toner, developer, image-forming apparatus and image-forming method

专利摘要:
TONER, DEVELOPER, IMAGE TRAINING EQUIPMENT AND IMAGE TRAINING METHOD. A toner including: a binder resin; a release agent; and a colorant, in which the binder resin contains a crystalline polyester resin and a non-crystalline polyester resin, in which the release agent has an endothermic peak temperature of 60 ° C to 80 ° C at the second temperature raising in calorimetry of differential scanning, and the release agent is an ester wax that satisfies the following expressions (1) and (2): 1.1 Pa.s? ?*The ? 2.0 Pa.s ... Expression (1); 0.001? ? * b /? * a? 1.00 ... Expression (2); where in Expressions (1) and (2),? * denotes a complex viscosity (Pa.s) determined by measuring a dynamic viscoelasticity of the release agent at a measurement frequency of 6.28 rad / s, and? * b denotes a complex viscosity (Pa.s) determined by measuring a dynamic viscoelasticity of the release agent at a measurement frequency of 62.8 rad / s.
公开号:BR112014000266B1
申请号:R112014000266-5
申请日:2012-07-03
公开日:2020-11-10
发明作者:Mamoru Hozumi；Junichi Awamura；Teruki Kusahara；Daisuke Ito；Satoshi Ogawa；Takahiro Honda；Kiwako Hirohara；Osamu Uchinokura；Satoshi Kojima；Syouko Satoh；Tsuneyasu Nagatomo；Masaki Watanabe；Masaaki Oka；Yasuaki Ohta
申请人:Ricoh Company, Ltd；
IPC主号:

专利说明:

Technical Field
[0001] The present invention relates to a toner used appropriately, for example, in electrophotography, electrostatic recording and electrostatic printing; and a developer, an imaging device and an imaging method each using toner. Background of the technique
[0002] Copiers that are recently demanded can consistently form high quality images and are compact and capable of copying a greater number of slides at high speed. However, today's high-speed copiers do not necessarily achieve satisfactory high-speed processing. One possible reason for this is that optical equipment inside copiers is contaminated due to the evaporation of wax and dust particles that are released to the outside. In particular, the release of dust particles to the outside has recently been regulated from the point of view of environmental protection, since such dust particles cause a serious problem of adversely affecting human bodies. That is, it is possible for copiers to achieve a high speed process by reducing the amount of volatile components contained in the wax.
[0003] For example, PTL 1 proposes a latent electrostatic image development toner containing at least one binder resin, a colorant and an ester wax, in which the ester wax is contained in the toner in an amount of 3 parts in mass to 40 parts by mass per 100 parts by mass of the binder resin, where the ester wax contains an ester compound represented by the following formula RI-COO-R2 [where R2 and R2 each represent a linear alkyl group having 15 to 45 carbon atoms] and in which the ester wax contains ester compounds having the same total number of carbon atoms in an amount of 50% by mass to 95% by mass. The proposed electrostatic imaging imaging toner can exhibit good attachment properties at low temperatures. However, this proposal does not consider any attempts to reduce the amount of volatile components in order to achieve high-speed copier processing.
[0004] PTL 2 proposes a toner containing polyalkylene as a release agent and describes that the toner has a fixing property resistant to factors derived from the environments of use. However, this proposal does not consider the use of an ester wax or the use of an ester wax in a system containing a crystalline polyester resin.
[0005] Thus, at present, satisfactory toners or relevant techniques have not yet been provided which exhibit good fixation property at 150 ° C or lower to form good fixed images and which, even when using high-speed copiers, can greatly suppress contamination inside the copiers due to volatile wax dust particles and the release of dust particles to the outside. Citation List Patent Literature
[0006] PTL 1 Japanese Patent (JP-B) No. 3287733
[0007] PTL 2 Japanese Open Patent Application (JP-A) No. 2005-173315 Summary of the Invention Technical problem
[0008] An objective of the present invention is to provide: a toner that exhibits good fixing property at 150 ° C or lower to form good still images and that, even when used in high speed copiers, can greatly suppress contamination within copiers due to volatile wax dust particles and the release of dust particles to the outside; and a developer, an imaging method and an imaging device each using toner. Solution to the Problem
[0009] Means for solving the above problems are as follows.
[00010] A toner of the present invention includes:
[00011] a binder resin;
[00012] a release agent; and
[00013] a colorant,
[00014] wherein the binder resin contains a crystalline polyester resin and a non-crystalline polyester resin,
[00015] in which the release agent has an endothermic peak temperature of 60 ° C to 80 ° C in the second temperature raising in differential scanning calorimetry, and in which the release agent is an ester wax that satisfies the following expressions (1) and (2): 1.1 Pa.s η * to <2.0 Pa.s ... Expression (1)
[00016] 0,001 <η * b / η * a <1.00 ... Expression (2) where in Expressions (1) and (2), η * a denotes a complex viscosity (Pa.s) determined by the measurement of a dynamic viscoelasticity of the release agent at a measurement frequency of 6.28 rad / s, and η * b denotes a complex viscosity (Pa.s) determined by measuring a dynamic viscoelasticity of the release agent at a measurement frequency of 62.8 rad / s. Advantageous Effects of the Invention
[00017] The present invention can provide: a toner that exhibits good fixation property at 150 ° C or lower to form good still images and that, even when used in high speed copiers, can greatly suppress contamination inside copiers due to volatile wax dust particles and the release of dust particles to the outside; and a developer, an imaging method and an imaging device each using toner. These can solve the above problems and achieve the above goals. Brief Description of Drawings
[00018] Fig. 1 is a schematic view of an example of an imaging apparatus of the present invention.
[00019] Fig. 2 is a schematic view of another example of the imaging apparatus of the present invention.
[00020] Fig. 3 is an enlarged view of an imaging portion of the imaging apparatus of Fig. 2.
[00021] Fig. 4 is a schematic view of an example of a process cartridge of the present invention. Description of Modalities (Toner)
[00022] A toner of the present invention contains a binder resin, a release agent and a colorant; and, if necessary, additionally contains other components.
[00023] The toner of the present invention contains a crystalline polyester resin as the binder resin. The crystalline polyester resin has high crystallinity and thus exhibits such a hot melt property that the viscosity is rapidly decreased in the vicinity of a temperature at which fixation is initiated. That is, the use of crystalline polyester resin provides a toner having both good thermal resistance storage stability and good low temperature fastening property, since the crystalline polyester resin exhibits good thermal resistance storage stability while maintaining its crystallinity immediately before melting is initiated and has the viscosity rapidly decreased (acute melting property) to set at a temperature at which melting is initiated. In addition, the toner containing the crystalline polyester resin has an adequate difference between the lower limit of the fixing temperature and the temperature at which the hot displacement occurs (that is, a release range).
[00024] However, as part of the crystalline polyester resin present in the toner is in a state compatible with the non-crystalline polyester resin, the crystalline polyester resin tends to cause the formation of film in a developing device, potentially leading to contamination of the image development and degradation device. Thus, it is necessary for the release agent to exhale from the toner. In general, in polymeric release agents such as ester waxes, the kinetic state of your polymer chains changes with increasing temperature. The dynamic viscoelasticity that results from the change in its kinetic state depends on the frequency by measuring the dynamic viscoelasticity and on properties such as the molecular structure of the release agent. In addition, the dynamic viscoelasticity of the release agent is known to change quite close to its melting point. The release agent is heated and melted in a short time with fixing the toner, and the fixing property depends on the change in dynamic viscoelasticity close to the melting point of the same.
[00025] Therefore, the release agent used in the toner of the present invention is an ester wax that satisfies the following expressions (1) and (2): 1.1 Pa.sd η * ad 2.0 Pa.s .. Expression (1) 0.001 <η * b / η * a <1.00 ... Expression (2)
[00026] where in Expressions (1) and (2), η * a denotes a complex viscosity (Pa.s) determined by measuring a dynamic viscoelasticity of the release agent at a measurement frequency of 6.28 rad / s, and η * b denotes a complex viscosity (Pa.s) determined by measuring a dynamic viscoelasticity of the release agent at a measurement frequency of 62.8 rad / s.
[00027] In electrophotographic processes, the toner usage environments are varied with the imaging method used or the type of imaging device used. Toner vibration states in such usage environments can be replaced with frequencies by measuring dynamic viscoelasticity. When considering the environments in which toner is used to assess their response to frequencies, it is reasonable to employ two different measurement frequencies: 6.28 rad / s and 62.8 rad / s. Specifically, the ratio (η * b / η * a) between the complex viscosities at the different frequencies as shown in Expression (2) takes into account the dependence on the frequency in dynamic environments. The release agent that satisfies Expression (2) decreases in viscosity with fixation (at high frequencies) similar to crystalline polyester resin, not degrading the fixing property. Although the medium and high speed imaging apparatus involves a great deal of change in environments through an image formation process including fixation and image formation, and an unstable exhalation release agent volatilizes to contaminate the interior of the apparatus and to be discharged abroad as dust particles, the release agent that satisfies Expression (2) has high viscosity at low frequencies, being prevented from volatilizing.
[00028] The complex viscosity η * a reflects the exudation property of the release agent melted in the toner, where a greater η * a means that a smaller amount of the release agent leaves the toner, and a lower η * a means that a greater amount of the release agent leaves the toner.
[00029] The complex viscosity η * determined by measuring the dynamic viscoelasticity at a measurement frequency of 6.28 rad / s is 1.1 Pa.s to 2.0 Pa. S as shown in Expression (1), preferably 1.2 Pa.sa 1.8 Pa.s.
[00030] When the complex viscosity η * a is less than 1.1 Pa.s, it is not possible for the release agent to be exhaled from the toner with heating to fix to form a uniform coating layer on the image. In addition, when the image is heated and pressed with a fixing roller, the coating layer made of the release agent becomes non-uniform (broken), potentially leading to unevenness in delamination. When the complex viscosity η * a is greater than 2.0 Pa.s, the release agent is degraded in the exudation property, potentially leading to degradation in the release property.
[00031] Also, the ratio (η * b / η * a) between the complex viscosities at the different frequencies is 0.001 to 1.00 as shown in Expression (2), preferably 0.010 to 0.80.
[00032] When the ratio (η * b / η * a) of complex viscosities is less than 0.001, despite the release agent having a good toner-exuding property with fixation, the molecular state of the release agent becomes unstable with fixation or immediately after fixation and the release agent tends to volatilize, potentially leading to contamination from inside the device and discharge of the release agent to the outside as energy. When the ratio (η * b / η * a) of complex viscosities is greater than 1.00, the release agent is not sufficiently decreased in viscoelasticity with fixation, leading to degradation of the fixing property at low temperature. In addition, the exudation property of the toner release agent is degraded, potentially leading to degradation of the release property.
[00033] Here, to measure the dynamic viscoelasticity of the release agent, first, the release agent is extracted from the toner as follows.
[00034] Specifically, 30 g of a toner is added to 300 ml of ethyl acetate, followed by stirring at 35 ° C for 30 min. The obtained solution is filtered with a membrane filter having an opening of 0.2 pm, in order to remove resin components. Then, the material insoluble in ethyl acetate obtained is treated with a Soxhlet extractor to extract matter soluble in hexane from it. Specifically, the material insoluble in ethyl acetate is placed on a cylindrical filter paper having an internal diameter of 24 mm which is then defined for the extraction tube. The flask equipped with a condenser containing 300 mL of hexane is placed in a blanket heater to cause the hexane to be refluxed at 70 ° C so that the hexane in the condenser is dripped into the matter insoluble in ethyl acetate and matter soluble in hexane is extracted into the vial. After extraction for 10 hours, the hexane in the extract is evaporated under reduced pressure, while the dissolved wax can be extracted. In addition, the residue is dissolved in chloroform to prepare a sample for gel permeation chromatography (GPC), and the sample is injected into a GPC measuring device (GPC.HLC-8120, product of TOSOH CORPORATION). A fraction collector is arranged at the GPC eluate exit port to collect one eluate at each predetermined count. The eluates corresponding to the peak of the GPC chromatograph are combined, and the chloroform of the combined eluate is evaporated to obtain the eluate target product. In this way, the release agent (wax) is extracted from the toner.
[00035] The dynamic viscoelasticity of the release agent extracted from the toner can be measured with, for example, the ARES measuring device (product of Rheometric Scientific Co.). Notably, the dynamic viscoelasticity of the release agent itself can also be measured with the same device.
[00036] First, the release agent sample is molded on a table. Then, parallel plates of 50 mm in diameter are defined for the top of the geometry and a 50 mm diameter cup is defined at the bottom of the same. After the 0 point adjustment is made so that the normal force becomes 0, sine wave vibration is applied to the table at a vibration frequency of 6.28 rad / s to 62.8 rad / s.
[00037] The interval between the parallel plates is set to 1.0 mm, and the measurement is carried out within - 15 ° C to + 15 ° C of the melting point of the release agent. <Release agent>
[00038] The release agent used is an ester wax having the dynamic viscoelasticity described above.
[00039] The ester wax is preferably a monoester synthesized from a monohydric alcohol and a linear fatty acid containing a long chain alkyl group or a saturated ester synthesized from a linear fatty acid and a polyhydric alcohol . The ester wax is particularly preferably such a monoester wax from the point of view of obtaining good fixing property and good releasing property.
[00040] The ester wax can be synthesized appropriately or it can be a commercially available one.
[00041] Ester wax in general is synthesized through the esterification reaction between a long-chain fatty acid or polycarboxylic acid and a long-chain higher alcohol or polyhydric alcohol.
[00042] Long-chain fatty acid or polycarboxylic acid and long-chain higher alcohol or polyhydric alcohol are generally obtained from natural products, and are generally mixtures containing acids or alcohols each having an even number of atoms of carbon.
[00043] Long-chain fatty acid is not particularly limited and can be selected appropriately depending on the intended purpose. Examples thereof include myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid and lignoceric acid. These can be used alone or in combination.
[00044] Examples of polycarboxylic acid include benzene dicarboxylic acids (e.g., phthalic acid, isophthalic acid and terephthalic acid) or anhydrides thereof; alkyl dicarboxylic acids (for example, succinic acid, adipic acid, sebacic acid and azelaic acid) or anhydrides thereof; unsaturated dibasic acids (for example, maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid and mesaconic acid); unsaturated dibasic acid anhydrides (for example, maleic anhydride, citraconic anhydride, itaconic anhydride and alkenyl succinic anhydride); trimellitic acid, pyromelitic acid, 1,2,4-benzene tricarboxylic acid, 1,2,5-benzene tricarboxylic acid, 2,5,7-naphthalene tricarboxylic acid, 1,2,4-naphthalene tricarboxylic acid, 1,2 , 4-butane tricarboxylic acid, 1,2,5-hexane tricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, tetrakis (methylenecarboxy) methane, 1,2,7,8-octane tetracarboxylic acid, Trimer acid Enpol; anhydrides thereof; and partial alkyl esters thereof. These can be used alone or in combination.
[00045] Superior long-chain alcohol is not particularly limited and can be selected appropriately depending on the intended purpose. Examples thereof include capryl alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol and lignoceryl alcohol. These can be used alone or in combination. Examples of polyhydric alcohol include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, sorbitol, 1,2,3,6-hexanetretrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanotriol, 1,2,5- pentanotriol, glycerin, 2-methylpropanotriol, 2-methyl-1,2,4-butanotriol, trimethylolethane, trimethylolpropane and 1,3,5-trihydroxybenzene. These can be used alone or in combination.
[00046] For example, the esterification reaction is carried out at a reaction temperature of less than 250 ° C under normal or reduced pressure. Preferably, the esterification reaction is carried out in an inert gas such as nitrogen gas. The ratio between the amount of long-chain fatty acid or polycarboxylic acid and the amount of higher long-chain alcohol or polyhydric alcohol is not particularly limited and can be selected appropriately depending on the intended purpose. A small amount of an esterification catalyst or solvent can be used for the esterification reaction.
[00047] Examples of the esterification catalyst used include organic titanium compounds such as tetrabutoxy titanate and tetrapropioxy titanate; organic tin compounds such as butyl tin dilaurate and dibutyl tin oxide; organic lead compounds; and sulfuric acid. Examples of the solvent used include aromatic solvent such as toluene, xylene and mineral spirits.
[00048] When long-chain fatty acid or polycarboxylic acid and long-chain higher alcohol or polyhydric alcohol are directly subjected to esterification, by-products having structures similar to the intended ester compound are formed, adversely affecting various properties of the toner. Thus, when the starting materials and reaction products are purified by extraction with a solvent or distillation under reduced pressure, it is possible to obtain the ester wax suitably useful in the present invention.
[00049] The endothermic peak temperature of the release agent at the second temperature raising in differential scanning calorimetry is from 60 ° C to 80 ° C, preferably 70 ° C to 80 ° C. When the endothermic peak temperature of the release agent at the second rising temperature is less than 60 ° C, the release agent may adversely affect the thermal resistance storage stability of the formed toner. While when it is greater than 80 ° C, the toner formed is increased at the fixing temperature and also tends to cause cold displacement with fixation at low temperatures. As a result, it may be difficult to properly smooth the surface of the fixed image, which can lead to degradation in the color mixing property.
[00050] Here, the endothermic peak temperature of the ester wax can be measured at the second temperature by rising in the differential scanning calorimetry of the same.
[00051] Here, the endothermic peak temperature of the ester wax at the second temperature rise can be measured with a DSC (differential scanning calorimeter) system ("Q-200", product of TA INSTRUMENTS Co.) as follows .
[00052] First, about 5.0 mg of the ester wax to be measured is weighed accurately and placed in a sample container made of aluminum; the sample container is placed in a retainer unit; and the retainer unit is fitted in an electric oven. Then, in a nitrogen atmosphere (flow rate: 50 mL / min), the sample is heated from -20 ° C to 150 ° C under the following conditions: rate of temperature increase: 1 ° C / min ; temperature modulation cycle: 60 seconds; and temperature modulation range: 0.159 ° C; and then the sample is cooled from 150 ° C to 0 ° C at a temperature drop rate of 10 ° C / min. Then, the sample is again heated to 150 ° C at a temperature increase rate of 1 ° C / min. The DSC curve obtained using the differential scanning calorimeter ("Q-200," product of TA INSTRUMENTS Co.) is used to determine the endothermic peak temperature assigned to the ester wax at the second temperature rise.
[00053] The solubility of the release agent in ethyl acetate at 20 ° C is preferably 7% by mass, more preferably 0% by mass to 7% by mass. When the solubility of the same is greater than 7% by mass, the release agent dissolved in ethyl acetate is attached to the surface of the toner during desolvation, potentially causing degradation in the heat resistance storage stability, contamination in the developing device , and image flaws.
[00054] The melting viscosity of the ester wax is preferably 5 cps to 1,000 cps, more preferably 10 cps to 100 cps, as measured at a higher temperature by 20 ° C than the melting point thereof. Wax having a melt viscosity greater than 1,000 cps cannot satisfactorily improve the hot displacement resistance or the low temperature fastening property.
[00055] The ester wax preferably has a hardness of 0.5 to 5. When the hardness of the ester wax is less than 0.5, the fixing device depends a lot on the pressure and speed of the process, resulting in the fact that the ester wax can be bad in effect to prevent hot displacement. While when it is greater than 5, the storage stability of the toner decreases and the ester wax itself has poor self-aggregating property, resulting in the ester wax being poor in effect to prevent hot displacement.
[00056] The hardness of the ester wax is a Vickers hardness measured as follows. Specifically, the ester wax is formed into a cylindrical shape having a diameter of 20 mm and a thickness of 5 mm, and the Vickers hardness of the sample formed is measured using an ultra-micro dynamic hardness tester (DUH-200, product Shimadzu Corporation).
[00057] More specifically, the sample is moved a distance of 10 pm while a load of 0.5 g is being applied to the sample at a loading speed of 9.67 mm / s, and then the sample is held for 15 seconds. The shape of the formed tooth is measured to determine Vickers hardness.
[00058] The amount of the ester wax contained in the toner is preferably 3 parts by weight to 40 parts by weight, more preferably 5 parts by weight to 35 parts by weight, per 100 parts by weight of the binder resin.
[00059] When the amount of the same is less than 3 parts by mass, the toner formed is degraded in the hot displacement resistance and also tends to cause a displacement phenomenon when fixing the images on both the front and back surfaces. When it is greater than 40 parts by mass, the toner particles formed by the spraying method are easily fused in the production apparatus for this purpose, or the toner particles formed by the polymerization method are easily combined together during the granulation of the same, resulting in toner particles having a wide particle size distribution to be easily formed and toner life can be reduced.
[00060] Even in a color imaging method including: forming a toner image on a latent electrostatic imaging support member with a toner containing the ester wax in an amount of 3 parts by mass to 40 parts by weight 100 parts by mass of the binder resin; transferring the toner image from the electrostatic imaging support member to an intermediate transfer member; contacting a voltage transfer roller applied to the intermediate transfer member to electrostatically transfer the toner image from the intermediate transfer member to a recording medium; and heating and fixing the toner image to the recording medium with a heater - pressing device, toner fusion or film formation in the latent electrostatic image support member or the intermediate transfer member is suppressed.
[00061] A double-sided fixation method is a method where a fixed image is previously formed on one surface of the recording paper and then an image is formed on the other surface of the same. In this method, the previously fixed image is passed through the fixture again, and so it is necessary to consider the heat displacement resistance of the toner sufficiently. Therefore, in the present invention, it is preferable to add a relatively large amount of the ester wax. <Binder resin>
[00062] The binder resin contains a crystalline polyester resin and a non-crystalline polyester resin.
[00063] It is preferable that a modified polyester resin, an unmodified polyester resin (i.e., an unmodified polyester resin) and other binder resins are contained as the non-crystalline polyester resin. - Crystalline polyester resin -
[00064] Crystalline polyester resin is not particularly limited and can be selected appropriately depending on the intended purpose. The crystalline polyester resin is preferably that synthesized using alcohol components containing C2-20 diol compounds or derivatives thereof and acid components containing polycarboxylic acid compounds (for example, aliphatic dicarboxylic acids, aromatic dicarboxylic acids and alicyclic dicarboxylic acids) or derivatives of the themselves. Among these, particularly preferred are crystalline polyester resins synthesized using saturated aliphatic dicarboxylic acids and saturated aliphatic diols.
[00065] In the present invention, the crystalline polyester resin refers to that obtained using polyhydric alcohol components and polycarboxylic acid components such as polycarboxylic acids, polycarboxylic anhydrides and polycarboxylic acid esters. Polyester resins that have been modified; for example the precursor binder resin described below (prepolymer) and modified polyester resins obtained through crosslinking and / or elongation of prepolymer (i.e. modified polyester resins having at least one of a urethane bond and a urea bond) are not encompassed by the crystalline polyester resin in the present invention, but are treated as a binder resin precursor or a modified polyester resin.
[00066] The polyhydric alcohol component is not particularly limited and can be selected appropriately depending on the intended purpose. Examples thereof include C2-12 aliphatic diol compounds. Examples of the C2-12 aliphatic diol compounds include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol , 1,8-octanodiol, 1,10-decanediol, 1,12-dodecanediol, neopentyl glycol and 1,4-butenediol. These can be used alone or in combination.
[00067] The polycarboxylic acid component is not particularly limited and can be selected appropriately depending on the intended purpose. Examples of these include: aromatic carboxylic acids (for example, phthalic acid, isophthalic acid and terephthalic acid) or derivatives thereof; and C2-12 saturated dicarboxylic acids (for example, 1,4-butanedioic acid, 1,6-hexanedioic acid such as adipic acid, 1,8-octanedioic acid, 1,10-decanedioic acid and 1,12-dodecanedioic acid) or derivatives thereof. These can be used alone or in combination.
[00068] Among these, the crystalline polyester resin is particularly preferably formed between a C4-12 saturated aliphatic diol component which is 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol or 1,10-decanediol , 1,12-dodecanediol and a C4-12 saturated aliphatic dicarboxylic acid component which is 1,4-butanedioic acid, 1,6-hexanedioic acid, 1,8-octanedioic acid, 1,10-decanedioic acid or 1, 12- dodecanedioic. This is because the crystalline polyester resin obtained has high crystallinity and changes a lot in viscosity around its melting point.
[00069] The melting point of the crystalline polyester resin is not particularly limited and can be selected appropriately depending on the intended purpose. Preferably it is 55 ° C to 80 ° C. When the melting point is less than 55 ° C, there may be degradation in the thermal resistance storage stability. Whereas when it is greater than 80 ° C, there may be degradation in the fastening property at low temperature.
[00070] The melting point of the crystalline polyester resin refers to a temperature at which the crystalline polyester resin shows the maximum endothermic peak in a DSC curve of the same measurement with the differential scanning calorimeter.
[00071] The amount of crystalline polyester resin contained in the toner is not particularly limited and can be selected appropriately depending on the intended purpose. Preferably it is from 1% by mass to 10% by mass. When the amount is less than 1% by mass, there may be degradation in the fastening property at low temperature. Whereas when it is greater than 10% by mass, there may be degradation in the storage stability of thermal resistance. - Non-crystalline polyester resin -
[00072] The non-crystalline polyester resin is obtained using polyhydric alcohol components and polycarboxylic acid components such as polycarboxylic acids, polycarboxylic anhydrides and polycarboxylic acid esters.
[00073] In the present invention, non-crystalline polyester resin refers to that obtained using polyhydric alcohol components and polycarboxylic acid components such as polycarboxylic acids, polycarboxylic anhydrides and polycarboxylic acid esters, as described above. Polyester resins that have been modified; for example, the binder resin precursor described below (prepolymer) and modified polyester resins obtained by crosslinking and / or stretching the prepolymer (i.e., modified polyester resins having at least one of a urethane bond) and a urea bond) are not encompassed by the non-crystalline polyester resin in the present invention, but are treated as a modified polyester resin.
[00074] The polyhydric alcohol component is not particularly limited and can be selected appropriately depending on the intended purpose. Examples of these include: (C2-3) alkylene oxide bisphenol A adducts (mol of average addition: 1 to 10) such as polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene (2 , 2) -2,2-bis (4-hydroxyphenyl) propane; ethylene glycol, propylene glycol, neopentyl glycol, glycerin, pentaerythritol, trimethylolpropane, hydrogenated bisphenol A, sorbitol and alkylene (C2-3) adducts oxide (average addition: 1 to 10). These can be used alone or in combination.
[00075] The polycarboxylic acid component is not particularly limited and can be selected appropriately depending on the intended purpose. Examples thereof include: dicarboxylic acids such as adipic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid and maleic acid; substituted succinic acids having a C1-20 alkyl group or a C2-20 alkenyl group as a substituent, such as dodecenyl succinic acid and octyl succinic acid; trimellitic acid and pyromelitic acid; and anhydrides and alkyl esters (Cl-8) of these acids. These can be used alone or in combination.
[00076] The non-crystalline polyester resin, the binder resin precursor described below (prepolymer) and modified polyester resins obtained through crosslinking and / or elongation of the prepolymer (ie modified polyester resins having at least minus one of a urethane bond and a urea bond) are not particularly limited and can be selected appropriately depending on the intended purpose. They are preferably in an at least partially compatible state, since the toner formed can be increased in its low temperature fastening and hot displacement resistance. Thus, preferably, the non-crystalline polyester resin and the binder resin precursor described below (prepolymer) are similar in their constituent component of polyhydric alcohol and their constituent component of acid
[00077] The glass transition temperature (Tg) of the non-crystalline polyester resin is not particularly limited and can be selected appropriately depending on the intended purpose. Preferably it is 55 ° C to 65 ° C, more preferably 57 ° C to 62 ° C. When the glass transition temperature of the same is less than 55 ° C, the toner formed may be poor in the storage stability of thermal resistance and durability to tension due, for example, to agitation in the developing device. While when it is higher than 65 ° C, the toner formed can be increased in viscoelasticity during fusing, resulting in the fact that it can be degraded in the low temperature fastening property.
[00078] Notably, the glass transition temperature refers to a glass transition temperature measured by differential scanning calorimetry (DSC). The glass transition temperature can be measured using, for example, TG-DSC SYSTEM TAS-100 (product from Rigaku Corporation).
[00079] The amount of the non-crystalline polyester resin contained in the toner is not particularly limited and can be selected appropriately depending on the intended purpose, but is preferably 75 parts by mass to 95 parts by mass, more preferably 80 parts by mass to 90 parts by mass, per 100 parts by mass of toner. When the amount is less than 75 parts by weight, the colorant and the release agent are degraded in the dispersion capacity in the toner, easily causing the image to fog and causing image flaws. Whereas when it is greater than 95 parts by mass, the toner formed can be degraded in the fixing property at low temperature since the amount of the crystalline polyester resin becomes small. In addition, the toner formed can be degraded in the hot run resistance as the amount of the modified polyester resin becomes small. - Modified polyester resin -
[00080] The modified polyester resin can provide toner with an appropriate extension of cross-linked structures. The modified polyester resin is not particularly limited and can be selected appropriately depending on the intended purpose, as long as it is a resin having at least one of a urethane bond and a urea bond. The modified polyester resin is preferably resins obtained through an elongation reaction and / or crosslinking reaction between a compound containing active hydrogen group and a precursor of binder resin having a functional group reactive with the compound containing active hydrogen group (here the in the following, the precursor of the binder resin can be referred to as "prepolymer").
[00081] The prepolymer is not particularly limited and can be selected appropriately depending on the intended purpose, as long as it is a polyester resin having at least one functional group reactive with the compound containing active hydrogen group.
[00082] The functional group reactive with the compound containing hydrogen group active in the prepolymer is not particularly limited and can be selected appropriately from known constituents. Examples thereof include an isocyanate group, an epoxy group, carboxylic acid and an acid chloride group. These can be contained alone or in combination. Among these, an isocyanate group is preferred.
[00083] The method for synthesizing the prepolymer is not particularly limited and can be selected appropriately depending on the intended purpose. To produce a prepolymer that contains an isocyanate group, the following method can be employed, for example. Specifically, a polyol and a polycarboxylic acid are heated to a temperature of 150 ° C to 280 ° C in the presence of a known esterification catalyst such as tetrabutoxy titanate or dibutyltin oxide. Subsequently, the formed water is removed under reduced pressure if necessary, to prepare a polyester having a hydroxyl group. Then, the polyester prepared in this way is reacted with a polyisocyanate at a temperature of 40 ° C to 140 ° C to prepare the prepolymer containing isocyanate group.
[00084] The polyol is not particularly limited and can be selected appropriately depending on the intended purpose. Examples of these include: diols such as alkylene glycols (for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol and 1,6-hexanediol), alkylene ether glycols (for example , diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol), alicyclic diols (eg, 1,4-cyclohexane dimethanol and hydrogenated bisphenol A), bisphenols (eg, bisphenol A, bisphenol F and bisphenol S), alicyclic diol adducts listed above with alkylene oxides (for example, ethylene oxide, propylene oxide and butylene oxide); bisphenol adducts listed above with alkylene oxides (for example, ethylene oxide, propylene oxide and butylene oxide); trihydric or higher polyols such as polyhydric aliphatic alcohols (eg, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and sorbitol), trihydric or higher phenols (eg, phenol novolak and cresol novolak) and alkylene oxide adducts trihydric or higher polyphenols; and mixtures of diols and trihydric or higher polyols. These can be used alone or in combination.
[00085] In particular, the polyol preferably is the above diol alone or mixtures of the above diol and a small amount of the trihydric or higher polyol. The diol is preferably C2-12 alkylene glycols or bisphenol alkylene oxide adducts (eg, 2 mole adducts of bisphenol A ethylene oxide, 2 mole adducts of bisphenol A propylene oxide and 3 mole adducts of bisphenol propylene oxide A).
[00086] Polycarboxylic acid is not particularly limited and can be selected appropriately depending on the intended purpose. Examples thereof include: alkylene dicarboxylic acids (for example, succinic acid, adipic acid and sebacic acid); dicarboxylic alkenylene acids (for example, maleic acid and fumaric acid); aromatic dicarboxylic acids (for example, terephthalic acid, isophthalic acid, and naphthalene dicarboxylic acid); and trivalent or higher valence polycarboxylic acids (for example, aromatic C9-20 polycarboxylic acids such as trimellitic acid and pyromelitic acid). These can be used alone or in combination.
