JP2005292072A - Flowability evaluation apparatus for powder, toner for electrostatic charge image development and its manufacturing method, development method therefor, toner cartridge, and process cartridge - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an apparatus capable of evaluating precisely flowability between powder and a member constituting the apparatus, without generating a personal error, and to stably manufacture powder, for example, a toner capable of obtaining an image of high quality, free from a problem about a conveyance property of the toner and image density lowering, and excellent in dot reproducibility, all the time, by using the device. <P>SOLUTION: A material of a conical rotor 36 is different from that of the powder, and surface irregularity thereof is 0,01-100μm, in a measuring apparatus 1 for evaluating the flowability of the powder by intruding the conical rotor 36 into a powder phase, while rotating it, to measure a torque or load generated when the conical rotor 36 is moved in the powder phase. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an apparatus for evaluating the fluidity of powder, a toner for developing an electrostatic image produced using the apparatus, a method for producing the toner, a developing method using the toner, a toner cartridge containing the toner, and a process It relates to the cartridge.

  Electrophotographic copying machines and printers have been improved in image quality, and recently, fine dot reproducibility has become very important. The dot reproducibility is greatly influenced by fluidity in addition to the charge amount of toner and developer, and it is necessary to stably supply a uniform toner layer or developer layer to a fine latent image portion. . For this purpose, in addition to the fluidity of the toner and the developer itself, the fluidity with the device member in contact with the toner is also important, and an evaluation method capable of accurately evaluating them is required.

  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, since the toner production method has changed from the pulverization method to another method such as a polymerization method, the change in flow characteristics with respect to manufacturing conditions has increased. Control and evaluation are required.

For example, a method is known in which the flowability of the developer in the developing machine is accurately evaluated by measuring the time required to pass through a narrow portion of a funnel to which a magnetic field is applied (PTL 1). reference). Also, a method is known in which toner is placed on a tiltable plate, the plate is gradually tilted, and the angle at the start of flow and the angle at the end of flow are measured (see Patent Document 2). Further, the sieves are stacked in several stages, and the toner is put thereon, the horizontal and vertical vibrations are applied to the sieve part, and the amount of toner remaining in each sieve part after a predetermined time is preset. A method of calculating by multiplying coefficients is known (see Patent Document 3). However, all of these methods have large variations 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.
JP-A-1-203941 JP-A-4-116449 JP 2000-292967 A

  The present invention has been made in view of the above circumstances. Therefore, the present invention has developed a device capable of evaluating the fluidity between the powder and the device constituent members with high accuracy and without individual differences, and using the device, There is no problem in the transportability of the toner, for example, the electrostatic charge image developing toner, there is no problem in image density reduction, and the electrostatic charge image developing toner can be stably produced so that a high-quality image with good dot reproducibility can be obtained at any time. The purpose is to do so.

  As a result of investigations to achieve the above-mentioned problems, the inventors of the present invention have made a conical rotor made of a material having a smooth surface and a powder different from the powder into the powder phase while rotating. By measuring the torque or load generated when moving inside, it is possible to quantitatively evaluate the fluidity of the powder accurately, without individual differences, and to accurately evaluate the fluidity difference between fine powders. I knew it and came to the present invention.

The present invention
As a first aspect, the fluidity of the powder is controlled by allowing the conical rotor to enter the powder phase while rotating, and measuring the torque or load generated when the conical rotor moves in the powder phase. In the apparatus to be evaluated, the conical rotor is formed of a material different from that of the powder, and the surface roughness is 0.01 to 100 μm. It is.

  As a second aspect, in the powder fluidity evaluation apparatus according to the first aspect, the powder phase is preliminarily brought into a compacted state by a compacting means, and the conical rotor is allowed to enter the compacted powder phase while rotating. It is an object of the present invention to provide a powder fluidity evaluation apparatus characterized by

  As a third aspect, in the powder fluidity evaluation apparatus according to the second aspect, the powder phase is stabilized by a vibrator provided in advance under a container for storing the powder. The present invention provides an apparatus for evaluating the fluidity of a powder, characterized in that measurement is performed in a compacted state by the compacting means.

  As a fourth aspect, in the powder fluidity evaluation apparatus according to the second aspect or the third aspect, the powder phase is adjusted so that the porosity of the powder phase becomes 0.4 to 0.7 by the compaction means. It is intended to provide a powder fluidity evaluation apparatus characterized by performing measurement.

  As a fifth aspect, in the powder fluidity evaluation apparatus according to any one of the first to fourth aspects, the conical rotor is detachably provided with a mounting screw. A sex evaluation device is provided.

  As a sixth aspect, in the powder fluidity evaluation apparatus according to any one of the first to fifth aspects, the apex angle of the conical rotor is 20 to 150 °. An evaluation apparatus is provided.

  As a seventh aspect, in the powder fluidity evaluation apparatus according to any one of the first to sixth aspects, the rotational speed of the conical rotor is 0.1 to 100 rpm. A sex evaluation device is provided.

  As an eighth aspect, in the powder fluidity evaluation apparatus according to any one of the first to seventh aspects, the rotational speed of the conical rotor is 0.1 to 100 rpm. A sex evaluation device is provided.

  As a ninth aspect, while rotating the conical rotor using the powder fluidity evaluation apparatus according to any one of the first to eighth aspects, in the powder phase of the toner mixed with the additive, The present invention provides a toner for developing an electrostatic charge image, characterized in that the torque value when 20 mm penetrates is adjusted in a range of 0.1 to 7.5 mNm.

  As a tenth aspect, while rotating the conical rotor using the powder fluidity evaluation apparatus according to any one of the first to eighth aspects, in the powder phase of the toner mixed with the additive. An object of the present invention is to provide a toner for developing an electrostatic charge image, characterized in that the load value when entering 20 mm is adjusted in the range of 0.01 to 1.04 N.

  As an eleventh aspect, in the electrostatic image developing toner according to the ninth or tenth aspect, the toner contains at least one of a charge control agent and a release agent in the toner. Toner for use is provided.

