JP2006259062A - Electrostatic charge image developing toner, cartridge and development method using the toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrostatic charge image developing toner having such toner hardness to enable the toner of the permanently stable amount of charge to be supplied a developing section without allowing the toner to be crushed by the friction with another members even when a number of sheets by is developed by running, a method for manufacturing the same, and a developing means using the same. <P>SOLUTION: The electrostatic charge image developing toner has an average value of micro Vickers hardness of 8 to 11 kg/mm<SP>2</SP>, when a toner kneaded material obtained by mixing at least a resin, a pigment, and a release agent and mixing, melting, solidifying and pulverizing the mixture is measured a plurality of times at a measuring temperature 50°C under a load 10 g. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an electrostatic charge developing toner used for one-component development or two-component development, a cartridge using the same, and a developing method.

Patent Document 1 describes a toner composition comprising a resin having a hardness-imparting action having a Vickers hardness of ² to 8 kg / mm ² . The aim of the present invention is to provide stable shape retention, low-temperature fixability, and offset resistance over a long period of time.
However, the present invention uses three types of resins that are functionally separated, and does not consider anything about the hardness of the toner after melt-kneading. Therefore, when developing a large number of sheets by running, the toner is pulverized by friction with other members, and there is a problem that toner having a stable charge amount cannot be supplied to the developing unit indefinitely.

JP-A 62-209466

  It is an object of the present invention to provide a toner that can supply a toner having a stable charge amount to the developing unit forever without being pulverized by friction with other members even when developing a large number of sheets by running. The object is to provide a toner for developing electrostatic charge having hardness, a method for producing the toner, and a developing means using the toner.

In the first aspect of the present invention, a toner kneaded product obtained by mixing, melting, solidifying, and pulverizing a composition containing at least a resin, a pigment, and a release agent was measured a plurality of times at a measurement temperature of 50 ° C. and a load of 10 g. The present invention relates to an electrostatic charge developing toner characterized in that the average value of micro Vickers hardness is 8 to 11 kg / mm ² .
The second of the present invention relates to the electrostatic charge developing toner according to claim 1, wherein the content of the releasing agent is 1.0 to 3.0 parts by weight with respect to 50 parts by weight of the resin.
3. The electrostatic charge developing toner according to claim 2, wherein the composition further comprises 1.5 to 3.5 parts by weight of an additive for dispersing a release agent in an amount of 50 parts by weight of the resin. About.
According to a fourth aspect of the present invention, a granular release agent portion (which looks round when viewed with an electron microscope) is interspersed inside the toner kneaded product, and an additive for dispersing the release agent is present in the vicinity thereof. The electrostatic charge developing toner according to claim 3.
According to the fifth aspect of the present invention, an ellipsoidal release agent portion (which looks like an ellipse when viewed with an electron microscope) is scattered inside the toner kneaded product, and an additive for dispersing the release agent is present in the vicinity thereof. The electrostatic charge developing toner according to claim 3.
The sixth aspect of the present invention relates to the electrostatic charge developing toner according to any one of claims 1 to 5, wherein the weight average particle diameter of the particles after the pulverization step of the toner kneaded product is 4 to 8 µm.
The seventh aspect of the present invention relates to the electrostatic charge developing toner according to any one of claims 1 to 6, which has an average circularity of 0.9 to 0.99.
An eighth 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 1 to 7.
A ninth aspect of the present invention relates to the one-component developing method according to claim 8, wherein a doctor roller and / or a supply roller are used.
A tenth 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 1 to 7 and a carrier having an average particle diameter of 20 to 100 μm.
An eleventh aspect of the present invention relates to a toner cartridge and a process cartridge that are filled with the electrostatic charge developing toner according to any one of the first to seventh aspects.
A twelfth aspect of the present invention relates to a micro Vickers hardness measuring apparatus for electrostatic charge developing toner, characterized in that a heating coil and a temperature sensor are provided under a sample stage.
According to the thirteenth aspect of the present invention, a toner kneaded product obtained by mixing, melting, solidifying, and pulverizing at least a resin, a pigment, and a release agent has a plurality of micro Vickers hardnesses under measurement conditions of a measurement temperature of 50 ° C. and a load of 10 g. The present invention relates to a method for evaluating a kneaded product for toner, wherein the suitability for toner is evaluated by measuring the number of times and obtaining an average value thereof.