[00087] Among these, the polycarboxylic acid is preferably a C4-20 alkenylene dicarboxylic acid or a C8-C20 aromatic dicarboxylic acid.
[00088] Notably, the polycarboxylic acid used can be an anhydride of the same or a lower alkyl ester of the same (for example, methyl ester, ethyl ester or isopropyl ester).
[00089] The mixing ratio between the polyol and the polycarboxylic acid is not particularly limited and can be selected appropriately depending on the intended purpose. The mixing ratio between them is preferably 2/1 to 1/1, more preferably 1.5 / 1 to 1/1, particularly preferably 1.3 / 1 to 1.02 / 1, in terms of the equivalent ratio [OH] / [COOH] from the hydroxyl group [OH] from the polyol group to the carboxyl [COOH] polycarboxylic acid.
[00090] Polyisocyanate is not particularly limited and can be selected appropriately depending on the intended purpose. Examples of these include: aliphatic polyisocyanates (eg tetramethylene diisocyanate, hexamethylene diisocyanate and 2,6-diisocyanatomethylcaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamide , trimethylhexane diisocyanate and tetramethylhexane diisocyanate); alicyclic polyisocyanates (for example, isophorone diisocyanate and cyclohexylmethane diisocyanate); aromatic diisocyanates (for example, tolylene diisocyanate and diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, diphenylene-4,4'-diisocyanate, 4,4'-diisocyanate-3,3 '- dimethylphenyl, 3-methyldiphenylmethane-4, 4'-diisocyanate and diphenyl ether-4,4'-diisocyanate); aromatic aliphatic diisocyanates (for example, OI, α, α ', α'-tetramethylxylylene diisocyanate); isocyanurates (for example, trisisocyanatoalkylisocyanurate, triisocyanatocycloalkylisocyanurate); phenol derivatives thereof; and products blocked from them with, for example, oxime or caprolactam. These can be used alone or in combination.
[00091] When the polyisocyanate is reacted with the hydroxyl-containing polyester, a solvent can be used if necessary. The useful solvent is not particularly limited and can be selected appropriately depending on the intended purpose. Examples of these include inert solvents for an isocyanate such as aromatic solvents (for example, toluene and xylene); ketones (for example, acetone, methyl ethyl ketone and methyl isobutyl ketone); esters (for example, ethyl acetate); amides (for example dimethylformamide and dimethylacetamide); ethers (eg, tetrahydrofuran). These can be used alone or in combination.
[00092] The mixing ratio between the polyisocyanate and the hydroxyl-containing polyester is not particularly limited and can be selected appropriately depending on the intended purpose. The mixing ratio between them is preferably 5/1 to 1/1, more preferably 4/1 to 1.2 / 1, particularly preferably 2.5 / 1 to 1.5 / 1, in terms of the equivalent ratio [NCO] / [OH] from the polyisocyanate isocyanate group [NCO] to the polyester hydroxyl group [OH]. When the equivalent [NCO] / [OH] ratio is greater than 5, the remaining polyisocyanate compound can adversely affect the loading capacity of the formed toner. Compound containing active hydrogen group
[00093] The compound containing active hydrogen group acts, in an aqueous medium, as a stretching agent or crosslinking agent at the time of the elongation reaction or the prepolymer crosslinking reaction.
[00094] The active hydrogen group is not particularly limited and can be selected appropriately depending on the intended purpose. Examples thereof include a hydroxyl group (for example, an alcoholic hydroxyl group or a phenolic hydroxyl group), an amino group, a carboxyl group and a mercapto group. These can be contained alone or in combination.
[00095] The compound containing active hydrogen group is not particularly limited and can be selected appropriately depending on the intended purpose. Examples of these include water. In cases where the prepolymer is a polyester prepolymer that contains an isocyanate group, amines are preferably used from the point of view of increasing the molecular weight of the reaction product.
[00096] The amines serving as the compound containing the active hydrogen group are not particularly limited and can be selected appropriately depending on the intended purpose. Examples of these include higher valence diamines, triamines or polyamines, amino alcohols, amino mercaptanes, amino acids, and compounds obtained by blocking amino groups of these amines. Examples of diamines include aromatic diamines (for example, phenylenediamine, diethyltoluenediamine and 4,4'-diaminodiphenylmethane); alicyclic diamines (e.g. 4, 4'-diamino-3,3'-dimethyldicyclohexylmethane, diaminacyclohexane and isophoronadiamine); and aliphatic diamines (for example, ethylenediamine, tetramethylenediamine and hexamethylenediamine). Examples of the higher valence triamines or polyamines include diethylenetriamine and triethylenetetramine. Examples of the amino alcohols include ethanolamine and hydroxyethylaniline. Examples of the amino mercaptan include aminoethyl mercaptan and aminopropyl mercaptan. Examples of the amino acids include propionic amino acid and capranoic amino acid. Examples of compounds obtained by blocking amino groups from the above amines include oxazoline compounds and satinine compounds obtained from any of the above amines (i.e., higher valence diamines, triamines or polyamines, amino alcohols, amino mercaptan and amino acids) and ketones (for example, acetone, methyl ethyl ketone and methyl isobutyl ketone). These can be used alone or in combination.
[00097] Among these, amines are particularly preferably diamines and mixtures of diamines and a small amount of higher valence triamines or polyamines.
[00098] The compound containing the active hydrogen group and the prepolymer are allowed to undergo an elongation reaction and / or crosslinking reaction in an aqueous medium, to obtain the modified polyester resin in this way.
[00099] The elongation reaction and / or crosslinking reaction can be terminated using a reaction terminator such as a monoamine (for example, diethylamine, dibutylamine, butylamine or laurylamine) or a compound obtained by blocking monoamine (for example, a satin compound).
[000100] In the synthesis of the modified polyester resin, the mixing ratio between the polyester containing isocyanate group which serves as the prepolymer and the amine which serves as the compound containing active hydrogen group is not particularly limited and can be selected appropriately depending on the intended purpose. The equivalent ratio [NCO] / [NHx] of the isocyanate group [NCO] of the polyester containing isocyanate group to the amino group [NHx] of the amine is preferably 1/2 to 2/1, more preferably 1 / 1.5 to 1 , 5/1, particularly preferably 1 / 1.2 to 1.2 / 1. - Other resins -
[000101] The other resins are not particularly limited and can be selected appropriately depending on the intended purpose. Examples thereof include styrene-acryl copolymer resins, polyol resins, vinyl resins, polyurethane resins, epoxy resins, polyamide resins, polyimide resins, silicon containing resins, phenol resins, melamine resins, resins urea, aniline resins, ionomer resins and polycarbonate resins. These can be used alone or in combination. <Coloring>
[000102] The dye is not particularly limited and can be any known dyes or pigments. Examples of the dye include carbon black, nigrosine dye, iron black, yellow naphthol S, yellow Hansa (10G, 5G and G), cadmium yellow, yellow iron oxide, ocher yellow, lead yellow, titanium yellow, yellow polyazzo, yellow oil, Hansa yellow (GR, A, RN and R), yellow pigment L, yellow benzidine (G and dxcGR), permanent yellow (NCG), yellow quick vulcan (5G, R), tartrazine lake, quinoline yellow lake, yellow anthrax BGL, yellow isoindolinone, colcothar, lead red, lead vermillion, cadmium red, mercury cadmium red, antimony vermilion, red permanent 4R, red, fiser red, aniline parachlor-ortonitro red, fast scarlet litol G, bright scarlet fast, bright BS , red permanent (F2R, F4R, FRL, FRLL and F4RH), VD fast scarlet, ruby fast vulcan B, bright scarlet G, ruby lithium GX, red permanent F5R, bright carmine 6B, scarlet pigment 3B, burgundy 5B, toluidine brown, permanent F2 board K, Helio burgundy BL, burgundy 10B, light brown BON, medium brown BON, eosin lake, rhodamine lake B, rhodamine Y lake, alizarin lake, red thioindigo B, brown thioindigo, oil red, quinacridone red, pyrazolone red, red polyazzo perinone orange orange benzidine chrome, oil orange, cobalt blue, cerulean blue, alkaline blue lake, peacock blue lake, victoria blue lake, metal-free phthalocyanine blue, phthalocyanine blue, fast sky blue, idanthrene blue (RS and BC), indigo, ultramarine, iron blue, anthraquinone blue, rapid violet B, methylviolet lake, cobalt purple, manganese violet, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, viridian, emerald green, green pigment B, naphthol green B, green gold, acid green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc flower, lithopone, and mixtures thereof. These dyes can be used alone or in combination.
[000103] The amount of the dye is preferably 1 wt% to 15 wt%, more preferably 3 wt% to 10 wt%, with respect to the toner.
[000104] The colorant can be mixed with a resin to form a master mixture. Examples of the resin that is used to produce a master mix or that is kneaded with a master mix include the modified and unmodified polyester resins mentioned above; styrene polymers and substituted products thereof (for example, polystyrenes, poly-p-chloro-styrenes and polyvinyl toluenes); styrene copolymers (for example, styrene - p-chloro styrene copolymers, styrene - propylene copolymers, styrene vinyl-vinyl copolymers, styrene-vinylnaphthalene copolymers, styrene-methyl acrylate copolymers, styrene copolymers - ethyl acrylates styrene butyl acrylate, styrene copolymers - octyl acrylate, styrene copolymers - methyl methacrylate, styrene copolymers - ethyl methacrylate, styrene copolymers - butyl methacrylate styrene copolymers, styrene copolymer acrylate, styrene copolymer, - vinyl methyl ketone, styrene - butadiene copolymers, styrene - isoprene copolymers, acrylonitrile - indene styrene copolymers, styrene - maleic acid copolymers and styrene - maleic acid ester copolymers); polymethyl methacrylate resins; polybutyl methacrylate resins; polyvinyl chloride resins; polyvinyl acetate resins; polyethylene resins; polypropylene resins, polyester resins; epoxy resins; epoxy polyol resins; polyurethane resins; polyamide resins; polyvinyl butyral resins; polyacrylic acid resins; rosina; modified rosin; terpene resins; aliphatic or alicyclic hydrocarbon resins; aromatic oil resins; chlorinated paraffins; and paraffin waxes. These can be used alone or in combination.
[000105] The master mix can be prepared by mixing and kneading a colorant with a resin for use in a master mix by applying high shear strength. An organic solvent can also be used to improve interactions between the dye and the resin. In addition, the intermittent method, in which an aqueous paste containing a colorant is mixed and kneaded with a resin and an organic solvent and then the colorant is transferred to the resin to remove water and the organic solvent is preferably used, since a cake wet dye can be used directly (ie no drying is required). For this mixing and kneading, a high shear dispersion device (for example, a three-roll mill) is preferably used. <Other ingredients>
[000106] The other ingredients are not particularly limited and can be selected appropriately depending on the intended purpose. Examples of these include a charge control agent, fine inorganic particles, a flow-enhancing agent, a cleaning-enhancing agent and a magnetic material.
[000107] - Cargo control agent -
[000108] The load control agent is not particularly limited and can be selected appropriately depending on the intended purpose. Examples thereof include nigrosine dyes, triphenylmethane dyes, metal complex dyes containing chromium, molybdic acid chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus, phosphorus compounds, tungsten, tungsten compounds, fluoroactive agents, metal salts of salicylic acid, and metal salts of salicylic acid derivatives.
[000109] Specific examples thereof include nigrosine dye BONTRON 03, quaternary ammonium salt BONTRON P-51, azo dye containing metal BONTRON S-34, metal complex of oxinaptoic acid E-82, metal complex of salicylic acid E- 84 and E-89 phenol condensate (these products are from ORIENT CHEMICAL INDUSTRIES CO., LTD), quaternary ammonium salt molybdenum complexes TP-302 and TP-415 (these products are from Hodogaya Chemical Co., Ltd.) , quaternary ammonium salt COPY CHARGE PSY VP 2038, derived from triphenylmethane COPY BLUE PR, quaternary ammonium salt COPY CHARGE NEG VP2036 and COPY CHARGE NX VP434 (these products are from Hoechst AG), LRA-901 and boron complex LR-147 (these products are from Japan Carlit Co., Ltd.), copper phthalocyanine, perylene, quinacridone, azo pigments, and polymeric compounds having, as a functional group, a sulfonic acid group, a carboxyl group and / or a quaternary ammonium salt .
[000110] The amount of the charge control agent is not flatly determined and is varied depending on the type of binder resin used, an optionally used additive, and the toner production method used (including the dispersion method used) . The amount of the charge control agent is preferably 0.1 parts by weight to 10 parts by weight, more preferably 0.2 parts by weight to 5 parts by weight, per 100 parts by weight of the binder resin. When the amount of the same is greater than 10 parts by mass, the formed toner has a very high loading capacity, resulting in the fact that the charge control agent exhibits reduced effects. As a result, the attractive electrostatic force increases between the developing roller and the toner, decreasing the flow capacity of the toner and forming an image with reduced color density. The charge control agent can be kneaded molten together with a main mixture or resin, and then dissolved or dispersed. It goes without saying that the charge control agent can be added to an organic solvent when it is dissolved or dispersed in it; or it can be fixed on the surfaces in the formed toner particles. - Fine inorganic particles -
[000111] The fine inorganic particles can be used as an external additive to provide toner particles with flow capacity, developing capacity and loading capacity.
[000112] Fine inorganic particles are not particularly limited and can be selected appropriately depending on the intended purpose. Examples of these include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, oxide chromium, cerium oxide, red iron oxide, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide and silicon nitride. These can be used alone or in combination.
[000113] Additional examples of fine inorganic particles include polystyrenes, methacrylic acid esters, acrylate ester copolymers, polycondensates from, for example, silicon, benzoguanamine and nylon, and polymer particles from the thermoset resins, which are produced by polymerization in soap-free emulsion, suspension polymerization and dispersion polymerization.
[000114] The primary particle diameter of the fine inorganic particles is preferably 5 nm to 2 pm, more preferably 5 nm to 500 nm. The specific surface area of the fine inorganic particles as measured with the BET method is preferably 20 m2 / g to 500 m2 / g.
[000115] The amount of the fine inorganic particles is preferably 0.01 wt% to 5 wt%, more preferably 0.01 wt% to 2.0 wt%.
[000116] The flow capacity enhancing agent refers to a compound that has increased hydrophobicity through surface treatment and can prevent toner from being degraded in flow capacity and load capacity even under high humidity conditions. Examples thereof include silane coupling agents, silylating agents, silane coupling agents that contain fluoroalkyl group, coupling agents that contain organic titanate, coupling agents that contain aluminum, silicone oil and modified silicone oil. - Cleaning capacity enhancement agent -
[000117] The cleaning capacity enhancing agent is added to the toner to remove the remaining developer after transferring it to a latent electrostatic image support member and a primary recording medium. Examples of the cleaning ability enhancing agent include metal salts of fatty acids such as stearic acid (for example, zinc stearate and calcium stearate), fine polymer particles formed by soap-free emulsion polymerization, such as fine polymethylmethacrylate and fine polystyrene particles. The fine polymer particles preferably have a relatively narrow particle size distribution. It is preferred that the average volumetric particle diameter of the particle is 0.01 pm to 1 pm. - Magnetic material -
[000118] The magnetic material is not particularly limited and can be selected appropriately depending on the intended purpose. Examples of these include powdered iron, magnetite and ferrite. The magnetic material is preferably white in terms of the color tone. <Method for producing toner>
[000119] The method for producing a toner is a method for producing the toner of the present invention where an oil phase which is obtained by dissolving or dispersing in an organic solvent a compound containing active hydrogen group, a binder resin precursor having a Reactive site with the compound containing active hydrogen group, a crystalline polyester resin, a colorant and an ester wax, is dispersed in an aqueous medium to prepare an emulsified dispersion liquid where the precursor of the binding resin and the compound containing group active hydrogen are allowed to react in the emulsified dispersion liquid, and then the organic solvent is removed. Specifically, the above method includes: an oil phase preparation step; an aqueous phase preparation step; a step of preparing toner dispersion liquid; and a solvent removal step; and, if necessary, additionally includes other steps. << Preparation stage of oil phase >>
[000120] The oil phase preparation step is not particularly limited and can be selected appropriately depending on the intended purpose, as long as it is a dissolution or dispersion step in an organic solvent, a compound containing active hydrogen group, a precursor of binder resin having a reactive site with the compound containing active hydrogen group, a crystalline polyester resin, a colorant and an ester wax, to prepare an oil phase in this way.
[000121] The method for preparing the oil phase is, for example, a method where the compound containing active hydrogen group, the precursor of the binder resin having a site reactive with the compound containing active hydrogen group, the crystalline polyester resin, the colorant, the ester wax, and a charge control agent used optionally are added gradually to the organic solvent under stirring so that these materials are dissolved or dispersed therein.
[000122] Notably, when a pigment is used as the colorant and / or when materials that are poorly dissolvable in the organic solvent such as the charge control agent are used, the particles of these materials are preferably micronized prior to addition to the organic solvent.
[000123] As described above, the colorant can be formed in a master mixture. Similarly, the ester wax and the charge control agent can be formed in a master mixture.
[000124] In another method, the colorant, the ester wax and the charge control agent can be dispersed through a wet process in the organic solvent, if necessary in the presence of a dispersion aid, to obtain in this way a main moist.
[000125] In yet another method, when the melted materials are dispersed at a temperature lower than the boiling point of the organic solvent, they are heated and dissolved under agitation in the organic solvent, if necessary in the presence of a dispersion aid, and agitated with the dispersoids; and the resulting solution is cooled with stirring or shearing so that the dissolved materials are crystallized, thereby producing microcrystals of the dispersoids.
[000126] After the colorant, the ester wax and the optionally used charge control agent, dispersed with any of the above methods, were dissolved or dispersed in the organic solvent together with the compound containing active hydrogen group, the resin precursor binder having a reactive site with the compound containing active hydrogen group, and the crystalline polyester resin, the resulting mixture can be further dispersed. The dispersion can be carried out using a known disperser such as a crimping mill or a disc mill.
[000127] In such a way that the toner has an increased mechanical resistance and does not involve hot displacement with the fixation, the toner is preferably produced in a state where the precursor of the binding resin having a functional group reactive with the compound containing active hydrogen group it is dissolved in the oil phase; in other words, in a state where the oil phase contains the compound containing the active hydrogen group and the precursor to the binding resin.
[000128] The organic solvent used in the oil phase preparation step is not particularly limited and can be selected appropriately depending on the intended purpose. The organic solvent used preferably has a boiling point of less than 100 ° C from the point of view of being easily removed. Examples of these include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichlorethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone and methyl isobutyl ketone. These can be used alone or in combination.
[000129] When the binder resin to be dissolved or dispersed in the organic solvent has a polyester backbone, preferably ester solvents (for example, methyl acetate, ethyl acetate and butyl acetate) or ketone solvents (for example , methyl ethyl ketone and methyl isobutyl ketone) since these solvents have a high dissolution capacity for the binder resin having a polyester skeleton. Among these, methyl acetate, ethyl acetate and methyl ethyl ketone are particularly preferred since they can be removed more easily. << Stage of preparation of aqueous phase »
[000130] The aqueous phase preparation step is not particularly limited and can be selected appropriately depending on the intended purpose, as long as it is an aqueous phase preparation step.
[000131] The aqueous medium used in the aqueous phase preparation step is not particularly limited and can be selected appropriately depending on the intended purpose. Examples of these include water. The aqueous medium can be water alone or a mixture of water and a water-miscible organic solvent. Examples of the water-miscible organic solvent include alcohols (for example, methanol, isopropanol and ethylene glycol), dimethylformamide, tetrahydrofuran, celosolves (for example, methyl celosolve) and minor ketones (for example, acetone and methyl ethyl ketone).
[000132] Preferably, the aqueous medium additionally contains a surfactant.
[000133] The surfactant is not particularly limited and can be selected appropriately depending on the intended purpose. Examples thereof include anionic surfactants such as alkylbenzene sulfonic acid salts, α-olefin sulfonic acid salts, phosphoric acid esters and disulfonic acid salts; cationic surfactants such as amine salts (for example, alkyl amine salts, amino acid fatty acid derivatives, polyamine and imidazoline fatty acid derivatives) and quaternary ammonium salts (for example, alkyl trimethylammonium salts, dimethylammonium salts , alkyl dimethyl benzyl ammonium salts, pyridinium salts, alkyl isoquinolinium salts and benzethonium chloride); non-ionic surfactants such as fatty acid amide derivatives and polyhydric alcohol derivatives; and amphoteric surfactants such as alanine, dodecildi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine. Among these, a disulfonic acid salt having a relatively high HLB is preferably used, in order to efficiently disperse the oil droplets containing the solvent.
[000134] The amount of the surfactant contained in the aqueous medium is not particularly limited and can be selected appropriately depending on the intended purpose. The amount thereof is preferably 3% by mass to 10% by mass, more preferably from 4% by mass to 9% by mass, particularly preferably from 5% by mass to 8% by mass. When the amount thereof is less than 3% by mass, the oil droplets cannot be dispersed in a stable manner and as a result coarse oil droplets can be formed. While when it is greater than 10% by mass, each oil droplet becomes very small and also has an inverse micellar structure. Thus, dispersion stability is degraded due to the surfactant added in such an amount, to easily form coarse oil droplets in this way. << Toner dispersion liquid preparation step »
[000135] The step of preparing toner dispersion liquid is not particularly limited and can be selected appropriately depending on the intended purpose, as long as it is a dispersion step of the oil phase in the aqueous phase to prepare an emulsified dispersion liquid ( toner dispersion liquid).
[000136] The method for dispersion is not particularly limited and can be selected appropriately depending on the intended purpose. It can use a known disperser such as a low speed shear disperser, a high speed shear disperser, a friction disperser, a high pressure jet disperser or an ultrasonic disperser. Among these, a high speed shear disperser is preferably used to form toner-based particles having a particle diameter of 2 pm to 20 pm. The rotation speed of the high-speed shear disperser is not particularly limited but is preferably 1,000 rpm at 30,000 rpm, more preferably 5,000 rpm at 20,000 rpm. The dispersion time is not particularly limited and can be selected appropriately depending on the intended purpose, but is preferably 0.1 min to 5 min in a batch method. When the dispersion time exceeds 5 min, small unwanted particles remain and excessive dispersion is carried out to make the dispersion system unstable, potentially forming aggregates and coarse particles. The dispersion temperature is not particularly limited and can be selected appropriately depending on the intended purpose. It is preferably 0 ° C to 40 ° C, more preferably 10 ° C to 30 ° C. When the dispersion temperature is less than 0 ° C, the dispersion liquid is increased in viscosity to require high energy for the dispersion, leading to a decrease in production efficiency. Whereas when the dispersion temperature exceeds 40 ° C, molecular movements are excited to degrade the dispersion stability, easily forming coarse aggregates and particles.
[000137] The amount of the organic solvent contained in the toner dispersion liquid is not particularly limited and can be selected appropriately depending on the intended purpose. It is preferably 10% by mass to 70% by mass, more preferably 25% by mass to 60% by mass, particularly preferably 40% by mass to 55% by mass.
[000138] Notably, the amount of the organic solvent contained in the toner dispersion liquid is an amount with respect to the solid content (for example, the binder resin, the colorant, the ester wax and the charge control agent optionally used) in the toner dispersion liquid state. << Solvent removal step >>
[000139] The solvent removal step is not particularly limited and can be selected appropriately depending on the intended purpose, as long as it is a solvent removal step contained in the toner dispersion liquid. The solvent removal step is preferably a complete removal step of the solvent contained in the toner dispersion liquid. In an employable method, the toner dispersion liquid is gradually increased in temperature under agitation, in order to completely evaporate the organic solvent contained in the liquid droplets. In another employable method, the toner dispersion liquid under agitation is sprayed into a dry atmosphere, in order to completely evaporate the organic solvent contained in the liquid droplets. In yet another employable method, the toner dispersion liquid is reduced in pressure with stirring to evaporate the organic solvent. The latter two means can be used in combination with the first means.
[000140] The dry atmosphere into which the toner dispersion liquid is sprayed is not particularly limited and can be selected appropriately depending on the intended purpose. The dry atmosphere uses heated gas such as air, nitrogen, carbon dioxide or flue gas.
[000141] The temperature of the dry atmosphere is not particularly limited and can be selected appropriately depending on the intended purpose, but preferably it is a temperature equal to or greater than the highest boiling point of the solvents used.
[000142] Spraying is carried out using, for example, a spray dryer, a belt dryer or a rotary oven. The use of it can provide satisfactory intended qualities through treatment even in a short time. << Other steps >>
[000143] The other steps are not particularly limited and can be selected appropriately depending on the intended purpose. Examples of these include an aging step, a washing step and a drying step. - Aging stage -
[000144] When the oil phase contains the polyester resin (prepolymer) containing a functional group reactive with the active hydrogen group of the compound containing the active hydrogen group, the aging step is preferably performed to proceed to the stretching and reaction crosslinking the prepolymer.
[000145] The aging step is preferably carried out after the solvent removal step but before the washing step.
[000146] The aging time in the aging stage is not particularly limited and can be selected appropriately depending on the intended purpose, but is preferably 10 min to 40 hours, more preferably 2 hours to 24 hours.
[000147] The reaction temperature in the aging step is not particularly limited and can be selected appropriately depending on the intended purpose, but is preferably 0 ° C to 65 ° C, more preferably 35 ° C to 50 ° C. - Washing step -
[000148] The washing step is not particularly limited and can be selected appropriately depending on the intended purpose, as long as it is a step performed after the solvent removal step or the aging and washing step of a toner (base particles toner) contained in the toner dispersion liquid.
[000149] The toner dispersion liquid contains not only the toner-based particles but also such subsidiary materials as a dispersing agent (for example, the surfactant). Thus, the dispersion liquid is washed to separate only the toner base particles from the toner dispersion liquid.
[000150] The washing method is not particularly limited and can be selected appropriately depending on the intended purpose. Examples of these include a centrifugation method, a reduced pressure filtration method and a filter press method. Any of the above methods forms a toner-based particle cake. When the toner-based particles are not sufficiently washed through just a washing process, the cake formed can be dispersed again in an aqueous medium to form a slurry, which is treated repeatedly with any of the above methods to remove the particles toner base. When a low pressure filtration method or a filter press method is employed for washing, an aqueous medium can be made to penetrate the cake to wash the subsidiary materials contained in the toner-based particles. The aqueous medium used for washing is water or a mixture of water solvent and an alcohol such as methanol or ethanol. Water is preferably used from the point of view of reducing the cost and the environmental burden caused, for example, by drainage treatment. - Drying step -
[000151] The drying step is not particularly limited and can be selected appropriately depending on the intended purpose, provided that it is a step carried out after the step of washing and drying the toner-based particles.
[000152] Washed toner-based particles containing a large amount are dried to remove water, while only toner-based particles can be obtained.
[000153] The method of removing water from the toner-based particles is not particularly limited and can be selected appropriately depending on the intended purpose. The method uses, for example, a spray dryer, a vacuum freeze dryer, a reduced pressure dryer, a ventilation rack dryer, a mobile shelf dryer, a fluidized bed dryer, a rotary dryer or a stirring type dryer.
[000154] The toner-based particles are preferably dried until their water content is finally decreased by less than 1% by weight. Also, when the dry toner-based particles flocculate to cause inconvenience in use, the flocculated particles can be separated from each other by tapping, using, for example, a jet mill, HENSCHEL MIXER, a super mixer, a coffee mill, an oster blender or a food processor. (Developer)
[000155] A developer of the present invention contains the toner of the present invention, and may additionally contain other components such as a carrier. It can be, for example, a one-component developer containing only the toner, or a two-component developer containing the toner and the carrier. When used in, for example, high-speed printers that respond to an increase in recent information processing speed, the developer is preferably used as a two-component developer from the point of view of extending its service life. Such a developer can be used for several known electrophotographs such as a method of developing a magnetic component, a method of developing a non-magnetic component and a method of developing two components.
[000156] When used as a component developer, the developer of the present invention involves less change in the diameter of each toner particle even after repetitive cycles of consumption and addition, which prevents the formation of toner film on a roll of toner. development and adhesion of toner on surrounding members such a blade to form a thin toner layer. Thus, even when used (shaken) in a developing device for a long period of time, the developer maintains excellent stable development capabilities.
[000157] Also, when used as a two-component developer, the developer of the present invention involves less change in the diameter of each toner particle even after repetitive long-term consumption cycles and addition. Thus, even when shaken in a developing device for a long period of time, the developer maintains an excellent stable developing capacity.
[000158] The amount of the carrier contained in the two-component developer is preferably 90% by mass to 98% by mass, more preferably 93% by mass to 97% by mass.
[000159] The carrier is not particularly limited and can be selected appropriately depending on the intended purpose, but preferably has a core and a resin layer that covers the core.
[000160] Examples of the material for the core include manganese - strontium (Mn-Sr) materials (50 emu / ga 90 emu / g) and manganese - magnesium (Mn-Mg) materials (50 emu / ga 90 emu / g) . These can be used alone or in combination. Notably, from the point of view of guaranteeing the desired image density, highly magnetized materials (for example, iron powder (100 emu / g or greater) and magnetite (75 emu / ga 120 emu / g)) preferably are used as the core. Meanwhile, from the point of view of advantageously achieving high image quality and weakening the impact on the photoconductor in which the toner particles are retained in a chain-like manner, poorly magnetized materials (eg copper - zinc materials (Cu -Zn) (30 emu / g to 80 emu / g)) are preferably used as the core.
[000161] The core preferably has an average volumetric particle diameter (D50) of 10 pm to 150 pm, more preferably 20 pm to 80 pm. When the D50 is less than 10 pm, the wearer has a particle size distribution in which most correspond to fine powder. Thus, particle magnetization decreases, potentially causing carrier spreading. While when the D50 is greater than 150 pm, the specific surface area of the wearer decreases, potentially causing toner to scatter. As a result, in the case of color images having a large solid portion, the reproducibility can degrade, among others, the solid portion.
[000162] The material for the resin layer is not particularly limited and can be selected appropriately depending on the intended purpose. Examples of the same include amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, polyester resins, polycarbonate resins, polyethylene resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polytrifluoroethylene resins, resins polyhexafluoropropylene, copolymers formed of vinylidene fluoride and an acrylic monomer, copolymers formed of vinylidene fluoride and vinyl fluoride, fluorotherpolymers such as terpolymers formed from tetrafluoroethylene, vinylidene fluoride and a non-fluorinated silicone monomer, and resins. These can be used alone or in combination.
[000163] Examples of amino resins include urea resins - formaldehyde, melamine resins, benzoguanamine resins, urea resins, polyamide resins and epoxy resins. Examples of polyvinyl resins include acrylic resins, polymethyl methacrylate, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol and polyvinyl butyral. Examples of polystyrene resins include polystyrene and styrene - acrylic copolymers. Examples of the halogenated olefin resins include polyvinyl chloride. Examples of polyester resins include polyethylene terephthalate and polybutylene terephthalate.