  According to a twelfth aspect, in the electrostatic image developing toner according to any one of the ninth to eleventh aspects, an additive is adhered or fixed to the surface of the toner. Is to provide.

  As a thirteenth aspect, there is provided an electrostatic image developing toner according to any one of the ninth to twelfth aspects, wherein the toner has an average particle diameter of 4 to 8 μm. To do.

  According to a fourteenth aspect, there is provided the electrostatic image developing toner according to any one of the ninth to thirteenth aspects, wherein the toner is produced by a polymerization method or a spray drying method. It is to provide.

  According to a fifteenth aspect, in the electrostatic image developing toner according to any one of the ninth to fourteenth aspects, the toner has an average circularity of 0.9 to 0.99. Toner for use is provided.

  According to a sixteenth aspect, the powder fluidity evaluation apparatus according to any one of the first to eighth aspects is used to perform evaluation in the toner manufacturing process, and the toner is manufactured based on the evaluation. The present invention provides a method for producing a toner for developing an electrostatic image.

  According to a seventeenth aspect, there is provided a developing method characterized by developing a latent image in contact or non-contact with the electrostatic charge developing toner according to any one of the ninth to fifteenth aspects. .

  As an eighteenth aspect, there is provided the developing method according to the seventeenth aspect, wherein at least one of a doctor roller and a supply roller is used.

  According to a nineteenth aspect, there is provided a developing method characterized by developing a latent image using the electrostatic charge developing toner according to any one of the ninth to fifteenth aspects and a carrier having a particle diameter of 20 to 70 μm. Is.

  As a twentieth aspect, there is provided a developing method according to any one of the seventeenth to nineteenth aspects, wherein the developing is performed by applying an AC bias voltage component.

  According to a twenty-first aspect, there is provided a toner cartridge characterized in that the electrostatic charge developing toner according to any one of the ninth to fifteenth aspects is accommodated.

  As a twenty-second aspect, there is provided a process cartridge characterized by containing the electrostatic charge developing toner according to any one of the ninth to fifteenth aspects.

  According to the powder fluidity evaluation apparatus according to any one of the first to eighth aspects, the powder fluidity can be evaluated with high accuracy and without individual differences. In addition, since this method can measure the powder phase as it is in a short time, it can be introduced into the production line, and high-quality powder can be stably produced.

  According to the electrostatic image developing toner according to any one of the ninth to fifteenth aspects and the electrostatic charge developing toner manufacturing method according to the sixteenth aspect, a high-quality image can be obtained.

  According to the developing method according to any one of the seventeenth to twentieth aspects, there is no reduction in image density and dot reproducibility is good, so that a high-quality image can be obtained.

  According to the ner cartridge according to the twenty-first aspect, excellent fluidity can be maintained even when stored in a container. In addition, according to the process cartridge of the twenty-second aspect, excellent fluidity can be maintained even when stored in the toner storage portion.

Hereinafter, embodiments of the present invention will be described in detail.
In the powder fluidity evaluation apparatus of the present invention, the material is different from the powder in the powder phase, and the conical rotor having a surface unevenness of 0.01 to 100 μm is rotated (increased), The torque and load applied to the container containing the conical rotor and the powder phase at that time are measured, and the fluidity of the powder is evaluated based on the torque and load values.

  The powder fluidity evaluation apparatus of the present invention is provided with a compacting means, and after consolidating the powder phase, a conical rotor is inserted into the compacted powder phase to measure torque and load. is there. The conical rotor may have any shape, but a cone having an apex angle of 20 to 150 ° is suitable. If the apex angle of the cone is smaller than 20 °, the resistance to the powder phase is small, so that the torque and load are small, and a fine difference in fluidity cannot be evaluated. On the other hand, when the apex angle is larger than 150 °, the force in the direction of pressing the powder phase becomes large and the powder particles are easily deformed, which is not suitable for the evaluation of the fluidity of the powder. The length of the conical rotor needs to be long enough so that the conical rotor surface is continuously present in the powder phase.

  The powder fluidity evaluation apparatus of the present invention measures the frictional component between the surface of the conical rotor and the powder and evaluates the fluidity, and the surface of the conical rotor needs to be smooth. The surface unevenness needs to be 0.01 to 100 μm, and when the surface unevenness is smaller than 0.01 μm, it is difficult to process the rotor, and the cost becomes high. When the irregularities on the surface are larger than 100 μm, the powder enters the recesses, and the friction component between the powder and the powder is measured, and the friction component between the rotor surface and the powder cannot be measured. Any material can be used for the conical rotor, but a material that is easy to process, has a hard surface, and does not change quality is preferable. A material that is not charged is suitable. Examples of this are SUS, Al, Cu, Au, Ag, and brass. Further, the conical rotor can be made of the same material as the device constituent member (for example, plastic, rubber, ceramics, etc.), and the fluidity between the powder and the device constituent member can be evaluated.

The torque and load of the powder vary depending on the rotational speed of the conical rotor and the penetration speed of the conical rotor. In order to improve the measurement accuracy, the measurement was performed by lowering the rotational speed and penetration speed of the conical rotor so that the fine contact state between the powder particles can be measured. Therefore, the measurement conditions were as follows.
・ Rotation speed of conical rotor: 0.1 to 100 rpm
・ Intrusion speed of conical rotor: 0.5 to 150 mm / min

  When the rotational speed of the conical rotor is smaller than 0.1 rpm, it is easily affected by the delicate state of the powder phase, which causes a problem of torque measurement variation and is not suitable for measurement. If it is higher than 100 rpm, the powder will scatter, etc., which is not suitable because it cannot be measured stably. When the penetration speed of the conical rotor is slower than 0.5 mm / min, it is easily affected by the subtle state of the powder phase, and there is a problem of measurement variation, which is not suitable for measurement. If it is faster than 150 mm / min, the powder phase tends to be in a compacted state, and influences such as deformation of the powder particles appear, so it is not suitable for fluidity evaluation.

