toner and developer, imaging device, and process cartridge using the same

专利摘要:
TORNER AND REVELATION AGENT, IMAGE FORMATING EQUIPMENT, AND PROCESS CARTRIDGE USING THE SAME. A toner includes a coloring agent, a binder resin comprising a crystalline resin having a urethane skeleton and / or a urea skeleton, and a release agent (a microcrystalline wax). A developing agent, a process cartridge and an imaging device employ the toner to form images in the electrophotographically recording medium.
公开号:BR102012025123B1
申请号:R102012025123-0
申请日:2012-09-24
公开日:2021-01-12
发明作者:Atsushi Yamamoto；Suzuka Amemori；Shinya Nakayama；Hideyuki Santo；Daiki Yamashita；Masahide Yamada
申请人:Ricoh Company, Ltd.；
IPC主号:

专利说明:

[0001] This patent application is based on and claims priority in accordance with 35 USC §119 for Japanese Patent Application No. JP 2011-207195, filed on September 22, 2011, the full disclosure of which is incorporated into this document by reference . BACKGROUND OF THE INVENTION FIELD OF THE INVENTION
[0002] The present invention relates to a toner and a developing agent, an image forming apparatus and a process cartridge using the toner. DESCRIPTION OF THE PREVIOUS TECHNIQUE
[0003] Latent images formed electrically or magnetically are typically made visible by an electrophotographic imaging device using toner (electrophotographic toner).
[0004] For example, in electrophotography, electrostatic images (latent images) are formed on an image-conducting member (typically a photoreceptor) and developed with toner to form visible toner images. The toner image is then transferred onto a transfer medium, typically paper, and then attached to it. In the process in which the toner image is fixed on the transfer medium, a thermal fixation device such as a fixation system with heating cylinders or a heating belt fixing system is generally used for better energy efficiency.
[0005] In recent years, the demand for more energy-efficient imaging devices, which are getting faster and faster, continues to grow. Toner having excellent low temperature setting properties and providing quality images is one of the keys to meeting this demand.
[0006] In order to obtain a toner that has excellent fixation at low temperature, it is required that binder resins forming the toner have low softening temperatures. However, when the softening temperature of the binder resin is low, part of the toner image tends to adhere to the surface of the fixture when fixing the image and transferring the image onto the transfer medium (called an offset, also referred to as hot offset ). In addition, the ability of the toner to withstand high temperatures without decomposition also deteriorates, leading to agglomeration (where the toner particles adhere to one another) under particularly high temperature conditions.
[0007] In addition, there are other problems, such that the toner particles adhere to the interior of the developing device or to transport particles, thereby contaminating the developing device or causing the formation of film on the surface of the imaging member.
[0008] To solve these problems, the use of crystalline resins such as toner binder resins is known. Crystalline resins soften quickly at their melting points so that it is possible to decrease the softening point of the toner around their melting points while ensuring excellent stability at high temperature at melting points or lower temperatures than this. Therefore, such toner can have a good combination of low temperature setting and high temperature stability.
[0009] For example, JP Examined Patent Publication Nos. H04-24702 (JP-H04-24702-A) and JP-H04-24703-A describe toners using crystalline resins elongated from a crystalline polyester by diisocyanate as binding resins. The toners have excellent low temperature fastening properties, but insufficient resistance to hot offset, which is not satisfactory in terms of the level of quality currently required.
[0010] In addition, JP Patent No. 3910338 (JP-3910338-B) describes toner that uses crystalline resins that have an unsaturated bond crosslinked structure containing a sulfonic acid group and can overcome hot offset. In addition, JP Patent Application Publication No. 2010-77419 (JP-2010-77419-A) describes the regulation of the softening point ratio to the peak temperature of melt heating and viscoelasticity to obtain an excellent combination of low temperature fixation and high temperature stability.
[0011] However, toners that have crystalline resins as the main component of their binder resins, although they have excellent impact resistance, also demonstrate poor indentation and scraping hardness. As a consequence, images emitted with these toners are vulnerable to abrasion such as scraping and rubbing.
[0012] JP-3360527-B describes the regulation of the durometer hardness of crystalline resins in the toner and the inclusion of inorganic particles in the toner to improve the stress resistance of the toner. However, the abrasion resistance of the output image is not improved. In addition, the fixation properties worsen due to inorganic particles, thus degrading the crystalline resin's low temperature fixation. SUMMARY OF THE INVENTION
[0013] Briefly, this objective and other objectives of the present invention as hereinafter described will become more readily apparent and can be obtained, either individually or in combination, by a toner containing a coloring agent, a binder resin including a crystalline resin having a urethane structure and / or urea structure, and a release agent comprising a microcrystalline wax.
[0014] It is preferred that, in the toner mentioned above, in a toner diffraction spectrum obtained by X-ray diffraction, the ratio of C / (A + C) is 0.15 or greater, where C represents an integrated intensity of a spectrum deriving from a crystalline structure and A represents an integrated intensity of a spectrum deriving from a non-crystalline structure.
[0015] It is even more preferred that the toner mentioned above contains the binder resin including a crystalline resin having a urethane structure and / or urea structure in an amount of 50% by weight or more.
[0016] It is even more preferred that, in the toner mentioned above, the crystalline resin has a polyurethane resin obtained by elongating and / or cross-linking a diisocyanate or higher compound and a polyester resin.
[0017] It is even more preferred that, in the toner mentioned above, the crystalline resin contains a first crystalline resin and a second crystalline resin having a weight average molecular weight Mw greater than the first crystalline resin.
[0018] It is even more preferred that, in the toner mentioned above, the second crystalline resin is obtained by elongating a modified crystalline resin having an isocyanate group at one end.
[0019] It is even more preferred that, in the toner mentioned above, the second crystalline resin is obtained by elongating a modified crystalline resin that is modified from the first crystalline resin to have a functional group reactive with an active hydrogen group.
[0020] It is even more preferred that the toner mentioned above meets the following ratio: Ws (° C) ≤T (° C) ≤Wp (° C) where T (° C) represents the maximum peak temperature of toner fusion heat measured by a differential scanning calorimeter (DSC), Wp (° C) represents the maximum peak heat of fusion heat of the release agent measured by DSC, and Ws (° C) represents the start of melting temperature defined as the temperature at a tangent intersection for a DSC curve of the release agent measured by DSC at a temperature at which a slope of the curve, which is a negative value, on the side of the lowest temperature of Wp (° C) is maximum and a straight line extrapolating a baseline of the DSC curve of the release agent measured by the DSC.
[0021] It is even more preferred that the toner mentioned above has a penetration rate of 15 or lower at 25 ° C.
[0022] As another aspect of the present invention, a developing agent is provided, which contains a carrier and the toner mentioned above.
[0023] As another aspect of the present invention, an imaging apparatus is provided, which includes an electrostatic imaging conduction member, a charger for charging the surface of the electrostatic imaging conduction member, an irradiator for radiating the surface of the limb of conducting electrostatic imaging with light to form an electrostatic imaging on it, a developing device for developing the electrostatic imaging with the developing agent mentioned above to form a visual image, a transfer device for transferring the visual image to a recording medium for forming a transfer image thereon, and a fixing device for fixing the transfer image on the recording medium.
[0024] As another aspect of the present invention, a process cartridge is provided, which includes a latent electrostatic imaging member for conducting an electrostatic latent image and a developing device for developing the electrostatic latent image with the above developing agent to form a visual image. BRIEF DESCRIPTION OF THE DRAWINGS
[0025] Various other objectives, aspects and accompanying advantages of the present invention will be more fully appreciated as it becomes better understood from the detailed description when considered in connection with the accompanying drawings in which similar reference characters designate corresponding parts entirely and where: figure 1 is a schematic diagram illustrating an example of a two-component developing agent device of the image forming apparatus of the present disclosure; figure 2 is a schematic diagram illustrating an example of the process cartridge of the present disclosure; figure 3 is a schematic diagram illustrating an example of an image forming apparatus employing a tandem system of the present disclosure; figure 4 is an enlarged diagram illustrating each image forming element illustrated in figure 3; figure 5 is a graph illustrating a spectrum of the graph illustrating an example of a diffraction spectrum obtained by measuring X-ray diffraction; and figure 6 is a graph illustrating descriptions for the graph in figure 5. DETAILED DESCRIPTION OF THIS DISCLOSURE
[0026] In the present invention, a toner is provided that has a binder resin that has a crystalline resin that has a urethane structure and / or urea and microcrystalline wax structure serving as a release agent. The reason the images emit using a toner that has crystalline resins like the main binder resins in the toner have poor abrasion resistance is inferred to be that of the lamellar layers in displacing the crystal portion by stress from the outside.
[0027] The introduction of a urethane skeleton and a urea skeleton in the resins, the intermolecular interaction between the lamellar layers thus increases, reducing the displacement of the lamellar layers, resulting in an increase in the hardness of the resins.
[0028] However, it has been found that the hardness of the exit image is not improved sufficiently simply by introducing a urethane skeleton and a urea skeleton, but by a combination of introducing them and using microcrystalline wax as the release agent.
[0029] The microcrystalline wax demonstrates a good dispersion property for the crystalline resin that has a urethane structure and a urea structure and separates the phases quickly from the binder resin during thermal fixation so that the release agent penetrates the surface of the output image sufficiently even in a small amount. Therefore, the surface friction index of the output image deteriorates, which leads to the production of images having excellent abrasion resistance.
[0030] This disclosure is described in detail with reference to the Modalities.
[0031] The toner of the present disclosure contains at least one coloring agent, a binder resin and a release agent. The binder resin contains a crystalline resin having a urethane structure and / or a urea structure. Substantially, the main component of the binder resin is the crystalline resin.
[0032] To maximally demonstrate a good combination of the low temperature fixing property and the high temperature stability by the crystalline resin, the binder resin preferably has the crystalline resin which has a urethane structure and / or a urea structure in an amount of 50% , by weight, or more, more preferably 65% by weight or more, even more preferably 80% by weight or more, and particularly preferably 95% by weight or more.
[0033] When the crystalline resin content is very small, the drastic thermal property of the binder resin is not easily demonstrated on the viscoelasticity of the toner so that it is difficult to have a good combination of fixing properties at low temperature and stability at high temperature.
[0034] In addition, as the binder resins in the toner of the present disclosure other than the crystalline resin that has a urethane structure and / or urea structure, there are crystalline resins other than the crystalline resin that has a urethane structure and / or urea structure and non-crystalline resins.
[0035] There is no specific limitation on the content of binder resin in the toner unless it inhibits aspects of the binder resin. The content of the binder resin in the toner is preferably 50 parts or more, but preferably 70 parts or more, and more preferably 80 parts or more based on 100 parts of toner.
[0036] In addition, it is appropriate in terms of a combination of the fixing property and high temperature stability that the toner has a ratio of C / (A + C) is 0.15 or more, preferably 0.20 or more, more preferably 0 , 30 or more, and particularly preferably 0.45 or more in the toner diffraction spectrum obtained by X-ray diffraction, where "C" represents an integrated intensity of a spectrum derived from the crystalline structure and "A" represents an integrated intensity of a spectrum derived from the non-crystalline structure.
[0037] The diffraction peak attributable to the wax contained in the toner of this disclosure tends to appear at the position of 20 = 23.5 ° to 24 °. However, when the wax content (release agent) in the toner is 15% by weight or less, the contribution of the diffraction peak attributable to the wax is small and, thus, ignitable. When the wax content in the toner is greater than 15% by weight, the integrated intensity C deriving from the crystalline structure is defined as the value obtained to subtract the integrated intensity of the spectrum deriving from the crystalline wax structure from the integrated intensity of the spectrum derived from the crystalline structure.
[0038] The C / (A + C) ratio is an index of the crystalline portion content, which is an area ratio of the main diffraction peak to the halo derived from the crystalline structure in the diffraction spectrum obtained by measuring X-ray diffraction. X-ray diffraction measurement in the present disclosure is conducted by a two-dimensional detector installed on the X-ray diffractometer (D & DISCOVER with GADDS, manufactured by BRUKER CORPORATION).
[0039] The capillary for use in measurement is a wire marker (Lindemann glass) which has a diameter of 0.70 mm). The sample to be measured is filled at the top of the capillary tube. When filling the sample in the tube, the tube is drained 100 times. The detailed measurement conditions are as follows: Tube current: 40 mA Tube voltage: 40 kV 2θ axis of goniometer: 20.0000 ° Axis Ω of goniometer: 0.0000 ° Axis Φ of goniometer: 0.0000 ° Detector distance: 15 cm (wide angle measurement) Measuring range: 3.2≤2θ (°) ≤37.2 Measurement time: 600 s
[0040] A collimator having a pin hole that has a φ of 1 mm is used for the incident optics. The two-dimensional data obtained are integrated with fixed software (with an X axis from 3.2 ° to 37.2 °) to convert into unique dimension data of diffraction intensity and 2θ. The C / A ratio is calculated based on the results of X-ray diffraction measurement as follows.