[000164] If necessary, the resin layer can additionally contain, for example, electrically conductive powder. Examples of the material for the electrically conductive powder include metals, carbon black, titanium oxide, tin oxide and zinc oxide. The average particle diameter of the electrically conductive powder is not particularly limited and is preferably 1 pm or less. When the average particle diameter is greater than 1 pm, the electrical resistance can be difficult to control.
[000165] The resin layer can be formed, for example, as in the sequence. Specifically, a silicone resin and other materials are dissolved in a solvent to prepare a coating liquid, and then the coating liquid prepared in this way is applied to the core surface with a known coating method, followed by drying and cooking. Examples of the coating method include dipping methods, spraying methods and brush coating methods. Examples of the solvent include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone and celosolve acetate. The cooking method can be an internal or external heating method. Examples of these include methods that employ a fixed type electric oven, a fluid type electric oven, a rotary electric oven or a burner oven; and methods that employ microwave radiation.
[000166] The amount of resin layer contained in the carrier is preferably 0.01 mass% to 5.0 mass%. When the amount is less than 0.01% by mass, a uniform resin layer cannot be formed on the surface of a carrier in some cases. Whereas when the amount thereof is greater than 5.0% by mass, the resin layer formed becomes too thick to cause adhesion between carrier particles, potentially resulting in failure to form uniform carrier particles.
[000167] The developer of the present invention can be used appropriately in the formation of the image by various known electrophotographs such as a method of developing a magnetic component, a method of developing a non-magnetic component and a method of developing two components . <Container that holds the developer>
[000168] A container that accommodates the developer used in the present invention accommodates the developer of the present invention.
[000169] Its container is not particularly limited and can be selected appropriately from known containers. Examples thereof include those having a lid and a main container body.
[000170] The size, shape, structure and material of the main container body are not particularly limited and can be selected appropriately depending on the intended purpose. The main container body preferably has, for example, a hollow cylindrical shape. Particularly preferably, it is a hollow cylindrical body in which the inner surface has concave - convex portions arranged in a spiral some or all of which can suitably and in which the accommodated developer can be transferred to an exit door by rotation.
[000171] The material for the container that accommodates the developer is not particularly limited and is preferably that from which the main container body can be formed with high dimensional accuracy. Among these, resins are preferably used, and examples of preferred resins include polyester resins, polyethylene resins, polypropylene resins, polystyrene resins, polyvinyl chloride resins, polyacrylic acids, polycarbonate resins, ABS resins and polyacetal resins .
[000172] The container above that accommodates the developer has excellent handling capacity; that is, it is suitable for storage, transportation, and is used appropriately for the supply of a developer being detachably mounted, for example, for the process cartridge and the imaging apparatus described above. (Image-forming apparatus and image-forming method)
[000173] An imaging apparatus of the present invention includes a latent electrostatic imaging support member, a charging unit, an exposure unit, a developing unit, a transfer unit and a fixing unit; and, if necessary, additionally includes other units selected appropriately such as a load shedding unit, a cleaning unit, a recycling unit and a control unit. Notably, the charging unit and the display unit are collectively referred to as "latent electrostatic imaging unit."
[000174] An imaging method of the present invention includes a loading step, an exposure step, a developing step, a transfer step and a fixing step; and, if necessary, additionally includes other steps selected in an appropriate manner such as a load elimination step, a cleaning step, a recycling step and a control step. Notably, the charging stage and the exposure stage are collectively referred to as' "latent electrostatic imaging stage."
[000175] The imaging method of the present invention can be carried out appropriately by the imaging device of the present invention, where the loading step can be carried out by the loading unit, the exposure step can be carried out by the unit of exposure, the development step can be performed by the development unit, the transfer step can be performed by the transfer unit, the fixation step can be performed by the fixation unit, and the other steps can be performed by the other units. <Electrostatic imaging support member>
[000176] The material, shape, structure and size of the electrostatic imaging support member (hereinafter referred to as "electrophotographic conductor" or "photoconductor") are not particularly limited and can be selected appropriately from those known in the art. With respect to form, the latent electrostatic imaging support member is suitably in the form of a drum. Regarding the material, the latent electrostatic image support member, for example, is an inorganic photoconductor made from amorphous silicon or selenium and an organic photoconductor made from polysilane or phthalopolymetin. Among these, an amorphous silicon photoconductor is preferred as it has a long service life.
[000177] The amorphous silicon photoconductor can be, for example, a photoconductor having a support and an electrically photoconductive layer of a-Si, which is formed on the support heated to 50 ° C to 400 ° C with a film forming method such as vacuum vapor deposition, sputtering, ion plating, thermal CVD, photo-CVD or plasma CVD (hereinafter this photoconductor can be referred to as "" a-Si photoconductor "). Among them, plasma CVD is used in an appropriate manner, in which gaseous raw materials are decomposed through the application of direct or high frequency current or discharge of microwave shine to form an a-Si deposition film on the support. <Loading step and loading unit
[000178] The loading step is a step that loads a surface of the latent electrostatic image support member and performed by a loading unit.
[000179] Charging can be carried out, for example, by applying voltage to the surface of the electrostatic imaging support member using a charging device.
[000180] The charging device is not particularly limited and can be selected appropriately depending on the intended purpose. Examples of these include charging devices of the contact type known per se having, for example, an electrically conductive or semiconductor roller, brush, film and rubber blade; and non-contact charging devices that use colonic discharge such as corotron and scorotron.
[000181] The loading member can take any shape like a loading roller as well as a magnetic brush or a hair brush. The shape of the device can be selected appropriately according to the specification or configuration of the electrophotographic imaging device used. When the magnetic brush is used, it is composed of: a means of charging various ferrite particles such as Zn-Cu ferrite; an electrically conductive non-magnetic sleeve to support the ferrite particles; and a magnetic roller included in the non-magnetic conductive sleeve. Also, when the skin brush is used, it can be a skin that is treated to be electrically conductive with, for example, carbon, copper sulfide, a metal or a metal oxide as well as that is spiraled around or mounted to a metal or metal core treated to be electrically conductive.
[000182] The charging device is not limited to the charging devices of the contact type mentioned above. However, contact type charging devices are preferably used from the point of view of producing an imaging device in which the amount of ozone generated from the charging devices is reduced.
[000183] The charging device is preferably one that superimposes both DC and AC voltages to the latent electrostatic image support member, arranged to be in contact or non-contact with it.
[000184] Furthermore, the charging device is preferably a charging roller that charges the latent electrostatic imaging support member by overlapping both DC voltage and AC voltage to the latent electrostatic imaging support member. , arranged approximately for the same through a gap tape; that is, in a non-contact way. <Exposure stage and exposure unit
[000185] The exposure step is a step that reveals a surface of the latent electrostatic image support member loaded and carried out by the exposure unit.
[000186] Exposure can be carried out, for example, in the image direction by exposing the surface of the latent electrostatic image support member to light using the exposure unit.
[000187] The optical system in the exhibition is roughly classified into an analog optical system and a digital optical system. The analog optical system is an optical system in which a manuscript is designed directly onto an electrostatic imaging support member. The digital optical system is an optical system in which image information is given as electrical signals which are then converted to light signals, and a latent electrostatic image support member is exposed to the light signals to form an image.
[000188] The exposure unit is not particularly limited and can be selected appropriately depending on the purpose, as long as it achieves desired image exposure on the surface of the limb that supports latent electrophotographic image loaded with the charging unit. Examples thereof include various display devices such as an optical copy display device, a lens array display device, a laser optical display device, a liquid crystal shutter display device, and an exposure device. LED optics.
[000189] In the present invention, light can be applied in the direction of the image from the side that faces the support of the latent electrostatic image support member. <Development stage and development unit>
[000190] The development step is a step of developing the latent electrostatic image with the toner or developer of the present invention to form a visible image.
[000191] The visible image can be formed with the development unit, for example, developing the latent electrostatic image using the toner or developer of the present invention.
[000192] The development unit is not particularly limited and can be selected appropriately from the known development units, as long as it achieves development with the toner or developer of the present invention. For example, the developer unit is preferably one having a developer device that contains the toner or developer of the present invention and that can apply the toner or developer to the latent electrostatic image in a contact or non-contact manner. The developer unit is most preferably a developer device containing the container that accommodates the toner of the present invention.
[000193] The above development device may employ a dry or wet development process, and may be a single color or multiple color development device. For example, the developing device is preferably one having a rotating magnetic roller and a stirrer to load the toner or developer with friction generated during shaking.
[000194] In the developing device, toner particles and carrier particles are agitated and mixed in such a way that the toner particles are charged by friction generated between them. The charged toner particles are retained in a chain-like manner on the surface of the rotating magnetic roller to form magnetic brushes. The magnetic roller is arranged close to the electrostatic imaging developing member (photoconductor) and thus, some of the toner particles that form the magnetic brushes on the magnet roller are transferred to the surface of the electrostatic imaging developing member (photoconductor). by the action of electrically attractive force. As a result, the electrostatic imaging is developed with the toner particles to form a visual toner image on the surface of the electrostatic imaging development member (photoconductor).
[000195] The developer contained in the developer is a developer containing the toner of the present invention. The developer may be a one-component developer or a two-component developer. The toner contained in the developer is the toner of the present invention. <Transfer step and transfer unit>
[000196] The transfer step is a transfer step of visible images to a recording medium. In this step, preferably, the visible images are primarily transferred to an intermediate transfer member, and the visible images transferred in this way are transferred to the recording medium per second. In addition, toners of two or more colors are used; preferably, a color toner is used. More preferably, the transfer step includes: a primary transfer step of transferring the visible images to an intermediate member to form a composite transfer image; and a secondary transfer step of transferring the composite transfer image to a recording medium.
[000197] For example, the transfer of visible images can be performed with the transfer unit by charging the member of the electrostatic imaging support member (photoconductor) with a transfer charger. Preferably, the transfer unit includes: a primary transfer unit configured to transfer the visible images to an intermediate member to form a composite transfer image; and the secondary transfer unit configured to transfer the composite transfer image to a recording medium.
[000198] The intermediate transfer member is not particularly limited and can be selected appropriately from known transfer members depending on the intended purpose. For example, the intermediate transfer member is preferably a transfer belt.
[000199] The transfer unit (including the primary and secondary transfer units) preferably includes at least one transfer device that transfers the visible images from the latent electrostatic image support member (photoconductor) to the recording medium. The number of transfer units can be one or two or more. Examples of the transfer device include a corona transfer device that employs corona discharge, a transfer belt, a transfer roller, a pressing transfer roller and an adhesive transfer device.
[000200] The recording medium is not particularly limited and can be selected appropriately depending on the purpose, as long as it can receive an unfixed image developed. Examples of the recording medium include plain paper and a PET base for OHP, with plain paper being used typically. <Fixing step and fixing unit>
[000201] The fixing step is a fixing step, using a fixing unit, the toner image that has been transferred to the recording medium. When two or more color toners are used, the fixing step can always be performed after a toner image of each color is transferred to the recording medium; or the fixing step can be performed at a time after toner images of all colors are superimposed over each other in the recording medium. The fixation unit is not particularly limited and can employ a method of thermal fixation using a known pressure heating device. Examples of the heating pressing device include: a combination of a heating roller and a pressing roller; and a combination of a heating roller, a pressing roller and an endless belt. The heating temperature is generally 80 ° C to 200 ° C. Optionally, a known photo-fixation device or a similar device can be used in conjunction with the fixation unit.
[000202] In a conventional manner, when such a thermal fixation method is employed for a fixation unit, half or more of the total energy consumed by the imaging device is used to heat the toner with the fixation unit that employs the fixation method thermal fixation. Meanwhile, from the point of view of countermeasures to environmental problems in recent years, demand has arisen for an imaging device that consumes less energy (energy savings).
[000203] For example, the International Energy Agency (IEA) DSM (Demand Side Management) program in fiscal 1999 includes a technology search project for next generation copiers and describes its requirement specification, where copiers at 30 cpm or more are needed for reliable energy savings compared to conventional copiers. Specifically, these copiers need to have a waiting time of 10 seconds or less during which the power consumption is set to 10 Watt up to 30 Watt (which is varied with the copy speed). Therefore, energy savings must be achieved in the clamping unit that consumes high energy consumption.
[000204] An essential technical matter to be achieved in order to satisfy the above requirement and shorten the waiting time is to reduce the temperature at which the toner starts to melt, thereby reducing the fixing temperature during use. In order to respond to the reduction in the setting temperature, the imaging apparatus of the present invention uses the toner of the present invention.
[000205] The fixing unit has been improved for energy saving. Among the thermal fixation methods, the thermal roller fixation method, where a heating roller is pressed directly against the toner image in the recording medium for fixation, was widely used because of the good thermal efficiency. In another employable method, a heating roller is made to have low thermal capacity, thereby improving the response of the toner to the temperature. However, the decreased specific thermal capacity of the heating roller results in a greater difference in temperature between the portions through which the recording medium has passed and portions through which the recording medium has not passed, causing toner to adhere to the fixing roller. . As a result, after the fixing roller is rotated once, the so-called hot-displacement phenomenon occurs where the toner is fixed to the portions that are not an image of the recording medium. Thus, there are stricter requirements on the toner for the low temperature fastening property and hot displacement resistance. Therefore, the imaging apparatus of the present invention uses the toner of the present invention which is excellent in both low temperature fastening properties and hot displacement resistance. <Other steps and other units> - Load shedding step and load shedding unit -
[000206] The charge elimination step is a step of applying a polarization that eliminates charge to the latent electrostatic image support member to eliminate charges from it, and can preferably be performed by a charge elimination unit.
[000207] The de-charging unit is not particularly limited and can be selected appropriately from known de-charging devices, as long as it can apply a de-charging bias to the latent electrostatic imaging member. For example, the de-charging device is preferably a de-charging lamp. - Cleaning step and cleaning unit -
[000208] The cleaning step is a step to remove the toner remaining in the electrostatic imaging support member, and can preferably be performed by a cleaning unit.
[000209] The cleaning unit is not particularly limited and can be selected appropriately from known cleaners, as long as it can remove the toner that remains in the electrostatic imaging support member. Examples of cleaners include a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a blade cleaner, a brush cleaner and a screen cleaner. - Recycling stage and recycling unit -
[000210] The recycling step is a step of recycling the toner removed in the cleaning step for the development unit, and can be carried out preferably by a recycling unit.
[000211] The recycling unit is not particularly limited and can, for example, be a known transport unit. - Control step and control unit -
[000212] The control step is a control step for each of the steps above, and can be performed preferably by a control unit.
[000213] The control unit is not particularly limited and can be selected appropriately depending on the purpose, as long as it can control the operation of each of the units above. Examples of these include devices such as a sequencer and a computer.
[000214] Fig. 1 illustrates an example of the imaging apparatus of the present invention. An imaging apparatus 100A in Fig. 1 includes: a photoconductive drum 10 which serves as the latent electrostatic image support member; a loading roller 20 that serves as the loading unit; a display device that serves as the display unit; developer devices each serving as the developer unit (i.e., a 40K black toner developer device, a 40Y yellow toner developer device, a 40M magenta toner developer device, and a toner developer device cyan 40C); an intermediate transfer member 50; a cleaning device 60 having a cleaning blade and serving as the cleaning unit; a de-charge lamp 70 that serves as the de-charge unit; and a clamping device that serves as the clamping unit.
[000215] The intermediate transfer member 50 is an endless belt and can be moved in a direction indicated by the arrow being stretched by three support rollers 51 which are provided in a cycle of the belt. Some of the three support rollers 51 also serve as a transfer bias roll capable of applying a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. A cleaning device 90 having a cleaning blade is arranged in the vicinity of the intermediate transfer member 50. In addition, a transfer roller 80 is arranged to face the intermediate transfer member 50 and serves as a transfer unit capable of applying a transfer bias to transfer (transfer per second) a toner image for recording paper 95. Around the intermediate transfer member 50, a corona loading device 52 for applying loads to the toner image on the intermediate transfer member 50 is disposed between a contact point of the transfer member intermediate 50 with the photoconductor drum 10 and a contact portion of the trans member intermediate transfer 50 with recording paper 95.
[000216] The black (K), yellow (Y), magenta (M) and cyan (C) toner developer (ie the 40K black toner developer, the 40Y yellow toner developer, the 40M magenta toner developer, and the 40C cyan toner developer each contain a developer housing section (41K, 41Y, 41M or 41C), a developer supply roller (42K, 42Y, 42M or 42C) and a developer roller (43K, 43Y, 43M or 43C).
[000217] In the imaging apparatus lOOA, the loading roller 20 uniformly loads the photoconductor drum 10. The photoconductor drum 10 is exposed in the image direction to the light L emitted from an exposure device to form an electrostatic latent image. The latent electrostatic image formed in the photoconductor drum 10 is developed with a developer provided from each of the development device 40, to thereby form a toner image. The toner image is transferred to the intermediate transfer member 50 (primary transfer) with a transfer bias applied from the rollers 51. The image transferred from the intermediate transfer member 50 is loaded with a corona loading device 52 and then it is transferred to recording paper 95 (secondary transfer). The image of the toner transferred to the recording paper 95 is sharpened and pressed by a heating roller and a pressure roller of the fixing unit, so that the toner image is fused and fixed on the recording paper 95. Notably , the toner particles remaining in the photoconductor drum 10 are removed by the cleaning unit 60, and the charges in the photoconductor drum 10 are eliminated by the charge eliminator lamp 70.
[000218] Fig. 2 illustrates another example of the imaging apparatus of the present invention. An imaging apparatus 100B in Fig. 2 is a colored imaging apparatus together, and includes a copy device main body 150, a paper feed table 200, a scanner 300 and a document feeder. automatic (ADF) 400.
[000219] The copying device main body 150 is provided in its central portion with an endless transfer member in the form of endless belt 50. The intermediate transfer member 50 can be rotated by being extended by support rollers 14, 15 and 16 in a direction indicated by the arrow. A cleaning unit 17 configured to remove the toner particles remaining in the intermediate transfer member 50 is disposed in the vicinity of the support roller 15. Around the intermediate transfer member 50 stretched by the support roller 14 and 15 a set is provided development device 120 in which four 18K, 18Y, 18M and 18C imaging units for yellow (Y), cyan (C), magenta (M) and black (K) toners are arranged in a row along the direction movement of the intermediate transfer member.
[000220] As illustrated in Fig. 3, each of the imaging units 18 includes: a photoconductor drum 10; a loading roller 20 which uniformly loads the photoconductor drum 10; a developing device 40 that forms a toner image by developing a latent electrostatic image formed on the photoconductor drum 10 with a black (K), yellow (Y), magenta (M) or cyan (C) developer; a transfer roller 80 that transfers the toner image to an intermediate transfer member 50; a cleaning unit 60; and a charge-free lamp 70.
[000221] In addition, an exposure unit 30 is provided in the vicinity of the developing device assembly 120. The exposure unit 30 applies L light to the photoconductor drum 10 to form an electrostatic latent image.
[000222] In addition, a secondary transfer unit 22 is provided in the intermediate transfer member 50 on the side opposite the side where the developing device assembly 120 is arranged. The secondary transfer device 22 includes a secondary transfer belt in the form of endless belt 24 and a pair of support rollers 23 that stretch the secondary transfer belt 24. The embossing paper carried on the secondary transfer belt 24 can come into contact. contact the transfer member
[000223] A clamping unit 25 is provided in the vicinity of the secondary transfer unit 22. The clamping unit 25 includes an endless clamping strap 26 and a pressing roller 27 arranged to be pressed against the clamping belt. fixing 26. One of the rollers that stretch the fixing belt 26 is a heating roller. In addition, when image formation is carried out on both sides of the recording paper, a blade reversing device 28 for reversing the recording paper is disposed in the vicinity of the secondary transfer device 22 and the fixation device 25.
[000224] Next, the formation of a color image (color copy) using a 100B image formation apparatus having the configuration described above will be described. First, an original document is defined on a document table 130 of the automatic document feeder (ADF) 400. Alternatively, the automatic document feeder 400 is opened and then an original document is defined on a contact glass 32 of the scanner 300, followed by the closing of the automatic document feeder 400. In the previous case, when a start switch is pressed, the scanner 300 is operated to run a first cartridge 33 and a second cartridge 34 after the original document has been transferred to the contact glass 32 In the previous case, when a start switch is pressed, the scanner 300 is operated immediately to run a first cartridge 33 and a second cartridge 34. At that moment, the first cartridge 33 radiates the original document with light from a source of light, and then the second cartridge 34 reflects, in its mirror, light reflected by the original document. The reflected light is thus received by a reading sensor 36 through an image-forming lens 35 to read the original document (color image), thereby generating image information that corresponds with black, yellow, magenta and cyan.
[000225] Additionally, based on the image information obtained in this way, a latent electrostatic image corresponding to each color is formed in the photoconductor drum 10 with the exposure device 30. Subsequently, the latent electrostatic image is developed with a developer provided developing device 40 for each color toner, to form color toner images in this way. The color toner images formed in this way are sequentially superimposed (transferred primarily) on top of each other on the intermediate transfer member 50 being rotated by the support roll 14, 15 and 16, while a composite toner image is formed on the member intermediate transfer 50.
[000226] On paper feed table 200, one of paper feed rolls 142 is selectively rotated to feed sheets of embossing paper from one of vertically stacked paper feed cassettes 144 housed in a paper bank 143. The blades fed in this way are separated from each other by a separating roller 145. The separated blade is thus fed through a paper feed path 146, then fed through a paper feed path 148 into the main body of the copying device. 150 by a transfer roller 147, and stopped on a registration roller 49. Alternatively, the engraving of paper slides positioned in a bypass tray 54 are fed, and the slides fed in this way are separated from each other by a separation roller 58. The separate blade is thus fed through a manual paper feed path 53, and stopped on a registration roller 49. Notably, the registration roller 4 9 is generally connected to the soil in use. Alternatively, it can be used while a polarization is being applied to it to remove paper dust from the embossing paper sheets.
[000227] The registration roller 49 is rotated to feed a sheet of embossing paper between the intermediate transfer member 50 and the secondary transfer unit 22 so that the composite toner image formed on the intermediate transfer member 50 can be transferred (secondarily transferred) to the recording paper sheet.
[000228] The embossing paper sheet having the composite toner image is fed by the secondary transfer unit 22 to the fixture unit 25. In the fixture unit 25, the fixation belt 26 and the pressing roller 27 fixes the image toner compound on the embossing paper sheet by applying heat and pressure. Subsequently, the embossing paper sheet is unloaded from an unloading roller 56 by a switch claw 55 and then stacked in an unloading tray 57. Alternatively, the embossing paper sheet is reversed with the sheet 28 by a switch claw 55 and transported again to a position where the transfer is carried out. Next, an image is also formed on the back surface of the same, and then the sheet thus obtained is unloaded from an unloading roller 56 and stacked in an unloading tray 57.
[000229] Notably, a cleaning unit 17 removes the toner particles that remain in the intermediate transfer member 50 after transferring the composite toner image. <Process cartridge>
[000230] A process cartridge used in the present invention includes at least one electrostatic imaging support member configured to support an electrostatic imaging image and a developing unit configured to reveal the electrostatic imaging formed on the electrostatic imaging support member with the toner of the present invention, to form a visible image in this way; and, if necessary, additionally includes other appropriately selected units such as a loading unit, a developing unit, a transfer unit, a cleaning unit and a load eliminating unit. The process cartridge of the present invention is detachably mounted to the main body of the imaging apparatus.
[000231] The developer unit includes at least one container that accommodates the developer that accommodates the toner or developer of the present invention, and a developer-supporting member configured to support and transfer the toner or developer that is accommodated in the developer container. The developer unit may additionally include other members such as a member for regulating the thickness of the toner to be born. The process cartridge of the present invention can be detachably mounted to various electrophotographic imaging machines, fax machines and printers. Preferably, the process cartridge of the present invention is detachably mounted to the imaging apparatus of the present invention.
[000232] As shown in Fig. 4, a process cartridge 110 includes a latent electrostatic image support member 10, a loading unit 52, a developing unit 40, a transfer unit 80 and a cleaning unit 90; and, if necessary, additionally includes other units. In Fig. 4, reference characters 95 and L denote a sheet of recording paper and light emitted from an exposure unit, respectively.
[000233] The developing unit includes at least one container that accommodates the developer that accommodates the developer of the present invention, and a developer support member configured to support and transfer the developer accommodated in the container that accommodates the developer. Notably, the developing unit may additionally include other members such as a member to regulate the thickness of the developer to be born.
[000234] Next, a description will be given to the image formation process by the process cartridge illustrated in Fig. 4. While rotating in a direction indicated by the arrow, the latent electrostatic image support member 10 is loaded with the imaging unit. charge 52 and is then exposed to the L light emitted from the exposure unit. As a result, an electrostatic imaging in response to the exposure pattern is formed on the surface of the imaging support member. The latent electrostatic image is developed with the toner in the development unit 40. The developed toner image is transferred with the transfer unit 80 onto the recording paper sheet 95, which is then printed. Next, the surface of the latent electrostatic image support member from which the toner image was transferred is cleaned with the cleaning unit 90, and the charge is eliminated with the charge erase unit. The process described above is carried out repeatedly.
[000235] The imaging method, the imaging apparatus and the process cartridge of the present invention can efficiently form high quality images over a long period of time, as they use the toner of the present invention that exhibits good holding property at 150 ° C or lower to form good still images and which, even when used in high-speed copiers, can greatly suppress contamination inside the copiers due to volatile wax dust particles and the release of particulate matter. dust to the outside. Examples
[000236] The following invention will be described by way of Examples, which are not to be construed as limiting the present invention. (Example of ester wax synthesis)
[000237] The fatty acid components shown in Table 1 and the alcohol components shown in Table 1 in the molar ratios shown in Table 1 were added to a reaction vessel along with an effective amount of sulfuric acid that serves as a catalyst. Under nitrogen flow, these fatty acid components and these alcohol components were esterified at 240 ° C to synthesize monoester waxes 1 to 11 and polyester waxes shown in Table 1.
[000238] Next, the obtained ester waxes were measured for various properties as in the sequence. The results are shown in Table 1. <Endothermic wax peak temperature measurement at the second temperature rise>
[000239] The peak endothermic temperature (melting point) of each ester wax at the second temperature rise was measured as follows using a DSC (differential scanning calorimeter) system ("Q-200," product of TA INSTRUMENTS Co.).
[000240] Specifically, first, about 5.0 mg of the wax to be measured was precisely weighed and placed in a sample container made of aluminum; the sample container was placed in a retainer unit; and the retainer unit was set in an electric oven. Then, in a nitrogen atmosphere (flow rate: 50 mL / min), the sample was heated from -20 ° C to 150 ° C under the following conditions: rate of temperature increase: 1 ° C / min ; temperature modulation cycle: 60 seconds; and temperature modulation range: 0.159 ° C; and then the sample was cooled from 150 ° C to 0 ° C at a temperature drop rate of 10 ° C / min. Then, the sample was heated again to 150 ° C at a temperature increase rate of 1 ° C / min. The DSC curve obtained using the differential scanning calorimeter ("Q-200," product of TA INSTRUMENTS Co.) was used to determine the peak endothermic temperature attributed to the ester wax at the second temperature rise. <Measurement of complex viscosities η * a and η * b of the wax>
[000241] The dynamic viscoelasticity of the ester wax was measured with the ARES measuring device (product of Rheometric Scientific Co.).
[000242] First, a wax sample was molded on a table. Then, parallel plates of 50 mm in diameter were defined for the top of the geometry and a glass of 50 mm in diameter was defined at the bottom of the same. After the 0 point adjustment has been made so that the normal force becomes 0, sine wave vibration was applied to the table at a vibration frequency of 6.28 rad / s to 62.8 rad / s. The interval between the parallel plates was set to 1.0 mm, and measurement was performed within -15 ° C to + 15 ° C of the melting point of the wax.
[000243] η * a denotes a complex viscosity (Pa.s) determined by measuring a dynamic viscoelasticity of the wax at a measurement frequency of 6.28 rad / s, and η * b denotes a complex viscosity (Pa.s) determined by measuring a dynamic viscoelasticity of the wax at a measurement frequency of 62.8 rad / s.