  FIG. 1 shows the overall configuration of a measuring apparatus 1 which is a powder fluidity evaluation apparatus according to the present invention. The measuring device 1 comprises a consolidation zone 2 and a measurement zone 3. The consolidation zone 2 includes a sample container 23 for containing powder, an elevating stage 24 for moving the container up and down, a piston 25 for consolidation, a weight 26 for applying a load to the piston 25, and the like. In addition, this structure is an example and does not limit this invention. In this configuration, the sample container 23 containing the powder is raised, brought into contact with the piston 25 for compaction, and further raised so that all the load of the weight 26 is applied to the piston 25, and the weight 26 is lifted from the support plate. Leave for a certain period of time so that it will be in a state. Thereafter, the elevating stage 24 on which the sample container 23 containing the powder is placed is lowered to separate the piston 25 from the powder surface. The piston 25 may be made of any material, but it needs to have a smooth surface on which the powder is pressed. Therefore, a material that is easy to process, has a hard surface, and does not change quality is preferable. Further, it is necessary to prevent the powder from adhering due to charging, and a conductive material is suitable. Examples of this material include SUS, Al, Cu, Au, Ag, and brass.

The measurement zone 3 is as shown in FIG. 1 and includes a container 33 for storing powder, an elevating stage 34 for moving the container up and down, a load cell 32 for measuring load, a torque meter 35 for measuring powder torque, and the like. In addition, this structure is an example and does not limit this invention. A conical rotor 36 is attached to the tip of the shaft, and the shaft itself is fixed (with respect to vertical movement). The elevating stage 34 on which the sample container 33 containing the powder is placed in the center can be moved up and down. By raising the container 33, the conical rotor 36 enters the center of the container 33 while rotating. Like that. Torque applied to the conical rotor 36 is detected by a torque meter 35 at the top, and a load applied to the container 33 containing powder is detected by a load cell 32 below the container 33. The moving amount of the conical rotor 36 is performed by a position detector (not shown). This configuration is an example, and other configurations such as moving the shaft up and down may be used.
Alternatively, the weight of the powder may be measured using the load cell 32 under the container 33, and the compacted state of the powder phase may be evaluated from the height information and weight information of the powder phase. The calculation of these information is performed using an electronic computer (not shown).

  As described above, the conical rotor 36 preferably has an apex angle of 20 ° (see FIG. 2B) to 150 ° (see FIG. 2A). The length of the conical rotor 36 needs to be long so that the portion of the conical rotor sufficiently enters the powder phase.

  The material of the material container 33 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 33 is important, and it is necessary to select a larger (diameter) size with respect to the diameter of the conical rotor 36 so that the wall of the container is not affected when the conical rotor 36 enters while rotating.

  The conical rotor 36 is attached to the torque meter 35 with a mounting screw 37 as shown in FIG. 3 so that various conical rotors 36 of various materials can be easily attached and detached. Since it is detachable with one screw, the conical rotor 36 made of different materials can be easily replaced, and the fluidity between various materials and powders can be evaluated.

  The torque meter 35 is preferably a high-sensitivity type, and a non-contact type is suitable. A load cell 32 having a wide load range and high resolution is suitable. The position detector includes a linear scale, a displacement sensor using light, etc., but the specification of 0.1 mm or less is suitable for accuracy. The elevator can be driven with high accuracy using a servo motor or a stepping motor.

In the measurement, a fixed amount of powder is put into the container 23 and set in the apparatus. Thereafter, the elevating stage 24 is raised in the compaction zone 2 and the powder surface is pressed by a piston under a certain load to create a compacted powder phase state. After consolidation for a certain time, the container 23 is lowered and returned to its original position.
Thereafter, the container 23 containing the powder whose compacted state has been measured is installed as a container 33 on the elevating stage 34 in the measurement zone 3. This operation may be moved from the consolidation zone 2 to the measurement zone 3 by rotating the elevating stage 34.
Thereafter, the conical rotor 36 is rotated to enter the powder phase in the container 33. When entering torque or load measurement, it is performed at the determined rotation speed and penetration speed. The rotational direction of the conical rotor 36 is arbitrary. If the penetration distance of the conical rotor 36 is shallow, the values of torque and load are small, which causes problems in data reproducibility and the like. As a result of experiments by the inventors, it was possible to perform almost stable measurement by intruding 5 mm or more.

The measurement mode can be performed under any conditions. For example, the measurement mode is as follows.
(1) The container 23 is filled with powder.
(2) The powder phase is consolidated by the piston 25 to create a consolidated state.
(3) The conical rotor 36 is inserted while rotating, and the torque and load at that time are measured.
(4) When the conical rotor 36 has penetrated from the toner surface layer to a preset depth, the penetration operation is stopped.
(5) The operation of pulling out the conical rotor 36 is started.
(6) When the tip of the conical rotor 36 comes off from the powder phase surface and becomes completely free (first home position), the drawing operation of the conical rotor 36 is stopped and the rotation is also stopped.
Measurement is performed by repeating the operations (1) to (6). It may be performed continuously.

Further, as another measurement method, the powder phase is stabilized by applying vibration by the vibrator 27 (see FIG. 1), and then compacted by the piston 25 and rotated into the compacted powder phase while being conical. The rotor 36 is intruded, the torque and load at that time are measured, the intrusion operation is stopped when reaching a preset depth, and then the conical rotor 36 is raised to the initial position (home position). This measurement may be performed once, but it is also effective to obtain this average torque and load by repeating this operation.
As another method, there is a method in which the conical rotor 36 is inserted into the compacted powder phase and the depth until reaching a preset torque value is examined.