[0041] Figures 5 and 6 are graphs of an example of a diffraction spectrum obtained by measuring X-ray diffraction. The X axis is 2θ and the Y axis is the X-ray diffraction intensity. Both are linear axes.
[0042] In the X-ray diffraction spectrum in figure 5, there are main peaks (P1 and P2) at 2θ of 21.3 ° and 24.2 ° and halo (h) is seen in a wide range including these two peaks. The main peaks are attributable to the crystalline structure and the halo to the non-crystalline structure.
[0043] These two main peaks and the halo are represented by the Gaussian functions of: fp1 (2θ) = aplexp {- (2θ-bpl) 2 / (2cpl2)} Relationship A1 fp2 (2θ) = ap2exp {- (2θ-bp2) 2 / (2cp22)} Relationship A2 fh (2θ) = ahexp {- (2θ-bh) 2 / (2ch2)} A3 relationship {fp1 (2θ), and fh (2θ) are the functions corresponding to the main peak P1, the main peak P2, and the halo, respectively}.
[0044] The sum of these three functions: f (2θ) = fp1 2θ) + fp2 (2θ) + fh (2θ) Ratio A4 is defined as the adjustment function (illustrated in figure 6) of the entire X-ray spectrum) where the adjustment is made using a less square approach.
[0045] The adjustment variables are nine from ap1, bp1, cp1, ap2, bp2, cp2, ah, bh and ch. As for the initial values to adjust the respective variables, the peak positions of the X-ray diffraction are fixed by bpl, bp2 and bh (bpl = 21.2, bp2 = 24.2, bh = 22.5 in figures 5 and 6) and appropriate values are assigned to the other variables so that two main peaks and the halo match the X-ray diffraction spectrum as close as possible. the adjustment can be conducted, for example, by Solver of Excel 2003, manufactured by MICROSOFT CORPORATION.
[0046] As for the integrated areas (Sp1, Sp2 and Sh) for the Gaussian functions fp1 (2θ) and fp2 (2θ) corresponding to the two main peaks P1 and P2 and the Gaussian function fh (2θ) corresponding to the halo, when (Sp1 + Sp2) is defined as C and Sh is defined as A, the C / A ratio indicating the content index of the crystalline portion can be calculated.
[0047] The crystalline property in the present disclosure represents the characteristic that drastically softens by heat with a ratio (softening temperature to the maximum peak temperature of melting heat) of the softening temperature measured by a flow tester for the maximum peak temperature measured by a differential scanning calorimeter from 0.8 to 1.55 and a resin having this characteristic is defined as the crystalline resin in the present disclosure.
[0048] In addition, the non-crystalline property represents a characteristic that softens slowly by heat with a ratio (softening temperature to the maximum peak temperature) of the softening temperature measured by a flow tester to the maximum peak temperature measured by a differential scanning calorimeter of more than 1.55 and a resin having this characteristic is defined as the non-crystalline resin in the present disclosure.
[0049] The crystalline resin of the present disclosure preferably has a maximum peak melting heat temperature of 45 ° C to 70 ° C, more preferably 53 ° C to 65 ° C, and moreover, preferably from 58 ° C to 62 ° C C in terms of having a good combination of low temperature fastening properties and high temperature stability.
[0050] When the maximum peak temperature is very low, the low temperature fastening property is improved, but the high temperature stability tends to deteriorate. When the maximum peak temperature is very high, high temperature stability is improved, but the low temperature fastening property tends to deteriorate.
[0051] The ratio (the softening temperature to the maximum peak temperature of the melting heat) of the softening temperature to the maximum peak temperature of the crystalline resin is 0.8 to 1.55, preferably 0.85 to 1.25, more preferably from 0.9 to 1.2, and furthermore, preferably from 0.9 to 1.19.
[0052] The resin with this ratio having a small value has a drastic softening characteristic and is excellent in terms of having a good combination of low temperature fastening properties and high temperature stability.
[0053] The softening temperature of the resin and toner can be measured by a flow tester (for example, CFT-500D, manufactured by SHIMADZU CORPORATION) as follows: Pass a load of 1.96 MPa to one gram of a sample resin through a plunger while heating the sample resin to an increasing speed temperature of 6 ° / min to extrude it from a nozzle having a diameter of 1 mm and a length of 1 mm; graph the descending quantity of the plunger of the tester against the temperature; and determining the temperature at which one half of the sample flowed as the softening temperature.
[0054] The maximum peak temperature of the resin melting heat for use in the present disclosure can be measured by a differential scanning calorimeter (DSC) (for example, TA-60W and DSC-60, manufactured by SHIMADZU CORPORATION) as follows: As a preliminary treatment, melt the supplied sample to measure the maximum peak temperature of the heat of fusion at 130 ° C; cool it from 130 ° C to 70 ° C at a drop speed temperature of 1.0 ° C / min; cool it from 70 ° C to 10 ° C at a drop speed temperature of 10 ° C / min; heat the sample by a DSC to a temperature of increasing speed of 20 ° C / min, once to measure the exchange of absorption and heat generation; draw a graph of "amount of absorption and heat generation" and "temperature"; set the observed peak endothermic temperature between 20 ° C to 100 ° C as "Ta *". If there are multiple endothermic peaks, the temperature at which the amount of endotherm is the highest is determined as Ta *; Then, preserve the sample at (Ta * -10) ° C for six hours and at (Ta * -15) ° C for another six hours;
[0055] Then, cool the sample by DSC to 0 ° C to a drop speed temperature of 0.5 ° C / min; heat it to a temperature of increasing speed of 20 ° C / min to measure the exchange of absorption and heat generation. Draw a graph as described above; determine the temperature corresponding to the maximum peak amount of absorption and heat generation as the maximum peak temperature of the heat of fusion.
[0056] With respect to the crystalline resin viscoelasticity, the elastic storage modulus G 'of the crystalline resin a (maximum peak temperature of the heat of fusion + 20 ° C) is preferably 5.0 x 106 Pa.s or less, more preferably 1 , 0 x 101 Pa.sa 5.0 x 105 Pa.s, and moreover, preferably 1.0 x 101 Pa.sa 1.0 x 104 Pa.s.
[0057] The elastic modulus of loss G "of the crystalline resin at (maximum peak temperature of the heat of fusion + 20 ° C) is preferably 5.0 x 106 Pa.s or less, more preferably 1.0 x 101 Pa.sa 5 , 0 x 105 Pa.se, moreover, preferably 1.0 x 101 Pa.sa 1.0 x 104 Pa.s.
[0058] With respect to the viscoelasticity of the toner for use in the present disclosure, the elastic storage module G 'and the elastic loss module G "are preferably in the range of 1.0 x 103 Pa.s to 5.0 x 106 Pa.s in terms resistance to fixation and resistance to hot offset. Considering that the coloring agent and laminated inorganic minerals are dispersed in the binder resin, which leads to an increase in the elastic storage module G "and in the elastic loss module G", the The viscoelasticity of the crystalline resin is preferably in the range specified above.
[0059] The viscoelasticity of the crystalline resin can be obtained, for example, by adjusting the relationship between the crystalline monomer and the non-crystalline monomer constituting the resin and their molecular weight. For example, the elastic storage module G 'of the crystalline resin a (maximum peak temperature of the heat of fusion Ta * + 20 ° C) becomes small as the crystalline monomer ratio increases.
[0060] The characteristic values of dynamic viscoelasticity (the elastic storage module G 'and the elastic drop module G ") of the resin and toner can be measured by a dynamic viscoelasticity measuring device (eg ARES, manufactured by TA INSTRUMENT JAPAN INC.) · The measurement is conducted at a frequency of 1 Hz.
[0061] Mold the sample onto a pellet having a diameter of 8 mm and a thickness of 1 mm to 2 mm. Fix the pellet to a parallel plate having a diameter of 8 mm; stabilize it at 40 ° C, and heat it to a frequency of 1 Hz (6.28 rad / a) with an amount of distortion (mode of amount distortion control) of 0.1% at 200 ° C at an increasing speed temperature of 2.0 ° C for measurement.
[0062] The weight average molecular weight (Mw) of the crystalline resin is preferably from 2,000 to 100,000, more preferably from 5,000 to 60,000, and particularly preferable from 8,000 to 30,000 in view of the fixing property.
[0063] When the molecular weight is very small, the resistance to hot offset tends to deteriorate and when the molecular weight is very large, the fastening property at low temperature tends to deteriorate.
[0064] In the present disclosure, the weight average molecular weight (Mw) of the resin can be measured using a gel permeation chromatography (GC) measuring device (e.g., GPC-8220 GPC, manufactured by TOSOH CORPORATION).
[0065] The column is a 15 cm TSK Super HZM-M gel triplet (manufactured by TOSOH CORPORATION).
[0066] Dissolve the resin to be measured in tetrahydrofuran (THF) (contained stabilizing agent, manufactured by WAKO PURE CHEMICAL INDUSTRIES, Ltd.) to obtain a 0.15% by weight solution followed by filtration with a 0.2 µm filter. Use the filtrate as a sample (THF sample solution).
[0067] Infuse 100 μl of the sample solution in THF inside the measuring instrument under the condition that the temperature is 40 ° C and the flow rate is 0.35 ml / min.
[0068] Calculate the molecular weight of the sample by the relationship between the standard curve logarithmic value made from various types of monodispersed polystyrene standard samples and the count value.
[0069] The standard samples of monodispersed polystyrene are: Showdex STANDARD Std. Nos. S-7300, S-210, S-390, S-875, S-1980, S10.9, S-629, S-3.0, and S- 0.580 manufactured by SHOWA DENKO KK) and toluene.
[0070] A refractive index (RI) detector is used as the detector.
[0071] Any crystalline resin having a urethane structure and / or urea structure that satisfies the conditions is used appropriately. Specific examples thereof include, but are not limited to, polyester resins, polyurethane resin, polyurea resins, and complex resins thereof which have a urethane structure and / or urea structure.
[0072] In particular, polyurethane resins or polyurea resins obtained by the elongation and / or crosslinking reaction of polyester resins and a diisocyanate compound or higher have such excellent hardness that they are preferable in terms of penetration of the release agent into the present disclosure.
[0073] In addition, among polyester resins, straight chain polyester resins and complex resins that contain straight chain polyester resins are preferable in terms of crystallinity.
[0074] Among polyester resins, polycondensed polyester resins synthesized with a diol component and a dicarboxylic acid component are preferable in terms of demonstrating crystallinity. Optionally, tri-alcohol or higher components and carboxylic acid components can be used.
[0075] In addition, among polyester resins, in addition to polycondensed polyester resins, lactone ring-opening polymers and polyhydroxycarboxylic acids are also preferable.
[0076] In addition, resins synthesized from a diol component and dicarboxylic acid component having a urethane structure or a urea structure can be used appropriately as the polyester resin that has a urethane structure and / or an urea resin .
[0077] Among polyurethane resins, polyurethane resins synthesized from a diol component and a diisocyanate component are used appropriately. Optionally, tri-alcohol or higher components and isocyanate components can be used.
[0078] Among polyurea resins, polyurea resins synthesized from a diamine component and a diisocyanate component are used appropriately. Optionally, triamine or higher components and isocyanate components can be used.
[0079] Among polyamide resins, polyamide resins synthesized from a diamine component and a dicarboxylic acid component are appropriately used. Optionally, the triamine components or higher and the carboxylic acid components can be used.
[0080] Next, the alcohol component, the carboxylic acid component, the isocyanate component, and the amine component for use in these crystalline polycondensed polyester resins, crystalline polyurethane resins, crystalline polyamide resins and crystalline polyurea resins are described below .
[0081] As the alcohol component, aliphatic diols are preferable as a polyalcohol component and the number of carbon atoms in the chain is preferably 2 to 36.
[0082] Aliphatic diols are classified into the straight-chain type and the branched-chain type. Straight chain aliphatic diols are preferable.
[0083] Like the diol component, multiple diol components can be used. The content of straight chain type aliphatic diols is preferably 80% per mol or higher, and more preferably 90% per mold or higher based on the total content of the diol component.
[0084] When the diol content is 80 mol% or higher, the crystallinity of the resin is improved, the combination of the low temperature fixing property and the high temperature stability is good, thereby improving the hardness of the resin.
[0085] Specific examples of straight chain type aliphatic diols include, but are not limited to, ethylene glycol, 1,3-propane diol, 1,4-butane diol, 1,5-pentane diol, 1,6-hexane diol, 1 , 6-hexane diol, 1,7-heptane diol, 1,8-octane diol, 1,9-nonane diol, 1,10-decane diol, 1,11-undecane diol, 1,12-dodecane diol, 1, 13-tridecane diol, 1,14-tetradecane diol, 1,18-octadecane diol, and 1,20-eicosano diol. Among these, considering availability, ethylene glycol, 1,3-propane diol, 1,4-butane diol, 1,6-hexane diol, 1,9-nonane diol and 1,10-decane diol are preferable.