Table 1-2
(Example 1) <Toner production> - Preparation of fine organic particle emulsion -
[000244] A reaction vessel equipped with a stirring rod and a thermometer was loaded with water (683 parts by mass), a sodium salt of sulfuric acid ester of methacrylic acid - ethylene oxide adduct (ELEMINOL RS-30 : product from Sanyo Chemical Industries, Ltd.) (11 parts by mass), styrene (83 parts by mass), methacrylic acid (83 parts by mass), butyl acrylate (110 parts by mass) and ammonium persulfate (1 part mass), and the resulting mixture was stirred at 400 rpm for 15 min to prepare a white emulsion. The emulsion thus obtained was heated to 75 ° C and left to react for 5 hours. Subsequently, a 1% by weight aqueous solution of ammonium persulfate (30 parts by weight) was added to the reaction mixture, followed by aging at 75 ° C for 5 hours, to prepare in this way an aqueous dispersion liquid. fine particle dispersion] of a vinyl resin (a copolymer of styrene / methacrylic acid / butyl acrylate / sodium salt of methacrylic acid sulfuric acid - ethylene oxide adduct).
[000245] The [fine particle dispersion liquid] prepared in this way was measured to the volumetric average particle diameter with a particle size analyzer (LA-920, product of Horiba, Ltd.) and was found to have a diameter volumetric mean particle of 0.10pm.
[000246] Part of the [fine particle dispersion liquid] was dried to separate the resin. The resin separated in this way was found to have a glass transition temperature (Tg) of 57 ° C and a mass average molecular weight of 121,000. - Preparation of aqueous phase -
[000247] Water (990 parts by weight), [fine particle dispersion liquid] (80 parts by weight), an aqueous solution of 48.5% by weight of sodium dodecildiphenyl ether disulfonate (ELEMINOL MON-7, product of Sanyo Chemical Industries Ltd.) (40 parts by mass) and ethyl acetate (90 parts by mass) were mixed and stirred to obtain an opaque white liquid, which was used as [aqueous phase 1]. - Synthesis of low molecular weight polyester resin -
[000248] A reaction vessel equipped with a condenser, a stirrer and a nitrogen introducing tube was charged with propylene oxide 3 mol bisphenol A adduct (781 parts by mass), terephthalic acid (218 parts by mass), acid adipic (48 parts by mass) and dibutyl tin oxide (2 parts by mass), followed by reaction at 230 ° C for 13 hours under normal pressure. Then, the reaction mixture was allowed to react for 7 hours at a reduced pressure of 10 mm Hg to 15 mm Hg. Then, trimellitic anhydride (45 parts by mass) was added to the reaction vessel, followed by reaction at 180 ° C for 2 hours under normal pressure, to obtain in this way [low molecular weight polyester resin].
[000249] The obtained [low molecular weight polyester resin] was found to have a numerical average molecular weight of 9,600, a mass average molecular weight of 28,000, a glass transition temperature (Tg) of 43 ° C and a value of acid of 12.2 mg KOH / g. - Synthesis of crystalline polyester resin -
[000250] A four-necked 5 L flask equipped with a nitrogen introducing tube, a drain tube, a stirrer and a thermo coupler was loaded with 1,12-dodecanediol (2,500 g), 1,8-octanoic acid ( 2.330 g) and hydroquinone (4.9 g), followed by the reaction at 180 ° C for 20 hours. Then, the reaction mixture was allowed to react at 200 ° C for 6 hours and additionally reacted at 8.3 kPa for 10 hours, to thereby produce [crystalline polyester resin 1].
[000251] The obtained [crystalline polyester resin 1] was found to have a melting point of 69 ° C, an SP of 9.9, and a mass average molecular weight of 15,000 as measured by GPC.
[000252] Notably, the melting point of the crystalline polyester resin was measured as the maximum endothermic peak using the differential scanning calorimeter TG-DSC SYSTEM TAS-100 (product of Rigaku Corporation). - Synthesis of prepolymer -
[000253] A reaction vessel equipped with a condenser, a stirrer and a nitrogen introducing tube was loaded with a 2 mol adduct of bisphenol A ethylene oxide (682 parts by mass), a 2 mol adduct of propylene oxide bisphenol A (81 parts by weight), terephthalic acid (283 parts by weight), trimellitic anhydride (22 parts by weight) and dibutyl tin oxide (2 parts by weight), followed by the reaction at 230 ° C for 8 hours under normal pressure. Then, the reaction mixture was allowed to react for 5 hours at a reduced pressure of 10 mm Hg to 15 mm Hg, to obtain the [intermediate polyester] in this way. The obtained [intermediate polyester] was found to have a numerical average molecular weight of 2,100, a mass average molecular weight of 9,500, a glass transition temperature (Tg) of 55 ° C, an acid value of 0.5 mg KOH / g and a hydroxyl value of 49 mg KOH / g.
[000254] Next, a reaction vessel equipped with a condenser, a stirrer and a nitrogen introducing tube was loaded with [intermediate polyester] (411 parts by mass), diisocyanate isophorone (89 parts by mass) and ethyl acetate (500 parts by mass), followed by the reaction at 100 ° C for 5 hours, to obtain in this way the [repolymer]. - Preparation of the main mixture -
[000255] Carbon black (REGAL 400R, product of Cabot Corporation) (40 parts by weight), a polyester resin (60 parts by weight) (RS-801, product of Sanyo Chemical Industries, Ltd., acid value: 10 mg KOH / g, mass average molecular weight (Mw): 20,000, glass transition temperature (Tg): 64 ° C) and water (30 parts by mass) were mixed using HENSCHEL MIXER, to obtain a mixture containing pigment aggregates impregnated with water.
[000256] The obtained mixture was kneaded for 45 minutes with a two-foil mill in which the roller surface temperature was adjusted to 130 ° C. the kneaded product was sprayed with a sprayer to have a diameter of 1 mm, while the [main mixture] was obtained. - Synthesis of the quetimine compound -
[000257] A reaction vessel equipped with a stirring rod and a thermometer was loaded with isophorone diamine (170 parts by mass) and methyl ethyl ketone (75 parts by mass), followed by the reaction at 50 ° C for 5 hours, to thus producing the [quetimine compound]. An amine value of the [quetimine compound] obtained was found to be 418. - Preparation of the oil phase -
[000258] A container to which a stirring rod and a thermometer were set was loaded with the [low molecular weight polyester resin] obtained above (378 parts by mass), the [crystalline polyester resin 1] obtained above (220 parts by mass), the [monoester wax 1] obtained above (110 parts by mass) and ethyl acetate (947 parts by mass), and the mixture was heated to 80 ° C with stirring. The resulting mixture was kept at 80 ° C for 5 hours and then cooled to 30 ° C for 1 hour, to obtain in this way the [raw material solution].
[000259] The obtained [raw material solution] (1,324 parts by mass) was placed in a container and treated with a crimping mill ("ULTRA VISCOMILL," product of AIMEX CO., Ltd.) under the following conditions: a liquid feed rate of 1 kg / h, a disc circumferential speed of 6 m / s, 0.5 mm zirconia beads packaged up to 80% in volume, and 3 passes.
[000260] Subsequently, the [main mixture] prepared above (500 parts by mass) and the [repolymer] synthesized above (109.4 parts by mass) were added to the [raw material solution], and the resulting mixture was passed once with the crimping mill under the conditions above, to obtain in this way the [oil phase dispersion liquid].
[000261] The concentration of solid content of the [oil phase dispersion liquid] obtained was found to be 50% by mass (130 ° C, 30 minutes). - Emulsification, deformation and desolvation -
[000262] The [oil phase dispersion liquid] prepared above (800 parts by mass) and the [quetimine compound] synthesized above (6.6 parts by mass) were added to a container, followed by mixing for 1 minute at 5,000 rpm with a TK homomixer (product from Tokushu Kika Kogyo Co., Ltd.). Then, the [aqueous phase] prepared above (1,200 parts by mass) was added to the container, and the resulting mixture was mixed with the TK homomixer at 13,000 rpm for 3 minutes, to obtain in this way the [emulsified slurry].
[000263] The obtained [emulsified slurry] was added to a container to which a stirrer and a thermometer were set and left to stand at 15 ° C for 1 hour, followed by desolvation at 30 ° C for 1 hour, to produce this forms the [dispersion slurry].
[000264] The obtained [dispersion slurry] was found to have an average volumetric particle diameter of 5, 95 pm and a numerical average particle diameter of 5.45 pm, which are measured with MULTISIZER II. - Washing and drying -
[000265] The obtained [dispersion slurry] (100 parts by mass) was filtered under reduced pressure. Ion exchange water (100 parts by mass) was added to the filter cake, followed by mixing with a TK homomixer (at 12,000 rpm for 10 min) and filtration. Then, 10% by weight of aqueous sodium hydroxide solution (100 parts by mass) was added to the filter cake, and the resulting mixture was mixed with a TK homomixer (at 12,000 rpm for 30 min) under the application of vibration. ultrasonic, followed by filtration under reduced pressure.
[000266] This washing with sodium hydroxide under the application of ultrasonic vibration was carried out again, twice in total.
[000267] Next, 10% by mass of aqueous hydrochloric acid solution (100 parts by mass) was added to the filter cake, and the resulting mixture was mixed with a TK homomixer (at 12,000 rpm for 10 min), followed by filtration. Then, the ion exchange water (300 parts by mass) was added to the filter cake, and the resulting mixture was mixed with a TK homomixer (at 12,000 rpm for 10 min), followed by filtration. This treatment of adding ion exchange water, mixing and filtration was carried out twice to obtain in this way [filter cake 1].
[000268] The obtained [filter cake 1] was dried with an air circulation dryer at 45 ° C for 48 hours, and then sieved with a mesh having an opening size of 75 pm to obtain the toner base particles. .
[000269] Hydrophobic silica (0.7 parts by mass) and hydrophobic titanium oxide (0.3 parts by mass) were mixed with the toner base particles obtained (100 parts by mass) using HENSCHEL MIXER, to produce in this way toner 1. (Example 2) - Toner production -
[000270] The procedure of Example 1 was repeated, except that [monoester wax 1] was changed to [monoester wax 2], to produce toner 2 in this way. (Example 3) - Toner production -
[000271] The procedure of Example 1 was repeated, except that [monoester wax 1] was changed to [monoester wax 3], to produce toner 3 in this way. (Example 4) - Toner production -
[000272] The procedure of Example 1 was repeated, except that [monoester wax 1] was changed to [monoester wax 4], to produce toner 4 in this way. (Example 5) - Toner production -
[000273] The procedure of Example 1 was repeated, except that [monoester wax 1] was changed to [monoester wax 5], to produce toner 5. In this way (Example 6) - Toner production -
[000274] The procedure of Example 1 was repeated, except that [monoester wax 1] was changed to [monoester wax 6], to produce toner 6 in this way. (Example 7) - Toner production -
[000275] The procedure of Example 1 was repeated, except that [monoester wax 1] was changed to [monoester wax 7], to produce toner 7 in this way. (Example 8) - Toner production -
[000276] The procedure of Example 1 was repeated, except that [monoester wax 1] was changed to [olyester waxes], to produce toner 8 in this way. (Comparative Example 1) - Toner production -
[000277] The procedure of Example 1 was repeated, except that [monoester wax 1] was changed to [monoester wax 8], to thereby produce toner 9.
[000278] (Comparative Example 2)
[000279] The procedure of Example 1 was repeated, except that [monoester wax 1] was changed to [monoester wax 9], to produce toner 10 in this way. (Comparative Example 3) - Toner production -
[000280] The procedure of Example 1 was repeated, except that [monoester wax 1] was changed to [monoester wax 10], to produce toner 11 in this way. (Comparative Example 4) - Toner production -
[000281] The procedure of Example 1 was repeated, except that [monoester wax 1] was changed to [monoester wax 11], to produce toner 12 in this way. (Comparative Example 5) - Toner production -
[000282] The procedure of Example 1 was repeated, except that [monoester wax 1] was changed to [araffin wax] (product of NIPPON SEIRO CO., LTD.)], In order to produce toner 13 in this way. (Comparative Example 6) - Toner production -
[000283] The procedure of Example 1 was repeated, except that [monoester wax 1] was changed to [microcrystalline wax] (product of NIPPON SEIRO CO., LTD.)], In order to produce this toner 14. ( Comparative Example 7) - Toner production -
[000284] The procedure of Example 1 was repeated, except that [monoester wax 1] was changed to [olyalkylene wax] (product of NIPPON SEIRO CO., LTD.)], In order to produce 15 toner in this way. - Developer development>
[000285] 5% by mass of each of the toners produced were mixed with 95% by mass of silicone particles of copper - zinc ferrite carrier coated with silicone resin having an average particle diameter of 40 pm using a ball mill, to produce the developers in this way.
[000286] Next, each of the toners and developers was evaluated for various properties as follows. The results are shown in Table 2. <Release property>
[000287] Each developer was used to print 1,000 sheets of copy paper <55> paper (product of NBS Inc.) with an image forming device (IMAGIONEO450, product of Ricoh Company, Ltd.) capable of printing 45 sheets A4 size paper per minute. During the printing process, the number of paper jams was measured and evaluated for the release property according to the following criteria. Evaluation criteria A: No paper jams have occurred. B: Paper jam occurred one to three times. C: Paper jam has occurred four to ten times. D: Paper jam has occurred eleven times or more. <Fixing property
[000288] The fixing portion of a copier (MF2200, product of Ricoh Company, Ltd.) using a TEFLON roller (trademark) as a fixing roller has been modified so that the fixing temperature can be changed as desired . Then, copy testing was performed using the device modified in this way and Type 6200 paper (product of Ricoh Company, Ltd.).
[000289] Specifically, the cold travel temperature (the minimum fixing temperature) was obtained by changing the fixing temperature.
[000290] The evaluation conditions for the minimum fixing temperature were as follows: the linear paper feed speed: 120 mm / second at 150 mm / second, the surface pressure: 1.2 kgf / cm2, and the narrowing width: 3 mm.
[000291] The minimum fixing temperature is preferably lower as the energy consumption can be monitored. The minimum fixing temperature of 130 ° C or less is a problem-free level in practical use. [Evaluation criteria] A: The minimum fixing temperature was less than 125 ° C. B: The minimum fixing temperature was 125 ° C or higher but 130 ° C or lower. C: The minimum fixing temperature was 130 ° C but cold displacement occurred slightly. D: The minimum fixing temperature was greater than 130 ° C. <Heat resistance storage stability>
[000292] Each toner was loaded into a 50mL glass container, which was then left to rest in a 50 ° C thermostat bath for 24 hours, followed by cooling to 24 ° C. The toner treated in this way was measured for the degree of penetration according to the penetration test (JIS K2235-1991) and evaluated for storage stability of hot resistance according to the following criterion. Notably, the higher degree of penetration means more excellent heat resistance storage stability. A toner having a penetration rate of less than 5 mm is very likely to cause problems in use. [Evaluation criteria] A: The degree of penetration was 25 mm or greater B: The degree of penetration was 15 mm or greater but less than 25 mm. C: The degree of penetration was 5 mm or greater but less than 15 mm. D: The degree of penetration was less than 5 mm. <Contamination in the device
[000293] Contamination in the device was assessed as follows. Specifically, a particle counter (KC01E, product of Riontech Co., Ltd.) was mounted to the gas outlet port of a copier's main body (MF2200, product of Ricoh Company, Ltd.). Then, the copier was allowed to issue sheets of paper each having an image occupancy rate of 20% at a fixing temperature of 180 ° C for 1 min. Contamination in the device was assessed based on the number of dust particles. [Evaluation criteria] A: No dust particles were detected. B: The number of dust particles detected was less than 50,000. C: The number of dust particles detected was 50,000 or more but less than 100,000. D: The number of dust particles detected was 100,000 or more.