  As a method for evaluating the consolidated state, there is a method of calculating a space ratio. In this measurement method, the porosity of the powder phase is important. According to the results of experiments by the inventors, stable measurement was possible when the porosity was 0.4 or more. If it is less than 0.4, a subtle difference in the compacted state affects the torque and load, and stable measurement is difficult. The range of the space ratio of the powder phase was 0.4 to 0.7 including the cases of various measurement methods. If it is larger than 0.7, the powder is scattered and is not suitable for measurement. However, this does not apply to the measurement system and measurement conditions.

  When the powder used in the powder fluidity evaluation apparatus of the present invention is an electrostatic charge image developing toner, it is necessary that the average particle diameter of the toner is 4 to 8 μm in order to realize a high quality image. is there. The toner has a weight average particle diameter of 4 to 8 μm, more preferably 5 to 7 μm. 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 diameter exceeds 8 μm, the resolution of fine 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.

  A 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.

Details of the toner and developer are shown below.
As resin which is a toner component, polystyrene resin, epoxy resin, polyester resin, polyamide resin, styrene acrylic resin, styrene methacrylate resin, polyurethane resin, vinyl resin, polyolefin resin, styrene butadiene resin, phenol resin, polyethylene resin, silicone resin, Examples include butyral resin, terpene resin, and polyol resin.

  Examples of vinyl resins include styrene such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene, and homopolymers thereof: styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer. Polymer, styrene-vinyl naphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methacrylic copolymer Acid methyl copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer Coalescence, styrene-vinyl ethyl acetate Copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester Styrene copolymers such as copolymers: polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate and the like.

  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 trihydric or higher alcohol as shown in the group C. Alternatively, 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.

  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, or 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, or two active hydrogens that react with the epoxy resin in the molecule. There are those obtained by reacting with a compound having at least one.

The following pigments are used as the toner component.
Examples of the black pigment 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. .

  Examples of the orange pigment 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.

  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, fast sky blue, and indanthrene blue BC.

  Examples of green pigments include chrome green, chromium oxide, pigment green B, and malachite green lake.

These pigments can be used alone or in combination of two or more.
Especially for 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 assist dispersibility. However, there is a problem of environment and the like, and in the present invention, water is used for dispersion. When water is used, temperature control is important so that residual moisture in the masterbatch does not become a problem.

  In the toner according to the present invention, a charge control agent is blended (internally added) inside the toner particles. However, the charge control agent may be mixed (externally added) with 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.

  Further, a release agent can be internally added to the toner according to the present invention in order to prevent offset at the time of fixing. Release agents include natural waxes such as candelilla wax, carnauba wax and rice wax, montan wax and derivatives thereof, paraffin wax and derivatives thereof, polyolefin wax and derivatives thereof, sazol wax, low molecular weight polyethylene, and low molecular weight polypropylene. And alkyl phosphate esters. 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 is likely 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.

  Additives may be added for the purpose of improving the dispersibility of a release agent or the like. Additives 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 resin, terpene resin, There is a polyol resin or the like, and a mixture of two or more of these resins may be used.

  As the resin, crystalline polyester may be used. The crystalline polyester is an aliphatic polyester having crystallinity, having a sharp molecular weight distribution, and increasing the absolute amount of the low molecular weight as much as possible. This resin undergoes a crystal transition at the glass transition temperature (Tg), and at the same time, the melt viscosity suddenly decreases from the solid state and exhibits a fixing function to paper. By using this crystalline polyester resin, low-temperature fixing can be achieved without excessively reducing the Tg and molecular weight of the resin. Therefore, there is no decrease in storage stability associated with a decrease in Tg. Further, there is no excessively high gloss and offset resistance deterioration due to the low molecular weight. Therefore, the introduction of the crystalline polyester resin is very effective for improving the low-temperature fixability of the toner.

  In the toner according to the present invention, the content of the crystalline polyester is 1 to 50 with respect to the total amount of the resin and the release agent in the toner in order to exhibit low-temperature fixability and ensure hot offset resistance. The content of the release agent is preferably 2 to 15% by weight. When the content of the crystalline polyester is less than 1% by weight, there is no effect on the low-temperature fixability, and when it exceeds 50% by weight, the hot offset property is deteriorated. When the release agent content is less than 2% by weight, the offset resistance may not be effective, and when it exceeds 15% by weight, the toner fluidity decreases.

  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, a pigment or dye as a colorant, a charge control agent, a 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 using a whirling stream or the Coanda effect 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 fluidity of the toner particles after the mixing step is evaluated using the powder fluidity evaluation apparatus of the present invention. In this case, after sampling, the sample is put in the sample container 23, and the sample container 23 is directly placed on the sample stage 24 of the powder fluidity evaluation apparatus shown in FIG. 1, and the toner powder phase is stirred and initialized. Consolidate and measure. The rotational speed of the conical rotor 36 was 0.1 to 100 rpm, and the penetration speed of the conical rotor 36 was 0.5 to 100 mm / min. The measurement is performed while the conical rotor 36 is rotated, and the intrusion is stopped after a predetermined intrusion distance of 5 mm or more. Thereafter, the conical rotor 36 is pulled out and returned to the original initial position. The torque and load when the conical rotor 36 enters the toner powder phase are measured to evaluate the fluidity of the toner.

When the toner fluidity is evaluated by the powder fluidity evaluation apparatus of the present invention, the measured value (torque, load) and the toner fluidity have the following relationship.
・ When torque is small, fluidity is good.
・ If the torque is large, the fluidity is poor.
-When the load is small, the fluidity is good.
・ If the load is large, the fluidity is poor.

The characteristics of the powder fluidity evaluation apparatus of the present invention using the conical rotor 36 are as follows, and the extracted sample can be measured quickly and simply as it is, so that it is possible to perform highly accurate measurement without individual differences.
(1) Non-destructive inspection.
(2) The sample can be measured as it is.
(3) It can be measured in a short time.
(4) 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 step, a sample extraction / measurement zone is provided in the middle of conveying the powder sample to the next step, and a shutter is opened and closed at a certain timing to convey 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 measured as it is with the measurement apparatus 1 of the present invention. Alternatively, the container is taken to the measuring apparatus 1 of the present invention in another nearby place, placed on the sample stage, and measured by the measuring apparatus 1 of the present invention. 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 FIG. 6).
It is also possible to use a toner evaluation apparatus having these functions alone as the measurement apparatus 1 at the development stage.