[0086] Specific examples of optional diols include, but are not limited to, aliphatic diols having 2 to 36 carbon atoms other than those specified above (for example, 1,2-propylene glycol, butane diol, hexane diol, octane diol, decane diol, dodecane diol, tetradecan diol, neopentyl glycol, and 2,2-diethyl-1,3-propane diol); alkylene ether glycols having 4 to 36 carbon atoms (e.g., diethylene glycol ether glycol, triethylene glycol, dipropylene glycol, Polyethylene glycol, polypropylene glycol, and polytetramethylene; alicyclic diols having 4 to 36 atoms carbon (for example, 1,4-cyclohexane dimethanol and hydrogenated bisphenol); alicyclic diol adducts specified above with 1 mol to 30 moles of alkylene oxide (hereinafter referred to as AO) such as ethylene oxide (hereinafter referred to as EO), propylene oxide (hereinafter referred to as PO), and butylene oxide (hereinafter referred to as BO); bisphenol adducts (for example, bisphenol A, bisphenol F and bisphenol S) with 2 moles a 30 moles of AO (EO, PO, BO, etc .; polylactone diols (e.g., polysaccharolactone diol); and polybutadiene diol).
[0087] In addition, diols having other functional groups can also be used. Specific examples thereof include, but are not limited to, diols having carboxyl groups, diols having sulfonic acid groups or sulfamic acid groups, and salts thereof.
[0088] Specific examples of diols having carboxyl groups include, but are not limited to, dialkylol alkane acid (C6 and C24, for example, 2,2-dimethylol propionic acid (DMPA), 2-dimethylol butane acid, 2,2-dimethylol heptane and 2,2-dimethylol octane acid).
[0089] Specific examples of diols having sulfonic acid groups or sulfamic acid groups include, but are not limited to, sulfamic diols such as [N, N-bis (2-hydroxyalkyl) sulfamate having one to six carbon atoms) and adducts of the same with 1 mol to 6 moles of AO (EO, PO, etc.).
[0090] As neutralizing bases of diols having these groups of neutralizing bases, tertiary amines (e.g., triethyl amine) having 3 to 30 carbon atoms and / or alkali metal (sodium salts) can be specified. Among these, it is preferable to use an alkylene glycol having 2 to 12 carbon atoms, a diol having a carboxyl group, a bisphenol adduct with AO, and a combination thereof.
[0091] Specific examples of optional tri-alcohol or higher components include, but are not limited to, higher aliphatic tripoliols having 3 to 36 carbon atoms (e.g., alkane polyols and dehydrated internal intermolecular compounds thereof, e.g., glycerin, trimethylol ethane , trimethylol propane, pentaerythritol, sorbitol, sorbitan and polyglycerin); sugars and derivatives thereof (for example, sucrose and methyl glycoside); trisphenol adducts (eg triphenol PA) with 2 moles to 30 moles of AO; adducts of novolac resins (for example, phenolic novolac and novolac cresol) with 2 moles to 30 moles of AO; and acrylic polyol copolymers (for example, hydroxyethyl (meth) acrylate copolymers and other vinyl based monomer).
[0092] Among these, aliphatic or higher tripoliols and adducts of novolac resins with AO are preferable adducts of novolac resins with AO are more preferable.
[0093] Preferred specific examples of carboxylic acid components include, but are not limited to, aliphatic dicarboxylic acids and aromatic dicarboxylic acids.
[0094] Aliphatic dicarboxylic acids are classified into the straight chain type and the branched chain type.
[0095] Straight chain type dicarboxylic acids are more preferable.
[0096] Specific examples of dicarboxylic acid include, but are not limited to, alkane dicarboxylic acids having 4 to 36 carbon atoms such as succinic acid, adipic acid, sebacic acid, azelaic acid, dodecane dicarboxylic acid, octadecane dicarboxylic acid and decyl succinic acid; alicyclic dicarboxylic acids having 6 to 40 carbon atoms such as dimeric acid (dimerized linolic acid); dicarboxylic alkene acids having 4 to 36 carbon atoms such as alkenyl succinic acids such as dodecenyl succinic acid, pentadecenyl succinic acid and octadecenyl succinic acid, maleic acid, fumaric acid and citraconic acid; and aromatic dicarboxylic acids having 8 to 36 carbon atoms such as phthalic acid, isophthalic acid, terephthalic acid, t-butyl isophthalic acid, 2,6-naphthalene dicarboxylic acid and 4,4'-biphenyl dicarboxylic acid.
[0097] Specific examples of optional polycarboxylic acids having three or more hydroxyl groups include, but are not limited to, aromatic polycarboxylic acids having 9 to 20 carbon atoms (e.g., trimellitic acid and pyromelitic acid).
[0098] Specific examples of dicarboxylic acid or tri-polycarboxylic acids or higher include, but are not limited to, lower alkyl anhydrides or esters having one to four carbon atoms (e.g., methyl esters, ethyl esters and isopropyl esters) as specified above.
[0099] Among these dicarboxylic acids, it is particularly preferable to use aliphatic dicarboxylic acids (preferably adipic acid, sebacic acid, dodecane dicarboxylic acid, terephthalic acid and isophthalic acid) only. Copolymers of aliphatic dicarboxylic acids and aromatic dicarboxylic acids (preferably isophthalic acid, terephthalic acid, t-butyl isophthalic acid and lower alkyl esters thereof) are also preferred.
[0100] The amount of copolymerized aromatic dicarboxylic acid is preferably 20 mol% or less.
[0101] Specific examples of isocyanate compounds include, but are not limited to, aromatic isocyanates, aliphatic isocyanates, alicyclic isocyanates and aromatic aliphatic isocyanates (among them, for example, aromatic diisocyanates having 6 to 20 carbon atoms, aliphatic diisocyanates having 2 to 18 atoms of carbon, alicyclic diisocyanates having 4 to 15 carbon atoms, aromatic aliphatic diisocyanates having 8 to 15 carbon atoms, modified diisocyanates thereof (modified compounds having an urethane group, an allophanate group, an urea group, a biuret group, an urethane group , a uretimine group, an isocyanulate group and an oxazoline group), and mixtures thereof, where the number of carbon atoms specified above excludes the number of carbon atoms in the NCO group).
[0102] Optionally, higher tri- or isocyanates can be used in combination with them.
[0103] Specific examples of aromatic isocyanates include, but are not limited to, 3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4'- and / or 4,4'-diphenyl methane diisocyanate (MDI), crude MDI (phosgene compound of diamino dimethyl methane (condensed products of formaldehyde and aromatic amine (aniline) or a mixture thereof; mixtures of a small amount of diphenyl methane diamine) example, 5% by weight to 20% by weight) of tri- or higher polyamines), aryl polyisocyanate (PAPI), 1,5-naphthylene diisocyanate, 4.4 ', 4 "-triphenyl methane triisocyanate and m- or p - phenyl sulfonyl isocyanate isocyanate.
[0104] Specific examples of aliphatic isocyanates include, but are not limited to, ethyl diisocyanate, tetramethylene diisocinate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 16,11-undecane triisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate, lysine methyl 2,6-diisocyanate, bis (ethyl 2-isocyanate) fumarate, bis (ethyl 2-isocyanate) carbonate and 2-isocyanatoethyl-2,6-diisocyanate hexanoate.
[0105] Specific examples of alicyclic isocyanates include, but are not limited to, isoformone diisocyanate (IPDI), dicyclohexyl methane-4,4'-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanate) -4-cyclohexene, 1,2-dicarboxylate, 2,5 and / or 2,6-norbornane diisocyanate.
[0106] Specific examples of aromatic aliphatic diisocyanates include, but are not limited to, m- and / or p-xylylene diisocyanate (XDI), a, a, a ', a'-tetramethyl xylylene diisocyanate (TMXDI).
[0107] Specific examples of modified diisocyanate compounds include, but are not limited to, modified compounds having a urethane group, a carbodiimide group, an allophanate group, an urea group, a biuret group, a urethane group, an uretimine group, an isocyanulate group, and an oxazoline group.
[0108] To be specific, there are: modified MDI such as urethane modified MDI, carbodiimide modified MDI, and trihydrocarbyl phosphate modified MDI), modified diisocyanate compounds such as urethane modified TDI, and mixtures thereof such as modified MDI and TDI modified with urethane (isocyanate containing prepolymer).
[0109] Among these, aromatic diisocyanates having 6 to 15 carbon atoms, aliphatic diisocyanates having 4 to 12 carbon atoms, alicyclic diisocyanates having 4 to 15 carbon atoms are preferable. Where the number of carbon atoms excludes the number of carbon atoms in the NCO group. Among these, TDI, MDI, HDI, hydrogenated MDI and IPDI are particularly preferable.
[0110] Specific examples of the amine component include, but are not limited to, aliphatic amines and aromatic amines. Among these, aliphatic diamines having 2 to 18 carbon atoms and aromatic diamines having 6 to 20 carbon atoms are appropriate. Optionally, tri-amines or higher can be used.
[0111] Specific examples of aliphatic diamines having 2 to 18 carbon atoms include, but are not limited to, alkylene diamines such as ethylene diamine, propylene diamine, trimethylene diamine, tetramethylene diamine and hexamethylene diamine, polyalkylene diamine having 4 to 18 carbon atoms such as diethylene triamine, iminobis propyl amine, bis (hexamethylene) triamine, triethylene tetramine, tetraethylene pentamine and pentaethylene hexamine; compounds substituted therefor with an alkyl having 1 to 4 carbon atoms or a hydroxy alkyl having 2 to 4 carbon atoms such as dialkyl aminopropyl amine, trimethyl hexamethylene diamine, aminoethyl ethanol amine, 2,5-dimethyl-2,5-hexamethylene diamine and methyl iminobispropyl amine; alicyclic or aliphatic heterocyclic diamines such as alicyclic diamine having 4 to 15 carbon atoms such as 1,3-diamino cyclohexane, isophorone diamine, mentene diamine, 4,4'-methylene dicyclohexane diamine (hydrogenated methylene dianiline and heterocyclic diamine having 4 to 15 carbon atoms such as piperazine, N-aminoethyl piperazine, 1,4-diaminoethyl piperazine, 1,4-diaminoethyl piperazine, 1,4-bis (2-amino-2-methylpropyl) piperazine, 3,9-bis (3- aminopropyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, and aromatic aliphatic amines having 8 to 15 carbon atoms such as xylylene diamine, tetrachlor-p-xylylene diamine.
[0112] Specific examples of aromatic diamines having 6 to 20 carbon atoms include, but are not limited to, unsubstituted aromatic diamines such as 1,2-, 1,3- or 1,4-phenylene diamine, 2,4'- or 4.4 '-diphenyl methane diamine, crude diphenyl methane diamine (polyphenyl polymethylene polyamine), diaminodiphenyl sulfone, benzidine, thiodianiline, bis (3,4-diaminophenyl) sulfone, 2,6-diaminopylidine; m-aminobenzyl amine; triphenyl methane-4,4 ', 4 "-triamine, and naphthylene diamine; aromatic diamines having a nuclear substitution alkyl group having one to four carbon atoms such as 2,4- or 2,6-tolylene diamine, crude tolylene diamine , diethyl tolylene diamine, 4,4'-bis (o-toluidine), dianisidine, diamino ditholyl sulfone, 1,3-dimethyl-2,4-diaminobenzene, 1,3-dimethyl-2,6-diaminobenzene, 1,4 -diisopropyl-2,5-diamino benzene, 2,4-diamino mesitylene, 1-methyl-3,5-diethyl-2,4-diamino benzene, 2,3-dimethyl-1,4-diamino naphthalene, 2,6 -dimethyl-1,5-diamino naphthalene, 3,3 ', 5,5'-tetramethyl bendizine, 3,3', 5,5'-tetramethyl-4,4'-diamino diphenyl methane, 3,5-diethyl- 3'-methyl-2 ', 4-diamino diphenyl methane, 3,3'dietyl-2,2'-diaminodiphenyl methane, 4,4'-diamino-3, 3'-dimethyl diphenylmethane, 3, 3', 5, 5'-tetraethyl-4,4'-diaminobenzophenone, 3,3 ', 5,5'-tetraethyl-4,4'-diaminodiphenyl ether, 3,3', 5,5'-tetraisopropyl-4,4'-diaminophenyl sulfone; mixtures of isomers thereof with various ratios; aromatic diamines having a group of ex nuclear substitution electron traction (such as Cl, Br, I and F), alkoxy groups such as methoxy group and ethoxy group, and nitro group) such as methylene bis-o-chloroaniline, 4-chlor-o-phenylene diamine, 2-chlor-1,4-phenylene diamine, 3-amino-4-chloroaniline, 4-bromo-1,3-phenylene diamine, 2,5-dichlor-1,4-phenylene diamine, 5-nitro-1,3 -phenylene diamine, 3-dimethoxy-4-aminoaniline, 4,4'-diamino-3,3'-dimethyl-5,5'-dibromo-diphenyl methane, 3,3'-dichlorobenzidine, 3,3'-dimethoxy benzidine , bis (4-amino-3-chlorophenyl) oxide, bis (4-amino-2-chlorophenyl) propane, bis (4-amino-2-chlorophenyl) sulfone, bis (4-amino-3-methoxyphenyl) decane, bis (4-aminophenylsulfide, bis (4-aminophenyl) telluride, bis (4-aminophenyl) selenide, bis (4-amino-3-methoxyphenyl) disulfide, 4,4'-methylene bis (2-iodoaniline), 4.4 ' -methylene bis (2-bromoaniline), 4,4'-methylene bis (2-fluroaniline), 4-aminophenyl-2-chloroaniline); aromatic diamines having a secondary amino group such as the unsubstituted aromatic diamines specified above, aromatic diamines having a nuclear substitution alkyl group having one to four carbon atoms, mixtures of isomers thereof with various mixing ratios, compounds in which part or the entire primary amino group of aromatic diamines having a nuclear substituted electron extraction group specified above is replaced with a lower alkyl group such as methyl group and ethyl group to be a tertiary amino group, 4-4'-di (methylamino ) diphenyl methane, and 1-methyl-2-methylamino-4-aminobenzene.