  The electrostatic charge developing toner of the present invention has a structure in which at least the surface of a powder comprising a resin, a pigment, and a release agent is covered with an additive, and the resin, the pigment, the release agent, etc. are in an island-like phase separation. The structure is adopted. Since the stability of the toner containing the release agent or the like greatly varies depending on the temperature state, in the present invention, the hardness characteristic in the temperature state is evaluated appropriately, and the conditions for obtaining the optimum toner are selected.

  The resin is preferably a polyester resin or / and a polyol resin conventionally used for 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 singly or in combination. In the case of using them together, even if one resin itself is insufficient in hardness, it is sufficient that the hardness of the combined mixture satisfies the hardness requirement of the present invention.

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, the toner may be mixed (externally added) with the toner particles. May be. 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 of the present invention, oilless fixing is realized, and 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.

  As an example of a method for producing the toner according to the present invention, first, the above-described resin, pigment or dye as a colorant, charge control agent, release agent, other additives, etc. are sufficiently obtained by a mixer such as a Henschel mixer. After mixing, batch type twin rolls, Banbury mixer and continuous twin screw extruder, for example, KTK type twin screw extruder manufactured by Kobe Steel, TEM type twin screw extruder manufactured by Toshiba Machine Co., Ltd., manufactured by KCK Thermal kneaders such as a twin screw extruder, a PCM type twin screw extruder manufactured by Ikekai Tekko Co., Ltd., a KEX type twin screw extruder manufactured by Kurimoto Ironworks Co., Ltd. The constituent materials are kneaded well, and after rolling and cooling, cutting is performed. The hardness of the chip-like kneaded material after the cutting is measured with a micro Vickers hardness measuring device (for example, AKK-G1 type manufactured by Akashi). The measurement method conforms to JIS Z2251-80 and JIS B7734-91. The measurement load needs to be selected under conditions where cracks and depressions do not occur within the range of 50 g or less, and in the present invention, it is desired to measure the hardness distribution of a minute part (preferably 50 μm square or less). The load was set to 10 g so that the size of the indentation was reduced.

  The micro Vickers hardness Hv of the toner kneaded product has a correlation with the sleeve fixing property of the developing portion and the filming property of the photosensitive member. When the Hv is small, the sleeve fixing property and the filming property of the photosensitive member are deteriorated and the durability property is deteriorated. Experiments have shown that it deteriorates. This tendency becomes prominent when a release agent such as WAX is added to the toner, and it is necessary to increase the micro Vickers hardness of the toner kneaded product.

  The phenomenon of durability deterioration is likely to occur when the temperature is high, and occurs as a problem when the internal temperature of the printer or copying machine is high. Therefore, as an accurate evaluation method according to the phenomenon, micro Vickers hardness Hv measurement was performed with the sample temperature raised to 50 ° C., and the toner stability was evaluated. The toner kneaded product was heated by providing a heating coil and a temperature sensor under the sample stage of the micro Vickers hardness measuring apparatus and controlling the temperature with a precision of ± 0.1 ° C. using a temperature control unit.

  The temperature characteristics of the micro-Vickers hardness Hv of the toner kneaded product are as shown in FIG. 1, and it can be seen that as the temperature is increased, the Hv gradually decreases and becomes softer. In the present invention, the micro Vickers hardness Hv measurement at 50 ° C. was performed, and the relationship between the sleeve fixing property and the filming characteristic of the photoreceptor was examined. The temperature was raised to 50 ° C. and left to stand for 5 minutes in the same state, after which the diamond indenter of a micro Vickers hardness measuring device was pressed against the toner kneaded product (load: 10 g) and measurement was performed. The measurement was repeated 2 to 10 times in order to increase the reliability of the measured value, and the average value was evaluated.

As a result, it was found that the average value of the repeatedly measured Hv values should be 8 to 11 kg / mm ² in order to improve the sleeve adhesion and the filming characteristics of the photoreceptor. In other words, when a release agent such as WAX is put in the toner kneaded product, the Hv becomes small, but if the average value of Hv when measured repeatedly at 50 ° C. is 8 to 11 kg / mm ^{2, there} is a problem such as sleeve adhesion. And the durability of the toner is improved. If Hv is less than 8 kg / mm ² , sleeve sticking, sticking to a doctor blade, filming, toner scattering, etc. are likely to occur. When Hv is greater than 11 kg / mm ² , the yield of pulverization is deteriorated, which affects environmental (energy) problems and cost problems.