  In the case of toner, as described above, the measured values of torque and load in the evaluation apparatus of the present invention indicate fluidity, and quantitative evaluation is possible. Conventional conventional evaluation methods can evaluate differences between toners, but there is a problem that evaluation cannot be performed on the same soil if the types of toner are different. However, the values measured by the evaluation apparatus of the present invention are torque values and load values as powder characteristics, which are values that can be evaluated on the same soil regardless of the type of toner or the particle size. It becomes a general-purpose evaluation value. Moreover, since the difference in fluidity after evaluating the consolidated state can be evaluated, multifaceted evaluation is possible. In addition, the fluidity between the toner and the device constituent member can be evaluated by making the conical rotor 36 from the device constituent member or covering the surface of the conical rotor 36 with the same material as the device constituent member.

The torque and load characteristics during movement of the conical rotor 36 in the toner powder phase are closely related to the fluidity of the powder. When the fluidity of the powder is good, each powder particle Since the adhesion force between them is small, it is easy to move, and even if the conical rotor is moved in the powder phase, the torque is small and the load change is small. However, when the flowability of the powder is poor, the adhesion force between the individual powder particles is large and the movement is difficult, and when the conical rotor is moved within the powder phase, the conical rotor is used. The torque applied to 36 increases, and the force (load) acting downwards also increases. Therefore, in the evaluation method of the present invention, the fluidity can be evaluated according to the following relationship.
Good fluidity → Torque and load when moving in the powder phase are small.
When the fluidity is poor → The torque and load when moving in the powder phase are 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 or the like is adhered or fixed to the surface of the toner particles.

  The toner mixing state varies depending on the mixing conditions (amount of charge, the number of revolutions, the 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.

Therefore, as a result of evaluating the fluidity of the toner with the powder fluidity evaluation apparatus of the present invention using the conical rotor 36 and investigating the relationship with the dot reproducibility, a very strong correlation exists, and the torque and load When is small, dot reproducibility improved. From the results, it was found that the toner having good dot reproducibility shows the following torque and load characteristics.
(1) The torque value when the conical rotor enters (when 20 mm enters) is 0.1 to 7.5 mNm.
(2) The load value when the conical rotor enters (when 20 mm enters) is 0.01 to 1.04 N.

  Note that there is no problem even if other methods are used for the evaluation mode. The evaluation item may be an entry distance until a certain load is reached, an entry distance until a certain torque is reached, or the like, or an integrated value of the torque or the load may be evaluated. Other evaluation items may be used.

  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, in the toner of the present invention, an oily dispersion in which at least a polyester-based prepolymer containing an isocyanate group is dissolved in an organic solvent, a pigment-based colorant is dispersed, and a release agent is dissolved or dispersed in an aqueous medium. A urea-modified polyester having a urea group which is dispersed in the presence of at least one of inorganic fine particles and polymer fine particles, and the prepolymer is reacted with a monoamine having at least one of a polyamine and an active hydrogen-containing group in the dispersion. It is obtained by forming a resin and removing the liquid medium contained in the dispersion containing the urea-modified polyester resin.

  In the urea-modified polyester resin, the Tg is 40 to 65 ° C, preferably 45 to 60 ° C. The number average molecular weight Mn is 2500 to 50000, preferably 2500 to 30000. The weight average molecular weight Mw is 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. The colorant is highly dispersed in the binder resin.

  The obtained toner powder after drying is air-classified, and an additive composed of inorganic fine particles or the like is adhered or fixed to the particle surface by a mixer under the optimum mixing conditions. Alternatively, the charge control agent may be applied to the surface of the toner powder after drying and fixedly injected. Further, thereafter, an additive made from inorganic fine particles or the like may be adhered or fixed to the particle surface. By placing the charge control agent on the surface, the charge amount of the toner can be easily controlled.

Specific means for mixing or fixing and injecting is a method of applying an impact force to the powder mixture with blades rotating at high speed. For example, there is a method of causing the particles to collide with an appropriate collision plate. As equipment, Ong mill (manufactured by Hosokawa Micron Co., Ltd.), I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) has been modified to reduce pulverization air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), kryptron system (Made by Kawasaki Heavy Industries, Ltd.), automatic mortar and the like.
In order to evaluate whether predetermined fluidity is obtained after this mixing process, it evaluates using the evaluation device of the present invention.

  Also in the case of these methods, for inspection after granulation, inspection after treatment with charge control agent, inspection after mixing process of additive, inspection after air sieving process after mixing process, inspection before filling, etc. 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 the dot reproducibility is excellent. Realization of image quality.

  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.

  The toner of the present invention 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 ones 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 tube.

  Further, the toner of the present invention has excellent fluidity when developed using an AC bias voltage component during development. Therefore, the toner of the present invention vibrates faithfully according to the electric field, and can faithfully develop fine latent images. Development with good reproducibility is possible.

  Further, in the one-component development method, the toner of the present invention is also used in a development method in which a roller-shaped blade for uniformizing the toner layer is provided at the outlet of the toner supply unit.

  Further, as shown in FIG. 7, for example, as shown in FIG. 7, the toner supplied from the toner supply hopper 73 and agitated by the agitating blade 74 is adhered to the surface of the developing roller 75 by the supply roller 71, thereby holding the image. You may employ | adopt for the structure which develops the latent image currently formed in the surface of the body 76. FIG. In the case of such a system, not only filming on the photoconductor but also filming on the doctor roller 72 and the supply roller 71 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 72 and the supply roller 71 does not occur, stable development is performed, and the system has excellent durability characteristics.