[0113] In addition to these, specific examples of diamines include, but are not limited to, polyamide polyamines (polyamide polyamines of low molecular weight obtained by condensation of dicarboxylic acid (eg dimeric acid) and excess polyamines (2 moles or more per mole of the acid (for example, alkylene diamines and polyalkylene diamines specified above) and hydrogenated polyether compounds cyanoethylated polyamines (for example, polyether polyols such as polyalkylene glycol).
[0114] Lactone-opening polymers such as polyester resin can be obtained, for example, by polymerizing with a ring-opening a lactone such as a monolactone (the number of ester groups is one in the ring) having 3 to 12 carbon atoms such as β -propiolactone, λ-butyl lactone, δ-valero lactone and ε-capro lactone using a catalyst such as a metal oxide and an organic metal compound.
[0115] Among these, ε-capro lactone is preferable in terms of crystallinity.
[0116] In addition, lactone ring-opening polymers having a hydroxyl group at their end obtained by ring-polymerizing the lactones specified above using a glycol (e.g., ethylene glycol and diethylene glycol) as an initiator are suitable. Also, the end can be modified to be a carboxyl group.
[0117] Products available on the market can also be used. These are, for example, high crystalline polycapro lactones such as PLACCEL series H1P, H4, H5 and H7 (manufactured by DAICEL CORPORATION).
[0118] Polyhydroxy carboxylic acids such as polyester resins are obtained by direct dehydrocondensation of hydroxycarboxylic acid such as glycolic acid, lactic acid (L, D and racemic forms). However, it is preferable to obtain them by opening the cyclic ester ring (the number of ester groups in the ring is two or three) having 4 to 12 carbon atoms corresponding to a dehydrocondensed compound of two or three intermolecules of such a hydroxycarboxylic acid as glycolide and lactide (L, D and racemic forms) with a catalyst such as a metal oxide and an organic metal compound in terms of controlling molecular weight.
[0119] Among these, the preferred cyclic esters are L-lactide and D-lactide in light of crystallinity.
[0120] In addition, these polyhydroxycarboxylic acids which are modified to have a hydroxy group or a carboxyl group at the end are also suitable.
[0121] Block resins having both crystalline and non-crystalline moieties are suitable as the crystalline resin of the present disclosure. The crystalline resins specified above can be used for the crystalline moieties.
[0122] As resins for use in forming the non-crystalline moieties, specified examples thereof include, but are not limited to, polyester resins, polyurethane resins, polyurea resins and polyamide resins.
[0123] The composition of these non-crystalline portions is the same as that of the crystalline portion. Specific examples of monomer for use include, but are not limited to, the diol components specified above, the dicarboxylic acid components specified above, the diisocyanate components specified above, and the diamine components specified above. Any combination of them that can form a non-crystalline resin is appropriate.
[0124] The crystalline resins of the present invention may contain a crystalline resin obtained by the elongation or cross-linking reaction during granulation in an aqueous medium using a modified crystalline resin having a functional group reactive with an active hydrogen group as a precursor to the binding resin. The crystalline resins specified above can be used as the modified crystalline resin.
[0125] The modified crystalline resin can increase its molecular weight by reacting with a resin having an active hydrogen group or a compound such as a crosslinking agent or a stretching agent having an active hydrogen group during the toner manufacturing process.
[0126] There is no specific limit for the reactive functional group with an active hydrogen group.
[0127] Specific examples thereof include, but are not limited to, functional groups such as an isocyanate group, an epoxy group, a carboxylic acid group and an acid chloride group. Among these, an isocyanate group is preferable in terms of the reaction property and stability.
[0128] Specific examples of modified crystalline resins include, but are not limited to, crystalline polyester resins, crystalline polyurethane resins, crystalline polyurea resins and crystalline polyamide resins that have the functional group specified above reactive with an active hydrogen group.
[0129] There is no specific limitation for compounds such as the resin specified above having a hydrogen group and the crosslinking agent or elongation agent specified above having an active hydrogen group and any compound having an active hydrogen group is appropriately used.
[0130] When the functional group specified above reactive with an active hydrogen group is isocyanate group, the active hydrogen group is hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), amino group, carboxyl group, mercapto group, etc. Amines are preferable in terms of reaction speed.
[0131] A resin obtained by reacting the modified crystalline resin having an isocyanate group at the end with an amine becomes a crystalline resin having a urethane structure and / or urea structure.
[0132] There is no specific limitation for amines. Specific examples thereof include, but are not limited to, phenylene diamine, diethyl toluene diamine, 4,4'-diamino diphenyl methane, 4,4'-diamino-3,3'-dimethyldicyclohexyl methane, cyclohexane diamine, isophorone diamine, ethylene diamine, tetramethylene diamine, hexamethylene diamine, diethylene triamine, triethylene tetramine, ethanol amine, hydroxyethyl aniline, aminoethyl mercaptan, aminopropyl mercaptan, amino propionic acid and amino capronic acid.
[0133] In addition, ketimine compounds and oxazolidine compounds in which these amino groups are blocked with ketones (acetone, methyl ethyl ketone and methyl isobutyl ketone) are also suitable.
[0134] The crystalline resin in the present disclosure preferably has a first crystalline resin and a second crystalline resin having a higher average molecular weight (Mw) than that of the first crystalline resin.
[0135] By transmitting the low temperature fixing property for the first crystalline resin and the hot offset resistance for the second crystalline resin, the two competing characteristics can be functionally separated so that the toner having a wide temperature range with respect to the fixation can be obtained.
[0136] In addition, the second crystalline resin is preferably a resin obtained by elongating the modified crystalline resin that has an isocyanate group. This is advantageous to form a crystalline resin that has a high molecular weight in the binder resin.
[0137] The second crystalline resin is preferably a resin obtained by elongating a modified crystalline resin having a functional group reactive with an active hydrogen group prepared by modifying the first crystalline resin.
[0138] The second crystalline resin is finely dispersed evenly in the binder resin so that a toner having an excellent combination of low temperature fastening properties and resistance to hot offset is obtained.
[0139] The weight average molecular weight of the first crystalline resin is preferably from 2,000 to 100,000, more preferably from 5,000 to 60,000, and particularly preferable from 8,000 to 30,000 in light of the fixing property.
[0140] When the molecular weight is very small, the hot offset resistance tends to deteriorate and when the molecular weight is very large, the low temperature fastening property tends to deteriorate.
[0141] The weight average molecular weight of the second crystalline resin is preferably greater than that of the first crystalline resin and preferably from 10,000 to 1,000,000, more preferably from 30,000 to 1,000,000, and particularly preferably from 50,000 to 500,000 in light of the resistance to offset hot.
[0142] When the molecular weight is very small, the resistance to hot offset tends to deteriorate and when the molecular weight is very large, the fastening property at low temperature tends to deteriorate.
[0143] Any binder resin can be used in the present disclosure. The crystalline resin and the non-crystalline resin can be used in combination.
[0144] There is no specific limit for non-crystalline resin. Any resin that has a non-crystalline property can be used appropriately.
[0145] Specific examples thereof include, but are not limited to, styrene monopolymers and substituted styrene polymers such as polystyrene, and polyvinyl toluene; styrene copolymers such as styrene-p-chloro-styrene copolymers, styrene-propylene copolymers, styrene-vinyl-vinyl copolymers, methyl styrene-acrylate copolymers, ethyl styrene-acrylate copolymers, copolymers -methyl methacrylate, copolymers of styrene-ethyl methacrylate, copolymers of styrene-butyl methacrylate, copolymers of styrene-a-methyl chloromethacrylate, styrene-acrylonitrile copolymers, styrene-vinyl copolymers, styrene-vinyl copolymers, methyl ketone, styrene-butadiene copolymers, styrene-isopropyl copolymers, and styrene-maleic acid copolymers, other resins such as polymethyl methacrylate resins, polybutyl methacrylate resins, polyvinyl chloride resins, resins , Polyethylene resins, polyester resins, polyurethane resins, epoxy resins, polyvinyl butyral resins, p resins oliacrylic, rosin resins, modified rosin resins, terpene resins, phenolic resins, aliphatic or aromatic hydrocarbon resins, and aromatic petroleum resins, and modified resins to have a reactive functional group with an active hydrogen group. These resins can be used alone or in combination.
[0146] The binder resin precursor in the present disclosure represents monomers or oligomers that form the binder resin specified above, the modified resins specified above to have a functional group reactive with an active hydrogen group, and compounds including oligomers that can lead to the elongation reaction or crosslinking reaction. Any crystalline resin or non-crystalline resin is appropriate.
[0147] The release agent in the present disclosure is limited to microcrystalline wax. Microcrystalline wax is a type of petroleum wax separated and refined from the reduced distillation residue of crude oil and a release agent containing isoparaffin and cycloparaffin in a large amount in addition to normal paraffin.
[0148] Microcrystalline wax has an excellent dispersion property for the crystalline resin for use in the present disclosure and quickly penetrates into the surface of a fixed image to cover its surface when the toner is thermally fused so that the obtained image has a excellent abrasion resistance.
[0149] There is no specific limit to the maximum peak temperature of the microcrystalline wax melting heat. The maximum peak temperature is usually 55 ° C to 90 ° C, preferably 60 ° C to 80 ° C, and particularly preferably 60 ° C to 70 ° C.
[0150] A maximum peak temperature that is very low tends to have an adverse impact on the hardness and high temperature stability of the toner. A maximum peak temperature that is too high tends to degrade the penetrating property of the release agent during fixation, thereby reducing the advantage of the present disclosure.
[0151] The maximum peak temperature T (° C) of the toner fusion heat of the present disclosure, the maximum peak temperature Wp (° C) of the heat of fusion of the release agent, and the start temperature of fusion Ws (° C ) of the release agent can be measured by a differential scanning calorimeter (DSC) (for example, TA-60W and DSC-60, manufactured by SHIMADZU CORPORATION.
[0152] Sample supplied for measurement is heated from 0 ° C to 150 ° C at an increasing speed temperature of 10 ° C / min, then cooled to 0 ° C at a falling speed temperature of 10 ° C / min, and heated again from 0 ° C at an increasing speed temperature of 10 ° C / min, to obtain a DCS curve (according to DSC). From the curve, the temperature corresponding to the maximum peak amount of heat absorption is determined as the maximum peak temperature T or Wp of the heat of fusion.
[0153] In addition, the melting initiation temperature Ws (° C) of the release agent is defined in the second DSC curve of the release agent as the temperature at the intersection of the tangent at the temperature at which the slope of the curve (slope is a negative value ) is maximum and the straight line extrapolating the baseline on the side of the lower temperatures than the maximum peak temperature Wp of the amount of heat absorption.
[0154] The maximum peak temperature T (° C) of the toner fusion heat of the present disclosure, the maximum peak temperature Wp (° C) of the heat of fusion of the release agent, and the start fusion temperature Ws (° C ) of the heat of fusion of the release agent preferably satisfy the following ratio: Ws≤T≤Wp.
[0155] Satisfying the ratio, the release agent effectively penetrates into the surface at the same time as the toner melts, resulting in improved abrasion resistance of the output image.
[0156] The release agent preferably has a melt viscosity of 5 cps to 1,000 cps and more preferably 10 cps to 100 cps at a temperature 20Â ° C higher than the melting point of the wax (release agent).