The hardness when the temperature of the toner kneaded product is raised depends on pre-mixing conditions, kneading conditions in the kneading process (screw shape, kneading rotation speed, temperature, degree of vacuum, cooling, etc.), rolling cooling conditions in the rolling cooling process ( The cooling temperature, the number of revolutions, the pressing pressure, etc.) and the composition and structure of the kneaded product vary. In particular, in the case of a toner kneaded product containing a release agent such as WAX, the influence of the additive is large, and the hardness is increased by adding the additive. The optimum range of the addition amount was 1.5 to 3.5 parts by weight with respect to 50 parts by weight of the resin based on our experimental results. The additive effect is large when the amount of the release agent such as WAX is 1.0 to 3.0 parts by weight with respect to 50 parts by weight of the resin, and the amount of the release agent such as WAX is greater than 3.0 parts by weight. As a result, the effect of the additive was reduced.
As a result of observing the structure of the kneaded material with an electron microscope, the hardness increased in the following state.
(A) Soft parts of release agents such as granular WAX having a particle size of 1 μm or more are scattered in the kneaded product, and additives are present in the vicinity thereof.
(B) Inside the kneaded product, soft portions of a release agent such as an elliptical WAX having a size of 10 μm or more are dotted, and additives are present in the vicinity thereof.
That is, the additive is present in the vicinity of a release agent such as WAX, and the support is provided with the additive in the soft part of the release agent such as WAX to increase the hardness. However, when the amount of the release agent such as WAX is increased, it becomes difficult to reinforce with the additive and the hardness cannot be increased.

These internal structures are also affected by granulation conditions such as the kneading conditions and rolling cooling conditions, and are formed by combining these conditions in a composite manner. Further, the present structure may be realized by artificially mixing and mixing fine materials and performing fine distribution.
In the case of such a structure, it is necessary to pay attention to the region other than the release agent and additive such as WAX, in which the toner is required to have a uniform material.
The difference in the state of the release agent part such as WAX can be controlled by the conditions of the kneading process. Specifically, it changes as follows.
Barrel temperature …………………… Low →→→→→→→→ High Release part of WAX etc. (b) Ellipse →→→→ (a) Fine dot kneading speed ... ……………………… Low →→→→→→→→ High Wax and other mold release agent parts… (b) Ellipse →→→→ (a) Fine dots However, these tendencies are complex It should be noted that other factors other than these two conditions are closely related.

The micro Vickers hardness Hv of the toner kneaded product may be used for process control by measuring the micro Vickers hardness of the toner kneaded product after the kneading step before pulverizing to produce a powder toner. In this case, the toner kneaded material after cutting may be extracted, and the sample may be measured after being heated as it is with a micro Vickers hardness measuring device. The number of measurements is suitably about 2 to 10 times. If the surface is smooth, it can be 2 to 5 times. It is also possible to control the kneading conditions of the kneader or the pulverizing conditions of the pulverizer based on the inspection result of the hardness.
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, passed through a sieve of 250 mesh or more, and coarse particles and aggregated particles are removed to obtain the toner of the present invention.

  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 weight average particle diameter of the toner is 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 tend to occur. 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.

  In order to achieve high image quality, the average circularity of the electrostatic charge developing toner needs to be 0.9 to 0.99. The shape of the toner particles also greatly affects the fluidity of the electrostatic charge developing toner, and those having an average circularity in the range of 0.9 to 0.99 are close to the fluidity of the electrostatic charge developing toner. Excellent image quality. The circularity of the toner particles was measured as an average circularity using a flow particle image analyzer FPIA-1000 (Toa Medical Electronics Co., Ltd.).

  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. .

  The electrostatic charge developing toner of the present invention is used as a one-component or two-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 electrostatic charge developing toner of the present invention, development efficiency is improved and image characteristics are improved.