[000294] As shown in Table 2, all toners in Examples 1 to 8 were found to be excellent in release property, in low temperature fixation property, in heat resistance storage stability, and in device contamination and form high quality images. In more detail, the toner of Example 2 was found to have a higher viscosity complex η * a than that of the toner of Example 1 and being less than the toner of Example 1 in quantity of the release agent that exhales from the toner. As a result, the toner in Example 2 was somewhat inferior to that in Example 1.
[000295] The toner in Example 3, compared to that in Example 1, was formed using the release agent having the lowest complex viscosity η * a. Thus, although a comparable release property is exhibited with that of the toner in Example 1, the amount of release agent that exhales from the toner was large, degrading the film formation and storage stability of hot resistance.
[000296] Also, the amount of release agent that exudes the toner from Example 4 was less than that of the toner from Example 1. As a result, the toner from Example 4 was somewhat less than that of Example 1.
[000297] The toner in Example 5 was formed using the release agent having a smaller ratio (η * b / η * a) between the complex viscosities, so the amount of release agent that exhales from the toner was large and the contamination on the device has been degraded in some way.
[000298] The toner from Example 6 was formed using the release agent having a higher melting point than that of the toner from Example 1, and thus the fixing property was degraded in some way.
[000299] The toner from Example 7 was formed using the release agent having a lower melting point than that of the toner from Example 1. Thus, the toner from Example 7 was found to be excellent in the heat resistance but degraded storage stability in the fixing property and release property.
[000300] The toner from Example 8 was formed using polyester waxes as the release agent. The toner from Example 8 was found to be somewhat degraded in the fixing property, release property and storage stability of hot resistance compared to the toner from Example 1 formed using monoester 1, but exhibits good results with respect to contamination on the device.
[000301] In contrast, the toners in Comparative Examples 1 to 7 have been found to be degraded into either release property, low hold property, heat resistance storage stability, and contamination in the apparatus. In more detail, the toner from Comparative Example 1 was formed using the release agent having a higher viscosity complex η * a than that of the toner in Example 1, and the amount of release agent that exhales from the toner was less, leading to degradation in the release property. Also, in the toner of Comparative Example 2, the molecular state of the release agent in the toner after fixation was unstable and easier to volatilize, resulting in the fact that the contamination in the device was poor. In addition, the toner from Comparative Example 2 has been degraded in the heat resistance storage stability. The toner from Comparative Example 3 was formed using the release agent having a higher melting point than that of the toner from Example 1. The toner from Comparative Example 3 was a practically useful level in terms of device contamination and storage stability, but it has been considerably increased in the minimum fixing temperature due to the release agent with the highest melting point and has also been degraded in the release property. The toner in Comparative Example 4 was formed using the release agent having a lower melting point than that of the toner in Example 1. Although the minimum fixing temperature of the toner in Comparative Example 4 is close to that of the toner in Example 1, the toner from Comparative Example 4 was found to be degraded in storage stability due to the lower melting point release agent. The toner from Comparative Example 5 was formed using paraffin wax and exhibited good release property, fixation property and storage stability of hot resistance. However, the toner releasing agent of Comparative Example 5 was easier to exhale than in the toner of Example 1 and was degraded by contamination in the apparatus. The toner from Comparative Example 6 was formed using microcrystalline wax and exhibited good release property, contamination in the apparatus and storage stability of hot resistance, but was degraded in the fixation property.
[000302] The toner from Comparative Example 7 was formed using polyalkylene wax as the release agent and exhibited good heat resistance storage stability since the polyalkylene wax has a high melting point. However, when polyalkylene wax was used in combination with crystalline polyester resin, it was difficult to obtain a viscoelasticity-reducing effect, leading to degradation in the minimum fixing temperature and release property.
[000303] Aspects of the present invention are as follows. <1> One toner including:
[000304] a binder resin;
[000305] a release agent; and
[000306] a colorant,
[000307] wherein the binder resin contains a crystalline polyester resin and a non-crystalline polyester resin,
[000308] in which the release agent has an endothermic peak temperature of 60 ° C to 80 ° C in the second temperature raising in differential scanning calorimetry, and
[000309] where the release agent is an ester wax that satisfies the following expressions (1) and (2): 1.1 Pa.s <η * to <2.0 Pa.s ... Expression (1 ) 0.001 <η * b / η * a <1.00 ... Expression (2)
[000310] where in Expressions (1) and (2), η * a denotes a complex viscosity (Pa.s) determined by measuring a dynamic viscoelasticity of the release agent at a measurement frequency of 6.28 rad / s, and η * b denotes a complex viscosity (Pa.s) determined by measuring a dynamic viscoelasticity of the release agent at a measurement frequency of 62.8 rad / s. <2> The toner according to <1>, in which the ester wax satisfies the following expressions (1 ') and (2'): 1.2 Pa.sd η * to <1.8 Pa.s .. Expression (1 ') 0.010 d η * b / η * a <0.80 ... Expression (2') <3> The toner according to <1> or <2>, where the endothermic peak temperature at the second temperature increasing in the differential scanning calorimetry 70 ° C to 80 ° C. <4> Toner according to any of <1> to <3>, where the release agent is a monoester wax. <5> The toner according to any of <1> to <4>, in which an amount of the ester wax contained in the toner is 3 parts by weight to 40 parts by weight per 100 parts by weight of the binder resin. <6> Toner according to any one of <l> to <5>, in which the toner is obtained by dispersion in an aqueous medium of an oil phase which is obtained by dissolving or dispersing in an organic solvent of a compound which contains active hydrogen group, a binder resin precursor containing a reactive site with the compound containing active hydrogen group, crystalline polyester resin, colorant and ester wax, to prepare in this way an emulsified dispersion liquid, where the precursor of the binding resin and the compound containing the active hydrogen group are allowed to react, followed by removal of the organic solvent. <7> 0 toner according to any of <1> to <6>, where the crystalline polyester resin has a melting point of 55 ° C to 80 ° C. <8> A developer including:
[000311] the toner according to any of <1> to <7>. <9> An imaging device including:
[000312] an electrostatic imaging support member;
[000313] a charging unit configured to charge a surface of the latent electrostatic image support member;
[000314] an exposure unit configured to expose the charged surface of the latent electrostatic image support member to light, thereby forming an latent electrostatic image;
[000315] a developing unit configured to reveal the latent electrostatic image with a toner, to form a visible image in this way;
[000316] a transfer unit configured to transfer the visible image to a recording medium; and
[000317] a fixation unit configured to fix the visible image transferred in the recording medium,
[000318] where the toner is the toner according to any of <1> to <7>. <10> An imaging method including:
[000319] forming an electrostatic imaging image on an electrostatic imaging support member;
[000320] reveal the latent electrostatic image with a toner, to form a visible image in this way;
[000321] transferring the visible image to a recording medium; and
[000322] fix the visible image transferred in the recording medium,
[000323] where the toner is the toner according to any of <1> to <7>. Reference Signal List 10 Photoconductor drum 18 Image forming unit 20 Loading roller 22 Secondary transfer unit 24 Secondary transfer belt 25 Fixing unit 30 Exposure unit 40 Developing device 50 Intermediate transfer member 52 Loading unit 60 Cleaning unit 70 Charge eliminator lamp 80 Transfer unit 90 Cleaning unit 100A Imaging device 100B Imaging device 110 Process cartridge 120 Developing device set