[0157] When the melt viscosity is very low, the release property can deteriorate. When the melt viscosity is very high, the effect of improved resistance to hot offset and the fastening property at low temperature can be reduced.
[0158] There is no specific limitation for the difference (Wp-Ws) (° C) between the maximum peak temperature Wp (° C) of the heat of release agent fusion and the start temperature of melting Ws (° C) of the heat melting agent.
[0159] The difference is usually 40 ° C or less, preferably from 10 ° C to 30 ° C, and particularly preferably from 10 ° C to 20 ° C.
[0160] When the difference is very large, the penetrating property of the release agent tends to deteriorate.
[0161] The degree of penetration (needle) of the release agent at 25 ° C is preferably 20 or less and particularly preferably 15 or less in terms of toner hardness.
[0162] In addition, the degree of penetration in the present disclosure can be measured by a method regulated in JIS K 2235 5.4.
[0163] The penetration value is ten times the length (mm) of the needle that has penetrated vertically. There is no specific limitation on the release agent content in the toner. For example, the content is preferably from 2% by weight to 15% by weight and more preferably from 4% by weight to 10% by weight.
[0164] When the content is very small, the abrasion resistance of the output image is not easily improved. When the content is very high, the hardness, the stability at high temperature, and the fluidity of the toner tends to deteriorate.
[0165] There is no specific limitation for coloring agents and any known dyes and pigments can be used appropriately. Specific examples thereof include, but are not limited to, carbon black, nigrosine dyes, black iron oxide, Yellow Naphthol S, Hansa Yellow (10G, 5G and G), Yellow Cadmium, yellow iron oxide, loess, yellow chromium , Yellow Titan, yellow polyazole, Yellow Oil, Yellow Hansa (GR, A, RN and R), Pigment Yellow L, Yellow Benzidine (GE GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G and R), Tartrazine Lago , Lake Yellow Quinoline, Yellow Anthrax BGL, yellow isoindolinone, red iron oxide, red tip, orange tip, red cadmium, cadmium red, antimony orange, Permanent Red 4R, Permanent Red 4R, Red Faise, p-chloro-o- red nitroaniline, Lithol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL and F4RH), Fast Scarlet VD, Vulcan Fast Rubine B, Brilliant Scarlet G, Lithol Rubine GX, Permanent Red F5R , Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, BON Maroon Light, BON Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarine Lake, Red Uncle Indigo B, Tioindigo Maroon, Red Oil, Red Quinacridone, Pyrazolone Red, Red Polyazole, Chrome Vermilion, Orange Benzidine, Orange Perinone, Orange Oil, Cobalt Blue, Cerulean Blue, Alkali Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal-free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS and BC), Indigo, oversea, Prussian blue, Anthraquinone blue, Fast Violet B, Methyl Violet Lake, cobalt violet, manganese violet, dioxane violet, Anthraquinone violet, Chrome green, Zinc green, chromium oxide, viridian, emerald green, Pigment Green B, Naphthol Green B, Gold Green, Acid Green Lake, Malachite Green Lake, Phthalocyanine Green, Anthraquinone Green, titanium oxide, zinc oxide, lithopone, and the like. These can be used alone or in combination.
[0166] There is no specific limitation for the color selection of the coloring agent. Pigments for black and color pigments can be used. These can be used alone or in combination.
[0167] Specific examples of black pigments include, but are not limited to, carbon black (CI Pigment Black 7) such as oven black, lamp black, acetylene black, and channel black, metals such as copper, iron (C. OI.Pigment Black 11), and titanium oxides and organic pigments such as aniline black (CI Pigment Black 1).
[0168] Specific examples of pigments for magenta include, but are not limited to, CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 , 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 48: 1, 49, 50, 51, 52, 53, 53: 1, 54, 55 , 57, 57: 1, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 163, 177, 179, 202, 206, 207, 209 , and 211; C.I. Pigment Violet 19; C.I.Vat Red 1, 2, 10, 13, 15, 23, 29, and 35.
[0169] Specific examples of pigments for cyan include, but are not limited to C.I. Pigment Blue 2, 3, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 60; Vat Blue 6; C.I. Acid Blue 45; copper phthalocyanine pigments in which one to five phthalimidomethyl groups are replaced in the phthalocyanine structure; and Green 7 and Green 36.
[0170] Specific examples of yellow pigments include, but are not limited to CI Pigment Yellow 0-16, 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 55, 65, 73, 74, 83, 97, 110, 151, 154, 180; C.I. Vat Yellow 1, 3, and 20; and Orange 36.
[0171] There is no specific limit on the amount of coloring agent in the toner. The content is preferably from 1% by weight to 15% by weight and more preferably from 3% by weight to 10% by weight.
[0172] When the coloring agent content is very small, the coloring performance of the toner tends to deteriorate. Conversely, when the coloring agent content is very large, the pigment dispersion in the toner tends to be weak, thereby degrading the coloring performance and electrical characteristics of the toner.
[0173] The coloring agent and resin can be used in combination as a master batch.
[0174] There is no specific limitation for the resin and any known resin can be appropriately selected. Specific examples thereof include, but are not limited to, styrene or substituted polymers thereof, styrene-based copolymers, polymethyl methacrylate resins, polybutyl methacrylate resins, polyvinyl chloride resins, polyvinyl acetate resins, Polyethylene resins, polypropylene resins, polyester resins, epoxy resins, polyol epoxy resins, polyurethane resins, polyamide resins, polyvinyl butyral resins, polyacrylic resins, rosin, modified rosin, terpene resins, aliphatic hydrocarbon resins, alkyd hydrocarbon resins , aromatic petroleum resins, chlorinated paraffin, and paraffin. These can be used alone or in combination.
[0175] Specific examples of styrene-based copolymers or styrene-substituted polymers include, but are not limited to polyester resins, polystyrene resins, poly (p-chloro-styrene) resins, and polyvinyl toluene resins.
[0176] Specific examples of styrene-based copolymers include, but are not limited to, styrene-p-chloro-styrene copolymers, styrene-propylene copolymers, styrene-vinyl-vinyl copolymers, styrene-vinylnaphthalene copolymers, styrene-acrylate copolymers, styrene-acrylate copolymers. ethyl styrene-acrylate, styrene-butyl acrylate copolymers, octyl styrene-acrylate copolymers, methyl styrene-methacrylate copolymers, ethyl styrene-methacrylate copolymers, styrene-methacryl copolymers, styrene-methacrylate copolymers, α-methyl chloromethacrylate, styrene-acrylonitrile copolymers, styrene-vinyl methyl ketone copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-acrylonitrile-indene copolymers and styrene-copolymers -maleic acid ester. These master batches can be the crystalline resins of the present disclosure.
[0177] The master batch is prepared by mixing and kneading the resin for the master batch resin mentioned above and the coloring agent mentioned above when applying high shear stress to it. In this case, an organic solvent can be used to reinforce the interaction between the coloring agent and the resin.
[0178] In addition, so-called washing methods and a wet cake of the coloring agent can be used as is, which is advantageous in that there is no need for drying.
[0179] The washing method is a method in which a water paste containing water from a coloring agent is mixed or kneaded with an organic solvent and the coloring agent is transferred to the resin side to remove water and the solvent component organic.
[0180] High-shear dispersing devices such as three-roller mill, etc. can be used for mixing or kneading.
[0181] The toner of the present disclosure may contain a charge control agent, an external additive, and other components in addition to the binder resin, the coloring agent, and the release agent as long as these do not have an adverse impact on the present disclosure.
[0182] There is no specific limitation for the selection of any load control agent, any load control agent can be used appropriately. However, colorless or white materials are preferable because colored materials can have an impact on the colorant. Specific examples of charge control agent include, but are not limited to, triphenylmethane dyes, molybdic acid chelate pigments, Rhodamine dyes, alkoxamines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus and compounds including phosphorus, tungsten and compounds including tungsten, fluorine containing activators, metal salts of salicylic acid, and metal salts of salicylic acid derivatives. These can be used alone or in combination.
[0183] Commercially available load control agents can be used.
[0184] Specific examples thereof include, but are not limited to, BRONTON P-51 (quaternary ammonium salt), E-82 (oxynaphonic acid metal complex), E-84 (salicylic acid metal complex), and E-89 (phenolic condensation product), which are manufactured by ORIENT CHEMICAL INDUSTRIES CO., LTD .; TP-302 and TP-415 (quaternary ammonium salt molybdenum complex), which are manufactured by HODOGAYA CHEMICALl CO., LTD .; COPY CHARGE PSY VP2038 (quaternary ammonium salt), COPY BLUE PR (derived from triphenyl methane), COPY CHARGE NEG VP2036 and NX VP434 (quaternary ammonium salt), which are manufactured by HOECHST AG; LRA-901, and LR-147 (boron complex), which are manufactured by JAPAN CARLIT CO., LTD .; quinacridone, azo pigments and polymers having a functional group such as a sulfonate group, a carboxyl group, and a quaternary ammonium group.
[0185] The charge control agent can be dissolved and / or dispersed after being melted, mixed and kneaded with the master batch. Alternatively, the charge control agent can be added together with each toner component when dissolving and / or dispersing these. Also, the charge control agent can be attached to the surface of the toner after making the toner particles.
[0186] The content of charge control agent in the toner depends on the type of binder resin, presence of additives, and dispersion method so that it is not simply regulated, but, for example, it is preferably from 0.1 part by weight to 10 parts by weight and more preferably from 0.2 parts by weight to 5 parts by weight based on 100 parts by weight of binder resin.
[0187] When the content is very low, the charge control property is not easily achieved. When the content is too high, the toner tends to have an overcharging capacity, thereby increasing the strength of the electrostatic attraction with the developing drum and attracting deterioration in the fluidity of the toner and a decrease in image density.
[0188] There is no specific limitation for external additives and any known external additives can be used appropriately.
[0189] Specific examples thereof include, but are not limited to, silica particles, hydrophobic silica, aliphatic acid metal salts (such as zinc stearate and aluminum stearate); metal oxides (such as titania, alumina, tin oxide, and antimony oxide), and fluoropolymers.
[0190] Among these, hydrophobic silica particles, hydrophobic titania particles, hydrophobic titanium oxide particles, and hydrophobic alumina particles are preferable.
[0191] Specific examples of silica particles include, but are not limited to HDK H 2000, HDK H 2000/4, HDK H 2050 EP, HVK21, HDK H 1303, (all manufactured by HOECHST AG), R972, R974, RX200, RY200, R202, R805, and R812 (manufactured by NIPPON AEROSIL CO., LTD.).
[0192] In addition, specific examples of titania particles include, but are not limited to, P-25 (manufactured by NIPPON AEROSIL CO., LTD.), STT-30 and STT-65C-S (manufactured by TITAN KOGYO, LTD.) , TAF-140 (manufactured by FUJI TITANIUM INDUSTRY CO., LTD.), And MT-150W, MT-500B, MT-600B, and MT-150A (manufactured by TAYCA CORPORATION).
[0193] Among these, specific examples of hydrophobic titanium oxide particulates include, but are not limited to T-805 (manufactured by NIPPON AEROSIL CO., LTD.), STT-30A and STT-65S-S (manufactured by TITAN KOGYO, LTD .), TAF-500T and TAF-1500T (manufactured by FUJI TITANIUM INDUSTRY CO., LTD.), MT-100S and MT-100T (manufactured by TAYCA CORPORATION), and IT-S (manufactured by ISHIHARA SANGYO KAISHA LTD.) .
[0194] Hydrophobic oxide particles, hydrophobic silica particles, hydrophobic titania particles and hydrophobic alumina particles can be obtained by treating the hydrophilic particles with a silane coupling agent such as methyl trimethoxysilane, methyltriethoxy silane and octyl trimethoxysilane.
[0195] Oxide particulates treated with silicon oil and inorganic particulates, which are optionally treated with heated silicone oil, are also preferable.
[0196] Specific examples of silicone oils include, but are not limited to, dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methylhydrogen silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, polyether modified silicone oil, alcohol modified silicone oil, amino modified silicone oil, epoxy modified silicone oil, epoxy / polyether silicone oil, phenol modified silicone oil, carboxyl modified silicone oil, oil mercapto-modified silicone oil, (meth) acrylic modified silicone oil, and α-methylstyrene modified silicone oil.
[0197] Specific examples of such inorganic particles include, but are not limited to, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, oxide tin, quartz sand, clay, mica, lime, diatomaceous earth, chromium oxide, cerium oxide, red iron oxide, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, carbonate calcium, silicon carbide, and silicon nitride. Among these, silica and titanium dioxide are particularly preferred.
[0198] The external additive content is preferably 0.1 wt% to 5 wt% and more preferably 0.3 wt% to 3 wt% based on the toner.
[0199] The inorganic particulate preferably has an average primary particle diameter of 100 nm or less and more preferably 3 nm to 70 nm.
