to evaluate.   The method for evaluating the fluidity of an electrostatic charge developing toner according to claim 1 or 2, wherein the flat member has a relative moving speed of 0.1 to 10 mm / sec. The method for evaluating the fluidity of the electrostatic charge developing toner according to claim 1, wherein the relative movement acceleration of the flat plate member is 0.001 to 1 mm / sec ² .   5. The method for evaluating the fluidity of an electrostatic charge developing toner according to claim 1, wherein the flat plate member is reciprocated relative to the toner powder phase by 1 to 10 times.   The method for evaluating the fluidity of an electrostatic charge developing toner according to any one of claims 1 to 5, wherein the amount of relative movement of the flat plate member is 5 to 50 mm.   The method for evaluating fluidity of an electrostatic charge developing toner according to any one of claims 1 to 6, wherein the toner powder phase is measured such that the space ratio is 0.45 to 0.70.   A flat member, a container containing toner, a means for horizontally burying the flat member in the toner powder phase in the container, a means for consolidating the toner powder phase from the top to the bottom of the container, in the toner powder phase And a means for moving the toner powder phase and the flat plate member relative to each other in the longitudinal direction of the flat plate member and a means for detecting a force acting on the flat plate member at this time. An apparatus for evaluating fluidity of toner for charge development.   An apparatus for evaluating the fluidity of toner for developing an electrostatic charge, wherein the surface of the flat plate member has a regular uneven shape.   An apparatus for evaluating the fluidity of toner for developing electrostatic charge, wherein the cross-sectional shape of the flat plate member is a square having a thickness (vertical) t of 0.1 to 5 mm and an aspect ratio w / t of 3 to 10. The compaction pressure on the toner powder phase is 50 g / cm ² , the cross-section in the moving direction of the flat plate member is 1 mm × 5 mm, the relative moving speed of the flat plate member is 1.40 mm / sec, and the relative moving acceleration is 0. An electrostatic charge developing toner containing at least a resin and a pigment having a value obtained by measuring the force acting on the plate-like member with a load cell when 0.05 mm / sec ² is set.   The electrostatic charge developing toner according to claim 11, wherein the toner has a weight average particle diameter of 4 to 8 μm.   The electrostatic charge developing toner according to claim 11, wherein the toner has an average circularity of 0.9 to 0.99.   14. A cartridge container selected from the group consisting of a toner cartridge and a process cartridge, containing the electrostatic charge developing toner according to claim 11.   A developing method using the electrostatic charge developing toner according to claim 11.   The developing method according to claim 15, wherein development is performed by applying an AC bias voltage component.   A one-component developing method comprising performing contact or non-contact development using the electrostatic charge developing toner according to claim 11.   The one-component developing method according to claim 17, wherein a doctor roller and / or a supply roller are used. 14. A two-component developing method, wherein development is performed using the electrostatic charge developing toner according to claim 11 and a carrier having an average particle diameter of 20 to 70 [mu] m.