  Further, in the one-component development method, it is effective to use the present toner in a development method in which a roller-shaped blade for making the toner layer uniform is provided at the outlet of the toner supply unit. In such a system, when conventional toner is used, not only filming on the sleeve and the photoconductor but also filming on the doctor roller occurs, and not only the toner layer cannot be formed uniformly, but also the toner is charged. The toner 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 to the doctor roller does not occur, stable development is performed, and the system has excellent durability characteristics.

Further, in the one-component development method, it is effective to use the present toner in a development method in which a supply roller for stabilizing the amount of toner drawn up is provided in the toner supply unit. In such a system, when conventional toner is used, not only filming to the sleeve and the photosensitive member, but also filming to the supply roller occurs, and not only the toner cannot be stably supplied, but also the toner is charged. The toner becomes non-uniform and the toner charge amount becomes small. For this reason, poor development occurs.
However, when this toner is used, filming on the supply roller does not occur, stable development is performed, and the system has excellent durability characteristics.

  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 100 μm. Preferably 20-70 micrometers is good.
When the average particle diameter of the carrier is within this range, the charge amount of the toner can be made more uniform by combining with the toner of the present invention when the toner concentration inside the developing device is in the range of 2 to 10% by weight. . When the thickness is 20 μm or less, carrier particles are likely to adhere to the photosensitive member, and the stirring efficiency with the toner is deteriorated, so that it is difficult to obtain a uniform charge amount of the toner. When the thickness exceeds 100 μm, fine image reproducibility is deteriorated.

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 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.

Since the electrostatic charge developing toner of the present invention is excellent in 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. Yes.
Examples of the cartridge container include a toner cartridge that is filled with electrostatic charge developing toner, and a process cartridge that includes at least a photosensitive member and developing means, and fills the toner storage portion of the developing means with electrostatic charge developing toner.

  According to the present invention, it is possible to provide a toner that enables oilless fixing, eliminates filming on a photosensitive member, a developing roller, a doctor roller, and the like, which has a problem with durability characteristics, and does not cause deterioration in image quality.

EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated, this does not limit this invention at all. In addition, all the parts in the following mixing | blending are a weight part.
This time, the toner composition and toner kneading conditions were changed to prepare a toner kneaded product, the toner kneaded material hardness was evaluated using this evaluation method, and 20,000 sheets were obtained using the toner prepared by pulverizing the toner kneaded product. The running durability test was conducted, and the sleeve fixing rank was evaluated by a 5-grade evaluation (rank 1: bad → rank 5: good). Further, a running durability test of 20,000 sheets was conducted to evaluate defects in image stability and fixability due to filming of the photoreceptor. The case where there was no defect was evaluated as ◯, and the case where there was a defect was evaluated as x. The evaluation conditions of the micro Vickers hardness measuring apparatus were as follows.
・ Temperature: 50 ℃
・ Temperature holding time: 5 minutes ・ Load: 10 g
・ Load holding time: 20 sec
・ Measurement repeat count: 10 times

Example 1
Resin Polyester resin 50 parts Pigment Carbon black 5 parts Charge control agent Zinc salicylate 0.5 parts Mold release agent Rice wax 2.5 parts Additives Styrene-acrylic resin 1.5 parts After thoroughly mixing the raw materials with a mixer The mixture was melt kneaded with a twin screw extruder at a kneaded material temperature of 100 ° C. and a kneader rotation 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 7 μm using a swirling air classifier. 1 part of silica fine powder was mixed with 100 parts of the base colored particles thus obtained with a super mixer.
The micro Vickers hardness of the toner kneaded product was repeatedly measured 10 times, and the average value was calculated. The results are shown in Table 1.
A large number of granular WAX portions and elliptical WAX portions of 10 μm or more existed in the toner kneaded product, and additives existed in the vicinity thereof.
The obtained toner was subjected to a durability test using a one-component developing device using an OPC drum and a doctor roller, and the sleeve adhesion rank was evaluated. Also, image and fixing problems were evaluated.