[0200] When the average primary particle diameter is very small, the inorganic particles are embedded in the toner, thereby inhibiting aspects of it.
[0201] When the average primary particle diameter is very large, the image-carrying member is easily damaged non-uniformly.
[0202] Inorganic particles and hydrophobic inorganic particles can be used in combination with external additives.
[0203] The hydrophobic particulates preferably have an average primary particle diameter of 1 nm to 100 nm and more preferably contain at least two types of inorganic particles having an average primary particle diameter of 5 nm to 70 nm.
[0204] In addition, external additives preferably contain at least two types of inorganic particulates having an average primary particle diameter of 20 nm or less and at least one type of inorganic particulate having an average primary particle diameter of 30 nm or more.
[0205] In addition, the specific surface area of such inorganic particles measured by the BET method is preferably from 20 m2 / g to 500 m2 / g.
[0206] Specific examples of surface treatment agents for external additives containing oxide particulates include, but are not limited to, silane coupling agents such as dialkyl dihalogenated silane, trialkyl halogenated silane, trihalogenated alkyl silane and hexyl alkyl disilazane; silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, coupling agents containing aluminum, silicone oil and silicone varnish.
[0207] Resin particles can be added as external additives.
[0208] Specific examples thereof include, but are not limited to, polystyrene prepared by a soap-free emulsion polymerization method, a suspension polymerization method, or a dispersion polymerization method; and methacrylic acid copolymers and esters and acrylic acid esters; polycondensation resins such as silicone resins, benzoguanamine resins and nylon resins, and particles polymerized by a thermosetting resin.
[0209] By use in combination with such resin particles, the toner loading capacity is improved, thereby reducing the inversely loaded toner, resulting in a decrease in background dirt.
[0210] The resin particulate content is PV of 0.01% by weight to 5% by weight, and more preferably 0.1% by weight to 2.0% by weight, based on toner.
[0211] There is no specific limitation for the other components.
[0212] Specific examples thereof include, but are not limited to, a fluidity enhancer, a cleaning property enhancer, a magnetic material and metal soap.
[0213] The fluidity enhancer is prepared by surface treatment to improve the hydrophobic property and prevent deterioration of fluidity and load capacity even in a high humidity environment.
[0214] Specific examples of fluidity enhancer include, but are not limited to, silane coupling agents, silylating agents, silane coupling agents including an alkyl fluoride group, organic titanate coupling agents, coupling agents containing aluminum, oil silicone and modified silicone oil.
[0215] The cleaning property enhancer is added to the toner to remove the remaining developing agent on the image driving member or an intermediate transfer element after transferring an image. Specific examples thereof include, but are not limited to, zinc stearate, calcium stearate and aliphatic metal salts of stearic acid, polymeric particles such as polymethyl methacrylate particles and polystyrene particles, which are prepared by a free emulsion polymerization method of soap.
[0216] The polymeric particulates preferably have a relatively narrow particle size distribution and the average particle diameter thereof is preferably 0.01 µm to 1 µm.
[0217] There is no specific limitation for magnetic materials and any known magnetic materials can be used appropriately. Specific examples thereof include, but are not limited to, iron powder, magnetite and ferrite. Among these, white materials are preferable in terms of coloring.
[0218] There is no specific limitation for any method of making the toner of this disclosure and any material therefrom that satisfies the conditions. For example, a method of mixing, kneading and spraying and a method of granulating toner particles in an aqueous medium, called chemical manufacturing methods, are appropriately used.
[0219] The crystalline resin of the present disclosure has excellent shock resistance.
[0220] Therefore, extremely high energy is required to spray the crystalline resin to a particle diameter of 10 µm or less. Therefore, the chemical manufacturing method in which crystalline resins are easily granulated is preferable.
[0221] In addition, since the toner obtained by mixing and kneading and spraying can be sprayed at the interface of the binder resin and the release agent, the release agent tends to be exposed to the surface of the toner, thereby reducing the hardness of the toner and causing film to form in the carriers and the image-carrying member.
[0222] On the other hand, the chemical manufacturing method is advantageous for dispersing the release agent in the toner particles.
[0223] Specific examples of a method for manufacturing toner particle chemical particles from toner particles in an aqueous medium include, but are not limited to, a suspension polymerization method, emulsification polymerization method, a seed polymerization method and a dispersion polymerization method that makes a toner using a monomer as the starting material, a suspension dissolving method of dissolving a resin precursor and a resin followed by dispersion and / or emulsification in an aqueous medium, an emulsification method with changing phases of adding water to a solution containing a resin, a resin precursor and an appropriate emulsifier, and a method of agglomerating granular particles having the desired size by agglomerating the resin particles obtained by these methods which are dispersed in the aqueous medium followed by heating, melting, etc.
[0224] Among these, the toner obtained by the suspension in dissolution method is preferable in light of the granulation capacity (ease of controlling the particle size distribution, controlling the particle shapes, etc.) of the crystalline resin. These methods are described in detail below.
[0225] In the mixing, kneading and spraying method, for example, a toner material containing at least one coloring agent, a binder resin and a releasing agent is melted and mixed and kneaded and then pulverized and classified to manufacture the toner mother particles described above.
[0226] In melting, mixing and kneading, the toner materials are mixed and placed in a melting, mixing and kneading machine, for melting, mixing and kneading. Single screw or double screw continuous kneading and mixing machines or batch type kneading and mixing machines by a roller mill can be used as the melting and mixing and kneading machine.
[0227] Specific examples thereof include, include, but are not limited to, KTK type twin screw extruders (manufactured by KOBE STEEL, LTD.), TEM type extruders (manufactured by TOSHIBA MACHINE CO., LTD.), Screw extruders double (manufactured by KCK), PCM type twin screw extruders (manufactured by Ikegai Corp.), and Ko-kneaders (manufactured by Buss).
[0228] This melting and mixing and kneading is required to be conducted under appropriate conditions not to serve the molecular chain of binder resins.
[0229] To be specific, the temperature in the melting and mixing and kneading operation is determined with reference to the softening point of the binder resin. When the temperature is too high with respect to the softening point, the molecular chain tends to be severely aggravated. When the temperature is too high with respect to the softening point, the dispersion tends not to proceed smoothly.
[0230] In the spraying process, the mixture obtained from mixing and kneading is sprayed.
[0231] In the spraying process, it is preferable to coarsely spray the mixed and kneaded materials first followed by fine spraying.
[0232] In the process, the kneaded mixtures are sprayed by collision with a plate of collision in a jet stream, collision between the particles in a jet stream, and spraying in narrow gaps between a stator and a rotor that is mechanically rotating, etc.
[0233] The grading process adjusts the pulverized material obtained in the grading spray process to have a predetermined particle diameter.
[0234] Sorting can be done by removing particulate portions using a cyclone, a decanter or a centrifuge. After spraying and sorting, the sprayed material is classified into an air stream by centrifuge, etc. to manufacture toner mother particles having a predetermined particle diameter.
[0235] In the chemical manufacturing method, for example, the toner mother particles of the present disclosure are granulated by dispersion and / or emulsification particles containing at least one coloring agent, a binding resin, and an aqueous release agent. .
[0236] There is no specific limitation on the method of preparing an aqueous liquid dispersion of organic resin particulates from a resin.
[0237] (a) Um método de fabricar uma dispersão líquida aquosa de particulado de resina diretamente a partir da reação de polimerízação por um método de polimerização em suspensão e método de pulverização em emulsificação, um método de polimerização de semente, ou um método de polimerização de dispersão a partir de um monômero como o material inicial no caso de uma resina baseada em vinila. (b) Um método de fabricar um elemento de dispersão aquoso de particulados de resina por: dispersar um precursor (monômero, oligômero, etc.) ou sua solução de solvente sob a presença de um agente de dispersão apropriado; e curar o resultando aquecendo e/ou adicionando um agente de cura no caso de uma resina de poliadição ou de policondensação tais como uma resina de poliéster, uma resina de poliuretano e uma resina epóxi. (c) Um método de emulsificação com troca de fase de dissolver um agente de emulsificação apropriado em um precursor (monômero, oligômero, etc.) ou sua solução de solvente (solução liquida é preferida, liquidificado por aquecimento também é permissivel) seguido pela adição de água para troca de fase no caso de uma resina de poliadição ou de policondensação tais como uma resina de poliéster, uma resina de poliuretano e uma resina epóxi. (d) Um método de pulverizar uma resina inicialmente fabricada por uma reação de polimerização (polimerização de adição, polimerização de cisão de anel, poliadição, condensação de adição, policondensação, etc.) com um moinho de moagem fino de um tipo de rotação mecânica ou tipo de jato, classificando o resultante para obter particulados de resina, e dispersar os particulados de resina em água sob a presença de um agente de dispersão apropriado. (e) Um método de pulverizar uma solução de resina em que uma resina inicialmente fabricada por uma reação de polimerização (polimerização de adição, polimerização de cisão de anel, poliadição, condensação de adição, policondensação, etc.) é dissolvida em um solvente em uma forma de uma névoa de liquido fina para obter particulados de resina seguidos por dispersão em água sob a presença de um agente de dispersão apropriado. (f) Um método de adicionar um solvente a uma solução de resina em que uma resina inicialmente fabricada por uma reação de polimerização (polimerização de adição, polimerização de cisão de anel, poliadição, condensação de adição, policondensação, etc.) é dissolvida em um solvente ou resfriar uma solução de resina preparada inicialmente dissolvendo a resina em um solvente, aquecendo para precipitar os particulados de resina; remover o solvente para obter os particulados de resina; e dispersar os mesmos em água sob a presença de um agente de dispersão apropriado. (g) Um método de dispersar uma solução de resina em que uma resina inicialmente fabricada por uma reação de polimerização (polimerização de adição, polimerização de cisão de anel, poliadição, condensação de adição, policondensação, etc.) é dissolvida em um solvente em um meio aquoso sob a presença de um agente de dispersão apropriado; e remover o solvente por aquecimento, reduzir a pressão, etc. (h) Um método de dissolver um agente de emulsificação apropriado em uma solução de resina em que uma resina inicialmente fabricada por uma reação de polimerização (polimerização de adição, polimerização de cisão de anel, poliadição, condensação de adição, policondensação, etc.) é dissolvida em um solvente; e adicionar água à solução para emulsificação de troca de fase. For example, the following methods from (a) to (h) can be used. (a) A method of making an aqueous liquid dispersion of resin particulate directly from the polymerization reaction by a suspension polymerization method and emulsification spray method, a seed polymerization method, or a dispersion polymerization method from a monomer as the starting material in the case of a vinyl based resin. (b) A method of making an aqueous dispersion element of resin particulates by: dispersing a precursor (monomer, oligomer, etc.) or its solvent solution in the presence of an appropriate dispersing agent; and curing the result by heating and / or adding a curing agent in the case of a polyaddition or polycondensation resin such as a polyester resin, a polyurethane resin and an epoxy resin. (c) A phase-shift emulsification method of dissolving an appropriate emulsifying agent in a precursor (monomer, oligomer, etc.) or its solvent solution (liquid solution is preferred, liquefied by heating is also permissible) followed by addition of water for phase change in the case of a polyaddition or polycondensation resin such as a polyester resin, a polyurethane resin and an epoxy resin. (d) A method of spraying a resin initially manufactured by a polymerization reaction (addition polymerization, ring split polymerization, polyaddition, addition condensation, polycondensation, etc.) with a fine grinding mill of a mechanical rotation type or type of jet, classifying the resultant to obtain resin particulates, and disperse the resin particulates in water under the presence of an appropriate dispersing agent. (e) A method of spraying a resin solution in which a resin initially manufactured by a polymerization reaction (addition polymerization, ring split polymerization, polyaddition, addition condensation, polycondensation, etc.) is dissolved in a solvent in a form of a fine liquid mist to obtain resin particles followed by dispersion in water in the presence of an appropriate dispersing agent. (f) A method of adding a solvent to a resin solution in which a resin initially manufactured by a polymerization reaction (addition polymerization, ring split polymerization, polyaddition, addition condensation, polycondensation, etc.) is dissolved in a solvent or cool a resin solution prepared initially by dissolving the resin in a solvent, heating to precipitate the resin particles; removing the solvent to obtain the resin particles; and dispersing them in water in the presence of an appropriate dispersing agent. (g) A method of dispersing a resin solution in which a resin initially manufactured by a polymerization reaction (addition polymerization, ring split polymerization, polyaddition, addition condensation, polycondensation, etc.) is dissolved in a solvent in an aqueous medium in the presence of an appropriate dispersing agent; and remove the solvent by heating, reducing the pressure, etc. (h) A method of dissolving an appropriate emulsifying agent in a resin solution in which a resin initially manufactured by a polymerization reaction (addition polymerization, ring split polymerization, polyaddition, addition condensation, polycondensation, etc.) it is dissolved in a solvent; and add water to the phase exchange emulsification solution.