权利要求:
Claims (10)
[0001]
1. Toner characterized by the fact that it comprises: a binder resin; a release agent; and a colorant, in which the binder resin contains a crystalline polyester resin and a non-crystalline polyester resin, in which the release agent has an endothermic peak temperature of 60 ° C to 80 ° C at the second temperature raising in calorimetry of differential scanning, and the release agent is a monoester wax that satisfies the following expressions (1) and (2): 1.1 Pa.sd η * to <2.0 Pa.s ... Expression (1 ) 0.001 <η * b / η * ad 1.00 ... Expression (2) where in Expressions (1) and (2), η * a denotes a complex viscosity (Pa.s) determined by measuring a dynamic viscoelasticity of the release agent at a measurement frequency of 6.28 rad / s, and η * b denotes a complex viscosity (Pa.s) determined by measuring a dynamic viscoelasticity of the release agent at a measurement frequency of 62.8 rad / s, where dynamic viscoelasticity measurements are performed within - 15 ° C to + 15 ° C of the melting point of the release agent.
[0002]
2. Toner according to claim 1, characterized by the fact that the monoester wax satisfies the following expressions (1 ') and (2'): 1.2 Pa.s <η * to E 1.8 Pa. s ... Expression (1 ') 0.010 <η * b / η * a E 0.80 ... Expression (2')
[0003]
3. Toner according to claim 1 or 2, characterized by the fact that the peak endothermic temperature at the second temperature increases in the differential scanning calorimetry from 70 ° C to 80 ° C.
[0004]
4. Toner according to any one of claims 1 to 3, characterized in that an amount of the monoester wax contained in the toner is 3 parts by weight to 40 parts by weight per 100 parts by weight of the binder resin.
[0005]
5. Toner according to any one of claims 1 to 4, characterized in that the toner is obtained by dispersion in an aqueous medium of an oil phase which is obtained by dissolving or dispersing in an organic solvent a compound containing active hydrogen group, a binder resin precursor containing a reactive site with the compound containing active hydrogen group, crystalline polyester resin, colorant and monoester wax, to prepare in this way an emulsified dispersion liquid, where the precursor of Binder resin and the compound containing the active hydrogen group are allowed to react, followed by the removal of the organic solvent.
[0006]
6. Toner according to any one of claims 1 to 5, characterized in that the crystalline polyester resin has a melting point of 55 ° C to 80 ° C.
[0007]
7. Toner according to any one of claims 1 to 6, characterized in that the monoester wax is synthesized through an esterification reaction between a long-chain fatty acid and a long-chain higher alcohol, in which the long-chain fatty acid is at least one selected from myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid and lignoceric acid, and in which the long-chain upper alcohol is at least one selected from caprylic alcohol, alcohol capric acid, lauryl alcohol, myristyl alcohol, cetyl alcohol, heavy alcohol, arachidyl alcohol, behenyl alcohol and lignoceryl alcohol.
[0008]
8. Developer characterized by the fact that it comprises the toner as defined in any one of claims 1 to 7.
[0009]
9. Imaging apparatus characterized by the fact that it comprises: a latent electrostatic image support member; a charging unit configured to charge a surface of the latent electrostatic imaging support member; an exposure unit configured to expose the charged surface of the latent electrostatic image support member to light, thereby forming an latent electrostatic image; a developing unit configured to reveal the latent electrostatic image with a toner, to form a visible image in this way; a transfer unit configured to transfer the visible image to a recording medium; and a fixation unit configured to fix the visible image transferred in the recording medium, wherein the toner is the toner as defined in any one of claims 1 to 7.
[0010]
10. Image formation method characterized by the fact that it comprises: forming an electrostatic latent image on a member of electrostatic imaging support; reveal the latent electrostatic image with a toner, in order to form a visible image; transferring the visible image to a recording medium; and fixing the visible image transferred to the recording medium, wherein the toner is the toner as defined in any of claims 1 to 7. FIG. 1 100A FIG. 2 WOB FIG. 3