  Since the toner of the present invention is excellent in fluidity, it can be sufficiently stored in a cartridge container, and is also suitable for an apparatus configured to convey toner from the cartridge container to the developing unit. Examples of the cartridge container include a toner cartridge that fills toner, and a process cartridge that includes at least a photosensitive member and a developing unit, and that fills a toner storage portion of the developing unit. An image is formed by attaching the cartridge to 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. Examples thereof include those treated with a silicone 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 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 a 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, Chlormethyldimethylchlorosilane, chloromethyltrichlorosilane, hexaphenyldisilazane, hexatolyldisilazane.

  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 such as a lubricating powder (PTFE powder, zinc stearate powder, polyvinylidene fluoride powder, etc.), an abrasive (cerium oxide) within a range that does not have a substantial adverse effect. Powder, silicon carbide powder, strontium titanate powder, etc.) and conductivity imparting agents (carbon black powder, zinc oxide powder, tin oxide powder, etc.) can be used in small amounts as developability improvers.

  The powder fluidity evaluation apparatus of the present invention can also be used for a toner prepared by a polymerization method or a spray drying method without using a kneading step or a pulverizing step, or a capsule toner.

Hereinafter, although an Example is described, this does not limit this invention at all.
In the following examples, toners with different toner compositions, toner preparation methods, and mixing conditions were prepared, toner fluidity was evaluated using the evaluation apparatus of the present invention, and dot reproducibility was considered as a rough feeling of the image. A five-step evaluation (rank 1: bad → rank 5: good) was made.

  In addition, a running durability test of 20,000 sheets was performed using a copying machine using OPC, and defects in toner transportability such as blocking in the developing unit were evaluated. The case where there was no defect was evaluated as ◯, and the case where there was a defect was evaluated as x.

The fluidity of the toner was evaluated using the powder fluidity evaluation apparatus of the present invention, and the torque and load values were measured when the conical rotor 36 entered 20 mm from the surface of the toner powder phase. The toner was preliminarily compacted by a compacting means, the space ratio was measured, and the torque and load were evaluated. The evaluation conditions for the conical rotor 36 were as follows. For the evaluation, torque and load when the space ratio was 0.53 were adopted.
-Conical rotor material: SUS (surface irregularities: 50 μm)
・ Vertical angle of conical rotor: 60 °
・ Rotation speed of conical rotor: 1rpm
・ Invasion speed of conical rotor: 5 mm / min
In addition, all the parts in the following mixing | blending are a weight part.

[Example 1]
Resin Polyester resin 100 parts Pigment Magenta pigment (CI Pigment Red 57) 4 parts Charge control agent Zinc salicylate 5 parts After thoroughly mixing the above raw materials with a mixer, barrel temperature 90 ° C kneader rotation speed 120rpm with a twin screw extruder And kneaded. 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 an average particle size of 6.5 μm using a swirling air classifier. Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner.
Additives Silica fine powder 0.9 parts
Titanium oxide fine powder 0.3 part Mixing rotation speed 900rpm
Mixing time 120sec
Mixer super mixer

  As a result of measuring the fluidity of the obtained toner using the powder fluidity evaluation apparatus of the present invention, it was as shown in Table 1. 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 an image evaluation experiment was performed. As a result, the dot reproducibility of the image was as shown in Table 1.

[Example 2]
Kneading, pulverization, and classification were performed using the same raw materials and production methods as in Example 1, and the particles were classified into a particle size distribution with an average particle size of 6.5 μm. Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner.
Additives Silica fine powder 0.9 parts
Titanium oxide fine powder 0.3 part Mixing rotation speed 1000rpm
Mixing time 120sec
Mixer super mixer

  As a result of measuring the fluidity of the obtained toner with the evaluation device of the present invention, it was as shown in Table 1. 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 an image evaluation experiment was performed. As a result, the dot reproducibility of the image was as shown in Table 1.

Example 3
Kneading, pulverization, and classification were performed using the same raw materials and production methods as in Example 1, and the particles were classified into a particle size distribution with an average particle size of 6.5 μm. Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner.
Additives Silica fine powder 0.9 parts
Titanium oxide fine powder 0.3 part Mixing rotation speed 1100rpm
Mixing time 120sec
Mixer super mixer

  As a result of measuring the fluidity of the obtained toner with the evaluation device of the present invention, it was as shown in Table 1. 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 an image evaluation experiment was performed. As a result, the dot reproducibility of the image was as shown in Table 1.

Example 4
Kneading, pulverization, and classification were performed using the same raw materials and production methods as in Example 1, and the particles were classified into a particle size distribution with an average particle size of 6.5 μm. Further, an additive was mixed with 100 parts of the base colored particles 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 1100rpm
Mixing time 120sec
Mixer super mixer

  As a result of measuring the fluidity of the obtained toner with the evaluation device of the present invention, it was as shown in Table 1. 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 an image evaluation experiment was performed. As a result, the dot reproducibility of the image was as shown in Table 1.

Example 5
Kneading, pulverization, and classification were performed using the same raw materials and production methods as in Example 1, and the particles were classified into a particle size distribution with an average particle size of 6.5 μm. Further, an additive was mixed with 100 parts of the base colored particles 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 super mixer

  As a result of measuring the fluidity of the obtained toner with the evaluation device of the present invention, it was as shown in Table 1. 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 an image evaluation experiment was performed. As a result, the dot reproducibility of the image was as shown in Table 1.

[Comparative Example 1]
Kneading, pulverization, and classification were performed using the same raw materials and production methods as in Example 1, and the particles were classified into a particle size distribution with an average particle size of 6.5 μm. Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner.
Additive silica fine powder 0.7 parts
Titanium oxide fine powder 0.3 part Mixing rotation speed 700rpm
Mixing time 120sec
Mixer super mixer

  As a result of measuring the fluidity of the obtained toner with the evaluation device of the present invention, it was as shown in Table 1. In addition, an image evaluation experiment was performed in the same manner as in Example 1. As a result, the dot reproducibility of the image was as shown in Table 1.