[0238] In addition, it is possible to use a surface active agent and a polymeric protective colloid for emulsification and dispersion in an aqueous medium.
[0239] Specific examples of surface active agents include, but are not limited to, anionic dispersing agents, for example, alkyl benzene sulfonic acid salts, sulfonic α-olefin acid salts, and phosphoric acid salts; cationic dispersing agents, for example, amine salts (for example, alkyl amine salts, amino alcohol fatty acid derivatives, polyamine and imidazoline fatty acid derivatives), and quaternary ammonium salts (for example, alkyltrimethyl ammonium salts , dialkylmethyl ammonium salts, alkylmethyl benzyl ammonium salts, pyridinium salts, alkyl isoquinoline salts and benzethonium chloride); non-ionic dispersing agents, for example, derivatives of fatty acid amide, derivatives of polyhydric alcohol; and ampholytic dispersing agents, for example, alanine, dodecildi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine.
[0240] The dispersion is improved with an extremely small amount of a surface active agent that has a fluoroalkyl group.
[0241] Preferred specific examples of anionic surface active agents having a fluoroalkyl group include, but are not limited to, fluoroalkyl carboxylic acids having 2 to 10 carbon atoms and their metal salts, perfluoro disodium octane sulfonylglutamate, 3- {omega-fluoroalkyl ( C6-C11) oxy} -1-alkyl (C3-C4) sodium sulfonate, 3- {Omega-fluoroalkanoyl (C6-C8) -N-ethylamino} -1-sodium propane sulfonate fluoroalkyl carboxylic acids (C11-C20) and its metal salts, perfluoroalkyl carboxylic acids and its metal salts, perfluoroalkyl sulfonate (C4-C12) and its metal salts, diethanol perfluorooctane sulfonic acid amides, N-propyl-N- (2-hydroxyethyl) perfluorooctane sulfone and perfluoroalkylammonylsulfonylammonyltrammonylammonyltrammonylammonylamide (C6-C10), perfluoroalkyl-N-ethylsulfonyl glycine salts (C6-C10), monoperfluoroalkylethyl phosphates (C6-C16), etc.
[0242] Specific examples of cationic surface active agents include, but are not limited to, the primary, secondary or tertiary, aliphatic amino acids having a fluoroalkyl group, aliphatic quaternary ammonium salts (for example, perfluoroalkyl sulfonoamidepropyltrimethyl ammonium salts (C6-C10), benzalkonium salts, benzethonium chloride, pyridinium salts, and imidazoline salts.
[0243] Specific examples of such polymeric protective colloids include, but are not limited to, polymers and copolymers prepared using monomers, for example, acids (for example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid and maleic anhydride), acrylic monomers having a hydroxyl group (for example, β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-acrylate γ hydroxypropyl, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylic acid esters, diethylene glycol methacrylic acid esters, glycerol methylacrylamide and methyl glycol acid ), vinyl alcohol and its ethers (for example, methyl vinyl ether, ethyl vinyl ether and propyl vinyl ether), vinyl alcohol esters with a co compound having a carboxyl group (i.e., vinyl acetate, vinyl propionate and vinyl butyrate); acrylic amides (for example, acrylamide, methacrylamide and diacetonoacrylamide) and their letiol compounds, acid chlorides (for example, acrylic acid chloride and methacrylic acid chloride), and monomers having a nitrogen atom or a heterocyclic ring having an atom nitrogen (eg vinyl pyridine, vinyl pyrrolidone, vinyl imidazole and ethylene imine). In addition, polymers, for example, polyoxyethylene compounds (eg, polyoxyethylene, polyoxypropylene, polyoxyethylenealkyl amines, polyoxypropylenealkyl amines, polyoxyethylenealkyl amides, polyoxypropylenealkyl amides, polyoxyethylene non-phenylethylenephenylethylphenylethylphenylphenylphenylphenylphenols ), and cellulose compounds, for example, methyl cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose, can also be used as the polymeric protective colloid.
[0244] The toner of the present disclosure is preferably obtained by dissolving or dispersing a toner composition that contains at least one coloring agent, a binder resin and / or a precursor thereof, and a release agent in an organic solvent to obtain an oil phase. and dispersing and / or emulsifying the oil phase in an aqueous medium to granulate the toner particles.
[0245] The organic solvent for dissolving or dispersing the toner composition having a binder resin and / or a precursor thereof, a coloring agent and a release agent is preferably volatile with a boiling point lower than 100 ° C in order to facilitate the removal of the last organic solvent.
[0246] Specific examples of organic solvents include, but are not limited to, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichlorethylene, chloroform, monochlorobenzene, dichloroethylidene, acetate methyl, ethyl acetate, methyl ethyl ketone and methyl isobutyl ketone. These can be used alone or in combination.
[0247] Among these, ester-based solvents such as methyl acetate and ethyl acetate, aromatic-based solvent such as toluene and xylene and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride are especially preferred .
[0248] The oil phase obtained by dissolving or dispersing the toner composition having a binder resin and / or a precursor thereof, a coloring agent, and a release agent has a solid portion concentration of about 40% to about 80% .
[0249] A concentration that is too high tends to make dissolution or dispersion difficult and the viscosity becomes high so that handling the solution or liquid dispersion is difficult. A concentration that is too high results in less toner production.
[0250] Toner compositions other than the coloring agent and resins such as the release agent and a master batch of toner compositions are dissolved separately or dispersed in the organic solvent and mixed with the resin solution or liquid dispersion described above.
[0251] The aqueous medium is not limited to plain water, and mixtures of water with a solvent that can be mixed with water are also used appropriately.
[0252] Specific examples of such a mixable solvent include, but are not limited to, alcohols (for example, methanol, isopropanol and ethylene glycol), dimethylformamide, tetrahydrofuran, cellosolves (for example, methyl cellosolve), lower ketones (for example, acetone and methyl ethyl ketone), etc.
[0253] The amount of aqueous medium is usually 50 parts by weight to 2,000 parts by weight and, preferably, from 100 parts by weight to 1,000 parts by weight based on 100 parts by weight of the toner composition.
[0254] When the amount of aqueous medium is very small, the dispersion state of the toner composition is diluted so that toner particles having a desired particle diameter are not obtained.
[0255] An excessively large amount of aqueous medium is not preferred in terms of economy.
[0256] It is possible to initially disperse an inorganic or particulate dispersion agent of organic resin in the aqueous medium, which is also preferable to have a marked particle size distribution and to stabilize the dispersion.
[0257] Specific examples of inorganic dispersing agent include, but are not limited to, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica and hydroxyapatite.
[0258] There is no specific limit to the selection of the resin that forms the resin particulates as long as the resin can form an aqueous dispersion element.
[0259] Any thermoplastic resins or thermosetting resins can be used. Specific examples thereof include, but are not limited to, vinyl based resins, polyurethane resins, epoxy resins, polyester resins, polyamide resins, polyimide resins, silicon based resins, phenolic resins, melamine resins, urea, aniline resins, ionomer resins and polycarbonate resins. These resins can be used alone or in combination.
[0260] Among these, vinyl resins, polyurethane resins, epoxy resins, polyester resins, and their use in combination, are preferred in terms of that a dispersion element having fine spherical resin particles is easy to obtain.
[0261] There is no particular limitation for the method of emulsification and dispersion in the aqueous medium. Known installations that employ a low speed shear method, a high speed shear method, a friction method, a high pressure jet method, ultrasonic methods etc. can be used.
[0262] Among these, the high speed shear method is preferable in terms of particle size reduction.
[0263] When a high-speed shear-type dispersion machine is used, there is no particular limitation on its speed of rotation. The rotation speed is typically from 1,000 rpm to 30,000 rpm, and preferably from 5,000 rpm to 20,000 rpm.
[0264] The temperature during the dispersion process is typically 0 ° C to 150 ° C (under pressure) and preferably 20 ° C to 80 ° C.
[0265] When the toner composition contains the precursor to the binder resin, it is possible to initially mix a compound having the active hydrogen group mentioned above, etc. required to conduct the elongation or crosslinking reaction of the binder resin precursor in the oil phase before dispersing the toner composition in the aqueous medium or mixing them in the aqueous medium.
[0266] Any known method can be used to remove the organic solvent from the obtained emulsified dispersion element.
[0267] For example, a method can be employed in which the system is gradually heated under normal pressure or with reduced pressure to evaporate and completely remove the organic solvent in the droplets.
[0268] When an agglomeration method is used in the aqueous medium, it is possible to agglomerate the liquid dispersion and / or liquid emulsification of the toner composition obtained as described above in the aqueous medium for granulation or an emulsified dispersion element obtained by separately dispersing and / or emulsifying the compositions of toner other than the coloring agent and resins such as the release agent and the master batch of the toner compositions in the aqueous medium together for granulation.
[0269] This emulsified dispersion element can be added at once on separate occasions.
[0270] To control the state of agglomeration, a method of heating, adding a metal salt, adjusting the pH, etc. it is preferably used.
[0271] There is no specific limitation for metal salt. Specific examples of monovalent metal that form the salt include, include, but are not limited to, sodium and potassium. Specific examples of divalent metal that forms the salt include, include, but are not limited to, calcium and magnesium. A specific example of trivalent metal that forms the salt is aluminum.
[0272] Specific examples of anions that form the salts include, include, but are not limited to, chloride ion, bromide ion, iodine ion, carbonate ion and sulfuric acid ion. Among these, magnesium chloride, aluminum chloride and complexes and polymers thereof are preferable.
[0273] In addition, it is possible to accelerate the melting of the resin particles by heating during or after agglomeration, which is preferable in terms of toner uniformity.
[0274] In addition, it is possible to control the form of toner by heating. As the toner is heated, the shape of the toner becomes almost spherical.
[0275] The known technologies are used in the process of washing and drying the toner mother particles dispersed in the aqueous medium.
[0276] That is, after separation into solid and liquid by a centrifuge or a filter press to obtain a toner cake, the cake obtained is redispersed in deionized water at room temperature at about 40 ° C.
[0277] Subsequent to the optional pH adjustment by an acid or alkali, the resultant is subjected to a separation of solid and liquid treatment again. This process is repeated several times to remove impurities and the active surface agent.
[0278] Then, the resulting product is dried by an air dryer, a circulation dryer, a reduced pressure dryer, a vibration flow dryer, etc. to obtain the toner powder.
[0279] The particulate components of the toner can be removed by a centrifuge and a known classifier can optionally be used after the drying process to obtain a toner that has a desired particle size distribution.
[0280] The toner powder thus prepared after the drying process can be mixed with other types of particles such as particulates of charge control agent and particulates of fluidizing agent. These other types of particles can be attached to and fused to the surface of toner particles by applying a mechanical impact to them.
[0281] Thus, it can be prevented that the other types of particles are detached from the surface of the complex particles thus obtained.
[0282] Specific examples of such methods of applying mechanical impact include, but are not limited to, a method in which an impact is applied to a mixture by a blade rotating at a high speed and a method of placing a mixture into a jet stream of air to accelerate the speed of the (complex) particles to collide with each other or with a collision plate.
[0283] Specific examples of such mechanical impact applicators include, but are not limited to, NGO MILL (manufactured by HOSOKAWA MICRON CO., LTD.), Modified I TYPE MILL (manufactured by Nippon Pneumatic Mfg. Co., Ltd.) where the spray air pressure is reduced, HYBRIDIZATION SYSTEM (manufactured by NARA MACHINE CO., LTD.), KRYPTRON SYSTEM (manufactured by KAWASAKI HEAVY INDUSTRIES, LTD.), and automatic mortars, etc.
[0284] The developing agent in the present disclosure contains the toner described above and other appropriately selected components such as carriers.
[0285] The developing agent can be a one-component developing agent and a two-component developing agent and the two-component developing agent is preferable around the life span particularly when used on a high speed printer that meets the demand for high-speed information processing from the latter.
[0286] When a component developing agent using the toner described above is used and refilled a number of times, the change in toner particle diameter is small, no formation of toner film occurs on the development cylinders, and no no fusing connection of toner on the limbs such as a blade to regulate the thickness of the toner layer. Therefore, good and stable developing capacity is sustained to produce quality images even when the developing agent is agitated for an extended period of time.
[0287] When a two-component developer using the toner described above is used and refilled a number of times over an extended period of time, the change in toner particle diameter is small.
[0288] In addition, good and stable developing capacity is maintained even when the developing agent is agitated in a developing device for an extended period of time.
[0289] There is no specific limitation for the carrier. A carrier is preferable, which contains a core material and a layer of resin that covers the core material.
[0290] There is no material specific limitation for the core material and any known material can be used appropriately.
[0291] For example, materials based on manganese-strontium (Μη-Sr) and materials based on manganese-magnesium (Mn-Mg) having 50 emu / g to 90 emu / g are preferable.