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JP2018151546A|2018-09-27|Toner, developer, toner storage unit, image forming apparatus, and image forming method

同族专利:

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JP2013015673A|2013-01-24|

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KR20140017679A|2014-02-11|

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WO2013005856A1|2013-01-10|

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RU2558009C1|2015-07-27|

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EP2729847A1|2014-05-14|

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CN103765319B|2017-07-28|

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AU2012278584B2|2014-09-04|

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EP2729847A4|2014-12-24|

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BR112014000266A2|2017-02-14|

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JP5628757B2|2014-11-19|

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CA2840881A1|2013-01-10|

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CN103765319A|2014-04-30|

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KR101492363B1|2015-02-10|

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CA2840881C|2016-01-26|

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US20140140731A1|2014-05-22|

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AU2012278584A1|2014-01-30|

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法律状态:
2018-12-11| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2020-01-14| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-06-23| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-07-07| B09W| Correction of the decision to grant [chapter 9.1.4 patent gazette]|Free format text: RETIFIQUE-SE, POR INCORRECOES NO TITULO. |

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2020-11-10| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 03/07/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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JP2011148332A|JP5628757B2|2011-07-04|2011-07-04|Toner, developer, image forming apparatus, and image forming method|

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JP2011-148332|2011-07-04|

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PCT/JP2012/067414|WO2013005856A1|2011-07-04|2012-07-03|Toner, developer, image forming apparatus and image forming method|

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