Example 2
Resin Polyester resin 50 parts Pigment Carbon black 5 parts Charge control agent Zinc salicylate 0.5 parts Mold release agent Rice wax 2.5 parts Additives Styrene-acrylic resin 1.5 parts After thoroughly mixing the raw materials with a mixer The mixture was melt kneaded with a twin screw extruder at a kneaded material temperature of 100 ° C. and a kneader rotation speed of 140 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 7 μm using a swirling air classifier. 1 part of silica fine powder was mixed with 100 parts of the base colored particles thus obtained with a super mixer.
The micro Vickers hardness of the toner kneaded product was repeatedly measured 10 times, and the average value was calculated. The results are shown in Table 1.
Many fine granular WAX portions existed in the toner kneaded product, and additives existed in the vicinity thereof.
The obtained toner was subjected to a durability test using a one-component developing device using an OPC drum and a doctor roller, and the sleeve adhesion rank was evaluated. Also, image and fixing problems were evaluated. The results are shown in Table 1.

Example 3
Resin Polyester resin 50 parts Pigment Carbon black 5 parts Charge control agent Zinc salicylate 0.5 parts Mold release agent Rice wax 2.5 parts Additives Styrene-acrylic resin 1.5 parts After thoroughly mixing the raw materials with a mixer The mixture was melt kneaded with a twin screw extruder at a kneaded material temperature of 100 ° C. and a kneader rotation speed of 160 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 7 μm using a swirling air classifier. 1 part of silica fine powder was mixed with 100 parts of the base colored particles thus obtained with a super mixer.
The micro Vickers hardness of the toner kneaded product was repeatedly measured 10 times, and the average value was calculated. The results are shown in Table 1.
Many fine granular WAX portions existed in the toner kneaded product, and additives existed in the vicinity thereof.
The obtained toner was subjected to a durability test using a one-component developing device using an OPC drum and a doctor roller, and the sleeve adhesion rank was evaluated. Also, image and fixing problems were evaluated. The results are shown in Table 1.

Example 4
Resin Polyester resin 50 parts Pigment Carbon black 5 parts Charge control agent Zinc salicylate 0.5 part Mold release agent Rice wax 2.5 parts Additive Styrene-acrylic resin 2.5 parts After mixing the raw materials with a mixer The mixture was melt kneaded with a twin screw extruder at a kneaded material temperature of 100 ° C. and a kneader rotation speed of 140 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 7 μm using a swirling air classifier. 1 part of silica fine powder was mixed with 100 parts of the base colored particles thus obtained with a super mixer.
The toner was mixed at a ratio of 2.5 parts to 97.5 parts of a carrier in which a silicon resin was coated on the surface of ferrite particles having an average particle diameter of 70 μm to prepare a two-component developer.
Table 1 shows the average value of micro Vickers hardness of the toner kneaded product.
Many fine granular WAX portions existed in the toner kneaded product, and additives existed in the vicinity thereof.
The developer thus obtained 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 endurance test was performed to evaluate the sleeve adhesion. Also, image and fixing problems were evaluated. The results are shown in Table 1.

Example 5
Resin Polyester resin 50 parts Pigment Carbon black 5 parts Charge control agent Zinc salicylate 0.5 part Mold release agent Rice wax 2.5 parts Additive Styrene-acrylic resin 3.5 parts After thoroughly mixing the raw materials with a mixer The mixture was melt kneaded with a twin screw extruder at a kneaded material temperature of 100 ° C. and a kneader rotation speed of 140 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 7 μm using a swirling air classifier. 1 part of silica fine powder was mixed with 100 parts of the base colored particles thus obtained with a super mixer.
The toner was mixed at a ratio of 2.5 parts to 97.5 parts of a carrier in which a silicon resin was coated on the surface of ferrite particles having an average particle diameter of 70 μm to prepare a two-component developer.
Table 1 shows the average value of micro Vickers hardness of the toner kneaded product.
Many fine granular WAX portions existed in the toner kneaded product, and additives existed in the vicinity thereof.
The developer thus obtained 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 endurance test was performed to evaluate the sleeve adhesion. Also, image and fixing problems were evaluated. The results are shown in Table 1.