Example 6
<Toner binder synthesis>
724 parts of bisphenol A ethylene oxide 2-mole adduct, 276 parts of isophthalic acid and 2 parts of dibutyltin oxide were placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and reacted at 230 ° C. under normal pressure for 8 hours. The reaction was further carried out at a reduced pressure of 10 to 15 mmHg for 5 hours, followed by cooling to 160 ° C., and 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.

<Production 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) 4 parts TK at 60 ° C in a beaker The mixture was stirred at 12,000 rpm with a homomixer and uniformly dissolved and dispersed to prepare a toner material solution.

706 parts of ion exchange water 10% suspension of hydroxyapatite
(Nippon Chemical Industry Co., Ltd. Superite 10) 294 parts Sodium dodecylbenzenesulfonate 0.2 part The above raw materials were placed 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. Next, this mixed liquid was transferred to a flask equipped with a stir bar and a thermometer, heated to 30 ° C., the solvent was removed under reduced pressure, filtered, washed, dried, and then classified by air to obtain toner particles. The volume average particle diameter was 6.3 μm.

To 100 parts of the toner particles, an additive was mixed under the following mixing conditions to obtain a toner.
Additives Silica fine powder 1.2 parts
Titanium oxide fine powder 0.3 part Mixing rotation speed 1000rpm
Mixing time 120sec
Mixer super mixer

  As a result of measuring the fluidity of the obtained toner with the evaluation device of the present invention, it was as shown in Table 1. Further, the toner obtained by the above production method and the carrier were mixed at a ratio of 2.5 parts with respect to 97.5 parts of the carrier to prepare a two-component developer. This two-component 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 an image evaluation experiment was performed. As a result, the dot reproducibility of the image was as shown in Table 1.

Example 7
Powders were produced and classified by the same raw materials and production methods as in Example 6, and classified into a particle size distribution with an average particle size of 6.3 μm. Further, an additive was mixed with 100 parts of the base colored particles 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 1100rpm
Mixing time 120sec
Mixer super mixer

As a result of measuring the fluidity of the obtained toner with the evaluation device of the present invention, it was as shown in Table 1. Further, a two-component developer was prepared in the same manner as in Example 6, and an image evaluation experiment was performed. As a result, the dot reproducibility of the image was as shown in Table 1.
Example 8
Powders were produced and classified by the same raw materials and production methods as in Example 6, and classified into a particle size distribution with an average particle size of 6.3 μm. Further, an additive was mixed with 100 parts of the base colored particles 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 super mixer

  As a result of measuring the fluidity of the obtained toner with the evaluation device of the present invention, it was as shown in Table 1. Further, a two-component developer was prepared in the same manner as in Example 6, and an image evaluation experiment was performed. As a result, the dot reproducibility of the image was as shown in Table 1.

[Comparative Example 2]
Powders were produced and classified by the same raw materials and production methods as in Example 6, and classified into a particle size distribution with an average particle size of 6.3 μm. Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner.
Additive silica fine powder 0.7 parts
Titanium oxide fine powder 0.3 part Mixing rotation speed 700rpm
Mixing time 120sec
Mixer super mixer

  As a result of measuring the fluidity of the obtained toner with the evaluation device of the present invention, it was as shown in Table 1. Further, a two-component developer was prepared in the same manner as in Example 6, and an image evaluation experiment was performed. As a result, the dot reproducibility of the image was as shown in Table 1.

Example 9
Resin Polyester resin 100 parts Pigment Carbon black 10 parts Charge control agent Zinc salicylate 2 parts Mold release agent Carnauba wax 5 parts Additive Styrene acrylic resin 3 parts After thoroughly mixing the above raw materials with a mixer, using a twin screw extruder Melt kneading was performed at a barrel temperature of 90 ° C. and a rotation speed of 100 rpm. The kneaded product was rolled and cooled, coarsely pulverized with a cutter mill, pulverized with a fine pulverizer using a jet stream, and then classified into a particle size distribution with an average particle size of 6 μm using a swirling air classifier. Further, an additive was mixed with 100 parts of the base colored particles 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 super mixer

  As a result of measuring the fluidity of the obtained toner with the evaluation device of the present invention, it was as shown in Table 1. Further, the toner obtained by the above production method and the carrier were mixed at a ratio of 2.5 parts with respect to 97.5 parts of the carrier to prepare a two-component developer. 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 an image evaluation experiment was performed. As a result, the dot reproducibility of the image was as shown in Table 1.

Example 10
Kneading, pulverization, and classification were performed using the same raw materials and production methods as in Example 9, and the particles were classified into a particle size distribution with an average particle size of 6 μm. Further, an additive was mixed with 100 parts of the base colored particles 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 1100rpm
Mixing time 120sec
Mixer super mixer

  As a result of measuring the fluidity of the obtained toner with the evaluation device of the present invention, it was as shown in Table 1. In addition, a two-component developer was prepared in the same manner as in Example 9, and an image evaluation experiment was performed. As a result, the dot reproducibility of the image was as shown in Table 1.

Example 11
Kneading, pulverization, and classification were performed using the same raw materials and production methods as in Example 9, and the particles were classified into a particle size distribution with an average particle size of 6 μm. Further, an additive was mixed with 100 parts of the base colored particles 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 super mixer

  As a result of measuring the fluidity of the obtained toner with the evaluation device of the present invention, it was as shown in Table 1. In addition, a two-component developer was prepared in the same manner as in Example 9, and an image evaluation experiment was performed. As a result, the dot reproducibility of the image was as shown in Table 1.

[Comparative Example 3]
Kneading, pulverization, and classification were performed using the same raw materials and production methods as in Example 9, and the particles were classified into a particle size distribution with an average particle size of 6 μm. Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner.
Additive silica fine powder 0.7 parts
Titanium oxide fine powder 0.3 part Mixing rotation speed 700rpm
Mixing time 120sec
Mixer super mixer

  As a result of measuring the fluidity of the obtained toner with the evaluation device of the present invention, it was as shown in Table 1. In addition, a two-component developer was prepared in the same manner as in Example 9, and an image evaluation experiment was performed. As a result, the dot reproducibility of the image was as shown in Table 1.