Example 6
Resin Polyester resin 50 parts Pigment Copper phthalocyanine blue pigment (CI Pigment Blue 15: 3)
2.5 parts Charge control agent Zinc salicylate 1 part Mold release agent Rice wax 1.5 parts Additive Styrene-acrylic resin 1.5 parts The raw materials are sufficiently mixed with a mixer and then kneaded with a twin screw extruder. Melt kneading was performed at a temperature of 100 ° C. and a kneader rotating speed of 140 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 7 μm using a swirling air classifier. 1 part of silica fine powder was mixed with 100 parts of the base colored particles thus obtained with a super mixer.
The toner was mixed at a ratio of 2.5 parts to 97.5 parts of a carrier in which a silicon resin was coated on the surface of ferrite particles having an average particle diameter of 70 μm to prepare a two-component developer.
Table 1 shows the average value of micro Vickers hardness of the toner kneaded product.
Many fine granular WAX portions existed in the toner kneaded product, and additives existed in the vicinity thereof.
The developer thus obtained 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 endurance test was performed to evaluate the sleeve adhesion. Also, image and fixing problems were evaluated. The results are shown in Table 1.

Example 7
Resin Polyester resin 50 parts Pigment Copper phthalocyanine blue pigment (CI Pigment Blue 15: 3)
2.5 parts Charge control agent Zinc salicylate 1 part Mold release agent Rice wax 1.5 parts Additives Styrene-acrylic resin 2.5 parts After sufficiently mixing the raw materials with a mixer, the mixture is kneaded with a twin screw extruder. Melt kneading was performed at a temperature of 100 ° C. and a kneader rotating speed of 140 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 7 μm using a swirling air classifier. 1 part of silica fine powder was mixed with 100 parts of the base colored particles thus obtained with a super mixer.
The toner was mixed at a ratio of 2.5 parts to 97.5 parts of a carrier in which a silicon resin was coated on the surface of ferrite particles having an average particle diameter of 70 μm to prepare a two-component developer.
Table 1 shows the average value of micro Vickers hardness of the toner kneaded product.
Many fine granular WAX portions existed in the toner kneaded product, and additives existed in the vicinity thereof.
The developer thus obtained 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 endurance test was performed to evaluate the sleeve adhesion. Also, image and fixing problems were evaluated. The results are shown in Table 1.

Example 8
Resin Polyol resin 50 parts Pigment Magenta pigment (CI Pigment Red 57) 3 parts Charge control agent Salicylic acid zinc salt 2 parts Mold release agent Low molecular weight polyethylene 3 parts Additives Polyethylene resin 1.8 parts Then, the mixture was melt-kneaded by a twin screw extruder at a kneaded material temperature of 100 ° C. and a kneader rotation 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 7 μm using a swirling air classifier. 1 part of silica fine powder was mixed with 100 parts of the base colored particles thus obtained with a super mixer.
The toner was mixed at a ratio of 2.5 parts to 97.5 parts of a carrier in which a silicon resin was coated on the surface of ferrite particles having an average particle diameter of 70 μm to prepare a two-component developer.
Table 1 shows the average value of micro Vickers hardness of the toner kneaded product.
A large number of granular WAX portions and elliptical WAX portions of 10 μm or more existed in the toner kneaded product, and additives existed in the vicinity thereof.
The developer thus obtained 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 endurance test was performed to evaluate the sleeve adhesion. Also, image and fixing problems were evaluated. The results are shown in Table 1.

Example 9
Resin Polyol resin 50 parts Pigment Magenta pigment (CI Pigment Red 57) 3 parts Charge control agent Salicylic acid zinc salt 2 parts Release agent Low molecular weight polyethylene 3 parts Additives Polyethylene resin 3 parts Thoroughly mix the raw materials with a mixer After that, the mixture was melt-kneaded with a twin screw extruder at a kneaded material temperature of 100 ° C. and a kneader rotation 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 7 μm using a swirling air classifier. 1 part of silica fine powder was mixed with 100 parts of the base colored particles thus obtained with a super mixer.
The toner was mixed at a ratio of 2.5 parts to 97.5 parts of a carrier in which a silicon resin was coated on the surface of ferrite particles having an average particle diameter of 70 μm to prepare a two-component developer.
Table 1 shows the average value of micro Vickers hardness of the toner kneaded product.
A large number of granular WAX portions and elliptical WAX portions of 10 μm or more existed in the toner kneaded product, and additives existed in the vicinity thereof.
The developer thus obtained 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 endurance test was performed to evaluate the sleeve adhesion. Also, image and fixing problems were evaluated. The results are shown in Table 1.

Comparative Example 1
A toner was produced in the same manner as in Example 1 except that no additive was added in Example 1, and the same evaluation as in Example 1 was performed.
The obtained toner was subjected to a durability test using a one-component developing device using an OPC drum and a doctor roller, and the sleeve adhesion rank was evaluated. Also, image and fixing problems were evaluated. The results are shown in Table 1.

Comparative Example 2
In Example 4, a two-component developer was prepared in the same manner as in Example 4 except that the amount of the additive styrene-acrylic resin was increased to 4.0 parts, and the same evaluation as in Example 4 was performed. .
The developer thus obtained 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 endurance test was performed to evaluate the sleeve adhesion. Also, image and fixing problems were evaluated. The results are shown in Table 1.

Comparative Example 3
In Example 4, a two-component developer was prepared in the same manner as in Example 4 except that the release agent and additives were not added, and the same evaluation as in Example 4 was performed.
The developer thus obtained 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 endurance test was performed to evaluate the sleeve adhesion. Also, image and fixing problems were evaluated. The results are shown in Table 1.

Comparative Example 4
In Example 4, a two-component developer was prepared in the same manner as in Example 4 except that the amount of rice wax as a release agent was 0.5 part, and no additive was added. Evaluation was performed.
The developer thus obtained 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 endurance test was performed to evaluate the sleeve adhesion. Also, image and fixing problems were evaluated. The results are shown in Table 1.

  The experimental results of the above examples are shown in the table below. The evaluation items are the average value when the micro-Vickers hardness Hv of the toner kneaded product is measured 10 times, the sleeve fixing rank in the forced deterioration test, the image stability, and the fixing property. Further, it can be seen from Table 1 that it is necessary to add a release agent in an amount of 1.0 to 3.0 parts by weight (when the resin is 50 parts by weight) in order to improve the fixability.

It is a graph which shows the relationship between the micro Vickers hardness average value of toner kneaded material, and temperature. 3 is a graph showing the relationship between the average value of micro Vickers hardness of a toner kneaded product and sleeve fixing property by data of Examples 1 to 9 and Comparative Examples 1 and 2. FIG.

Claims (13)

Average of micro Vickers hardness of a toner kneaded product obtained by mixing, melting, solidifying, and pulverizing a composition containing at least a resin, a pigment, and a release agent when measured multiple times at a measurement temperature of 50 ° C. and a load of 10 g. A toner for developing electrostatic charge, having a value of 8 to 11 kg / mm ² .   The electrostatic charge developing toner according to claim 1, wherein the content of the releasing agent is 1.0 to 3.0 parts by weight with respect to 50 parts by weight of the resin.   The electrostatic charge developing toner according to claim 2, further comprising 1.5 to 3.5 parts by weight of an additive for dispersing a release agent added to 50 parts by weight of the resin.   The electrostatic charge developing toner according to claim 3, wherein the toner kneaded material is dotted with granular release agent portions, and an additive for dispersing the release agent is present therearound.   The electrostatic charge developing toner according to claim 3, wherein the toner kneaded product is interspersed with elliptical release agent portions, and a release agent dispersing additive is present in the vicinity thereof.   The toner for electrostatic charge development according to any one of claims 1 to 5, wherein a weight average particle diameter of the particles after the pulverization step of the toner kneaded product is 4 to 8 µm.   The electrostatic charge developing toner according to claim 1, having an average circularity of 0.9 to 0.99.   A one-component developing method comprising performing contact or non-contact development using the electrostatic charge developing toner according to claim 1.   9. The one-component developing method according to claim 8, wherein a doctor roller and / or a supply roller are used.   8. A two-component developing method comprising developing using the electrostatic charge developing toner according to claim 1 and a carrier having an average particle diameter of 20 to 100 [mu] m.   A toner cartridge or a process cartridge, which is filled with the electrostatic charge developing toner according to claim 1.   A micro Vickers hardness measuring apparatus for electrostatic charge developing toner, characterized in that a heating coil and a temperature sensor are provided under a sample stage. The toner kneaded material obtained by mixing, melting, solidifying, and pulverizing at least a resin, a pigment, and a release agent was measured for its micro Vickers hardness several times under the measurement conditions of a measurement temperature of 50 ° C. and a load of 10 g, and the average value was obtained. To evaluate the suitability of the toner for use, and a method for evaluating a kneaded product for toner.

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