  The measurement results of Examples 1 to 11 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 by the fluidity evaluation device of the powder of the present invention in the toner powder phase and the dot reproducibility. It can be seen that dot reproducibility can be evaluated.

From the results shown in FIGS. 4 and 5, it is necessary to satisfy the following conditions in order to obtain a toner with good fluidity necessary for obtaining a high image quality with good dot reproducibility.
Under the following conditions, as can be seen from Table 1, when 20,000 sheets were run, there were no problems in toner conveyance such as blocking in the developing section.
(1) The torque value when the conical rotor enters is 0.1 to 7.5 mNm.
(2) The value of the load when the conical rotor enters is 0.01 to 1.04N.

  If the torque value when the conical rotor enters is less than 0.1 mNm, the charging characteristics other than the fluidity of the toner are deteriorated and the image quality is deteriorated. Become. When the load value at the time of entering the conical rotor is less than 0.01N, the charging characteristics of the toner are deteriorated and the image quality is deteriorated.

It is a schematic block diagram which shows an example of the fluidity | liquidity evaluation apparatus of the powder of this invention. (A), (b) is a schematic perspective view which shows the example of a conical rotor. It is a schematic perspective view which shows the example of attachment of a conical rotor. It is a graph which shows the relationship between the torque at the time of the conical rotor penetration | invasion of Examples 1-11 and Comparative Examples 1-3, and dot reproducibility. It is a graph which shows the relationship between the load at the time of the conical rotor penetration | invasion of Examples 1-11 and Comparative Examples 1-3, and dot reproducibility. It is the schematic which shows the example of the manufacturing apparatus of the toner which used the evaluation apparatus of this invention in the manufacture process of toner. It is the schematic which shows the example of the image development apparatus in which the toner manufactured using the evaluation apparatus of this invention is used.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Measuring apparatus 2 Consolidation zone 3 Measuring zone 23, 33 Sample container (container)
24 Lifting stage 25 Piston 26 Weight 32 Load cell 34 Lifting stage 35 Torque meter 36 Conical rotor 37 Mounting screw 71 Supply roller 72 Blade roller 73 Toner supply hopper 74 Stirring blade 75 Developing roller 76 Image carrier

Claims (22)

  In an apparatus for evaluating the fluidity of a powder by allowing a conical rotor to enter the powder phase while rotating, and measuring the torque or load generated when the conical rotor moves in the powder phase, The conical rotor is made of a material different from that of powder, and the surface irregularities are 0.01 to 100 μm.   2. The powder fluidity evaluation apparatus according to claim 1, wherein the powder phase is preliminarily brought into a compacted state by a compacting means, and measurement is performed by intruding the compacted powder phase while rotating the conical rotor. Powder flowability evaluation device.   3. The powder fluidity evaluation apparatus according to claim 2, wherein the powder phase is stabilized by a vibrator previously provided below a container for storing the powder, and then the powder phase is consolidated by the compaction means. An apparatus for evaluating the fluidity of powder, characterized in that   The powder fluidity evaluation apparatus according to claim 2 or 3, wherein the powder phase is measured by the compaction means so that the porosity of the powder phase is 0.4 to 0.7. Body fluidity evaluation device.   5. The powder fluidity evaluation apparatus according to claim 1, wherein the conical rotor is detachably provided with a mounting screw.   6. The powder fluidity evaluation apparatus according to claim 1, wherein the cone rotor has an apex angle of 20 to 150 degrees.   7. The powder fluidity evaluation apparatus according to claim 1, wherein the rotational speed of the conical rotor is 0.1 to 100 rpm.   8. The powder fluidity evaluation apparatus according to claim 1, wherein the conical rotor has an intrusion speed of 0.5 to 150 mm / min.   The torque when the conical rotor is rotated by 20 mm while rotating the conical rotor using the powder fluidity evaluation apparatus according to any one of claims 1 to 8 in the powder phase of the toner mixed with the additive Is adjusted to a range of 0.1 to 7.5 mNm.   The load when the conical rotor is rotated by 20 mm using the powder fluidity evaluation apparatus according to any one of claims 1 to 8 in the powder phase of the toner mixed with the additive. A toner for developing an electrostatic charge image, having a value adjusted to a range of 0.01 to 1.04 N.   11. The toner for developing an electrostatic charge image according to claim 9 or 10, wherein the toner contains at least one of a charge control agent and a release agent.   12. The electrostatic image developing toner according to claim 9, wherein an additive is attached or fixed to the surface of the toner.   13. The toner for developing an electrostatic charge image according to claim 9, wherein the toner has an average particle diameter of 4 to 8 [mu] m.   14. The electrostatic image developing toner according to claim 9, wherein the toner is produced by a polymerization method or a spray drying method.   The toner for developing an electrostatic charge image according to any one of claims 9 to 14, wherein the toner has an average circularity of 0.9 to 0.99.   9. A toner for developing an electrostatic charge image, wherein evaluation is performed in a toner manufacturing process using the powder fluidity evaluation apparatus according to claim 1, and the toner is manufactured based on the evaluation. Manufacturing method.   A developing method comprising developing the latent image in contact or non-contact using the electrostatic charge developing toner according to claim 9.   18. The one-component developing method according to claim 17, wherein at least one of a doctor roller and a supply roller is used.   16. A developing method comprising developing a latent image using the electrostatic charge developing toner according to claim 9 and a carrier having a particle diameter of 20 to 70 [mu] m.   20. The developing method according to claim 17, wherein an AC bias voltage component is applied for development.   A toner cartridge containing the electrostatic charge developing toner according to claim 9.   A process cartridge containing the electrostatic charge developing toner according to claim 9.

Images