[0292] To ensure image density, highly magnetized materials such as iron powder having 100 emu / g or more and magnetite having 75 emu / g to 125 emu / g are preferable.
[0293] In addition, weakly magnetized copper-zinc based materials (Cu-Zn) having 30 emu / g to 80 emu / g are preferable in terms of reducing the impact of contact between the toner filaments formed on the developing cylinder and the image conduction, which is advantageous in improving image quality. These can be used alone or in combination.
[0294] The core material preferably has a D50 weight average particle diameter of 10 µm to 200 µm and more preferably 40 µm to 100 µm.
[0295] When the weight average particle diameter D50 is very small, the amount of fine powder tends to increase the distribution of the carrier particles and the particle magnetization tends to decrease, which leads to the diffusion of the carrier particles.
[0296] When the weight average particle diameter D50 is very large, the specific surface area tends to decrease, resulting in toner diffusion.
[0297] In a fully colored image in which the solid portions occupy a large ratio, reproducibility tends to deteriorate particularly in the solid portions.
[0298] There is no specific limitation for materials for the resin layer mentioned above and any known resin can be used appropriately. Specific examples thereof include, but are not limited to, amino-based resins, polyvinyl-based resins, polystyrene-based resins, polycarbonate-based resins, Polyethylene resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polytrifluoroethylene, polyiexafluoropropylene resins, vinylidene fluoride and acrylic monomer copolymers, vinylidene fluoride and vinyl fluoride copolymers, fluorotherpolymers {non-tri- (polymer) copolymer fluoro) such as non-tetrafluoroethylene fluorine fluoride fluorine and silicone resins. These can be used alone or in combination. Among these, silicone resins are particularly preferred.
[0299] There is no specific limitation for silicone resins and any known silicone resins are used appropriately. Specific examples thereof include, but are not limited to, straight silicone resins formed only from organosiloxane bonding, and silicone resins modified by alkyl resins, polyester resins, epoxy resins, acrylic resins, urethane resins, etc.
[0300] Commercially available silicone resin products can be used. Specific examples of straight silicone resin include, but are not limited to, KR271, KR255, and KR152, manufactured by Shin-Etsu Chemical Co., Ltd .; and SR2400, SR2406, and SR2410, manufactured by DOW CORNING TORAY CO., LTD.
[0301] Commercially available modified silicone resin products can be used.
[0302] Specific examples thereof include, but are not limited to, KR206 (modified with alkyd), KR5208 (modified with acrylic), ES1001N (modified with epoxy and KR305 (modified with urethane) manufactured by Shin-Etsu Chemical Co., Ltd .; and SR2115 (modified with epoxy), and SR2110 (modified with alkyd), manufactured by DOW CORNING TORAY CO., LTD.
[0303] It is possible to use a simple silicone resin and it is also possible to use it with a component that conducts the crosslinking reaction, a load control component, etc., simultaneously.
[0304] The resin layer may contain electroconductive powder such as metal powder, carbon black, titanium oxide, tin oxide and zinc oxide.
[0305] The average particle diameter of such an electroconductive powder is preferably not greater than 1 μm.
[0306] When the average particle diameter is very large, control of electrical resistance can be difficult.
[0307] The resin layer described above can be formed, for example, by dissolving the silicone resin described above, etc. in a solvent to prepare a liquid application and apply the liquid application to the surface of the core material described above by a known application method followed by drying and cooking.
[0308] Specific examples of known application methods include, but are not limited to, dip coating method, spray coating method and brushing method.
[0309] There is no specific limitation for the solvent. Specific examples thereof include, but are not limited to, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, and cellosolve, and butyl acetate.
[0310] There is no specific limitation on cooking. An external heating system or an internal heating system can be used.
[0311] For example, a fixed electric oven, a fluid electric oven, a rotary electric oven, a method of using a firing oven and a method of using a microwave can be used appropriately.
[0312] The content of the carrier in the resin layer is preferably 0.01% by weight to 5.0% by weight.
[0313] A content that is too small tends to make it difficult to form a uniform layer on the surface of the core material. A content that is too large tends to result in an excessively thick layer, thus causing granulation between the carrier particles in a UE way, uniform carrier particles are not obtained.
[0314] When the developing agent described above is a two-component developing agent, there is no specific limitation on the carrier content in the two-component developing agent.
[0315] For example, the content is preferably from 90% by weight to 98% by weight and more preferably from 93% by weight to 97% by weight.
[0316] The toner mixing ratio for the carrier in the two-component developer is preferably 1 part by weight to 10.0 parts by weight based on 100 parts by weight of the carrier.
[0317] The imaging apparatus of the present disclosure includes at least one member carrying the latent electrostatic image (photoreceptor), a charger, an irradiator, a developing device, a transfer device, and a fixture with optional devices such as cleaners , a discharge device, a recycling device and a control device.
[0318] A combination of the charger and the radiator is also referred to as a latent electrostatic imaging device.
[0319] The developing device has a magnetic field generating device fixed inside and can have a developing agent driving member which is rotatable while driving the two developing agents of the present disclosure.
[0320] There is no specific limitation for the electrostatic imaging conduction member with respect to material, shape, structure, size, etc. Specific shape examples include, but are not limited to, a drum shape, a leaf shape and an endless belt shape.
[0321] As for the structure, a single layer structure or a laminate structure can be employed.
[0322] The size can be appropriately determined according to the size of the imaging device and the specifications.
[0323] Specific examples of materials include, but are not limited to, inorganic compounds such as amorphous silicon, selenium, CdS and ZnO; and organic compounds such as polysilane and phthalopolymethyl.
[0324] There is no specific limitation for the charger that can apply a voltage to the surface of the electrostatic imaging conduction member to charge it evenly. These are generally classified into (1): a contact type charger that charges the electrostatic imaging conduction member; and (2) a non-contact type charger that charges the latent electrostatic imaging member in a non-contact mode.
[0325] Specific examples of contact type charger from (1) include, but are not limited to, an electroconductive or semi-electroconductive charging cylinder, a magnetic brush, a hair brush, a film, and a rubber blade.
[0326] Among these, the loading cylinder possibly reduces the amount of ozone product compared to corona discharge and has excellent stability during repetitive use of the electrostatic imaging conduction member, which is suitable for preventing deterioration of image quality.
[0327] Specific examples of a non-contact type charger from (2) include, but are not limited to, a non-contact type charger, a needle electrode device, and a solid discharge element using corona discharge, and an electroconductive charging cylinder or semi-electroconductive disposed against the latent electrostatic image conduction member with an interval of 1 min between them.
[0328] There is no specific limitation for the radiator that radiates the surface of the electrostatic imaging conduction member charged by the charger with light according to the image data.
[0329] Specific examples of radiators include, but are not limited to, an optical photocopy system, a rod lens array system, a laser optical system, a liquid crystal shutter optical system, and an LED optical system.
[0330] The rear lateral irradiation system in which a latent electrostatic imaging member is irradiated from the rear side of the same can also be employed.
[0331] There is no specific limitation for the developing device as long as the developing device reveals latent electrostatic images with the developing agent and any known developing device can be used. For example, a developing device that accommodates and applies the two-component developing agent to the latent electrostatic image in a contact and non-contact mode is preferably used.
[0332] The developing device may employ a dry type development system or a wet type development system.
[0333] In addition, the developing device can be for a single color or multiple colors. For example, it is preferable to use a two-component developing device that includes an agitator to triboelectrically stir and charge the two-component developing agent, a magnetic field generating device fixed inside, and a conducting member of the developing agent. which is rotary while driving the two-component developer on its surface.
[0334] In the developing device, the toner and the carrier are mixed and agitated to triboelectrically charge the toner. The toner is then kept on the surface of the rotating magnet drum in a filament mode to form an magnet brush.
[0335] Since a magnetized cylinder is provided in the vicinity of the electrostatic imaging conduction member, part of the toner that forms the magnetized brush formed on the surface of the magnetized cylinder is electrically attracted to the surface of the electrostatic imaging conduction member.
[0336] As a result, the electrostatic imaging is developed with the toner and made visual as a toner image on the surface of the electrostatic imaging conduction member.
[0337] Figure 1 is a schematic diagram illustrating an example of a two-component developer 424 using a two-component developer containing the toner and the magnetic carrier.
[0338] In the two-component developer of Figure 1, the two-component developer is agitated and transferred by a screw 441 and supplied to a developer glove 442 that serves as a driving member of the developer.
[0339] The two-component developing agent supplied to the development sleeve 442 is regulated by a doctor blade 443 serving as a layer thickness regulator. The amount of developer agent supply is controlled by a doctor gap formed between the doctor blade 443 and the developer glove 442.
[0340] When this physician gap is very small, the amount of developing agent tends to be small, resulting in the shortening of the image density. When this physician gap is very large, the developing agent is easily over-supplied, which causes the wearer to attach to an image conduction drum 1 serving as the latent electrostatic image conduction member.
[0341] Therefore, within the development sleeve 442, a magnet is provided to serve as a magnetic field generating device that forms the magnetic field to maintain the development agent on the circumference surface of the development sleeve 442 in a filament mode. so that the magnetic filament brush is formed as a chain on the development sleeve 442 after the magnetic line in the general line direction generated by the magnet.
[0342] Developing sleeve 442 and image driving drum 1 are arranged in close proximity to each other with a constant gap (developing gap) to form developing areas on both opposing portions.
[0343] Developing sleeve 442 has a cylindrical shape made of non-magnetic substance such as aluminum, brass, stainless steel and electroconductive resin and is rotatable by a rotating driving mechanism.
[0344] The magnetic brush is transferred to the development area by rotating the development sleeve 442.
[0345] A development slope is applied to the development sleeve 442 by a source of development energy so that the toner in the magnetized brush is separated from the carrier by the development field formed between the development sleeve 442 and the image driving drum 1 for reveal the latent electrostatic image in the image conduction drum 1.
[0346] An AC voltage can be superimposed over the developing voltage.
[0347] The size of the developing gap is preferably about 5 times to about 30 times as large as the particle diameter of the developing agent.
[0348] If the developing agent has a particle diameter of 50 µm, an appropriate development gap is 0.25 mm to 1.5 mm.
[0349] When the development gap is very large, a desired image density is not easily achieved.
[0350] In addition, the physician gap is preferably the same as the disclosure gap or slightly larger than that.
[0351] The drum diameter of the image driving drum 1, the linear drum speed of the drum, the diameter of the developing sleeve glove 442, and the linear speed of the drum glove are determined by the limitation with respect to the photocopy speed and the device size.
[0352] The linear speed ratio of the sleeve to the linear speed of the drum is preferably 1.1 or greater to obtain a required image density.
[0353] It is also possible to supply a sensor to a position on the downstream side of the development to detect the amount of toner fixation from the optical reflectivity to control the process conditions.
[0354] The transfer device is classified into a transfer device that directly transfers the visual image on the electrostatic imaging conduction member to a recording medium and a transfer device that transfers the visual image secondarily to a recording medium after first transferring it. the visual image for an intermediate transfer body.
[0355] There is no specific limitation for both transfer devices, and any known transfer devices can be appropriately selected.
[0356] There is no specific limitation for the fixture. A fixture having a fixing member and a heating source that heats the fixing member is preferably used.
[0357] There is no specific limitation for the clamping device that forms a gripping portion with the members in contact with each other.
[0358] For example, a combination of an endless belt and a cylinder and a combination of cylinders are used appropriately.
[0359] It is preferable to use the combination of endless belt and cylinder and a method of heating the surface of the fastening member with induction heating in terms of shortening the heating time and saving energy.
[0360] The fixture is classified into (1) a system (internal heating system) in which a fixture has at least one of a cylinder and a belt and conducts heating from the side of the surface not in contact with the toner to fix a transfer image transferred on the heat and pressure recording medium; and (2) a system (external heating system) in which a fixture has at least one of a cylinder and a belt and conducts the heating from the side of the surface in contact with the toner to fix a transfer image on a heat recording medium and a pressure. It is possible to use both in combination.
[0361] As the fixture of the internal heating system of (1), for example, a fixture by itself having a heating device inside can be used.
[0362] A heat source such as a heater and a halogen lamp can be used as such a heating system.
[0363] As the fixture of the sternal heating system of (2), for example, a system is preferable in which at least part of the surface of at least one of the fixing members is heated by a heating device.
[0364] There is no specific limitation for the heating device.
[0365] Specific examples of this include, but are not limited to, an electromagnetic induction heating device
[0366] There is no specific limitation for the electromagnetic induction heating device. A system having a device for generating a magnetic field and a device for generating heat by electromagnetic induction is preferable.
[0367] Like the electromagnetic induction heating device, a device is preferable that has an induction coil arranged close to the fixing member (for example, the heating cylinder), a shield layer for which the induction coil is provided, and an insulation layer provided on the side of the shield layer which is inverse to the side on which the induction coil is provided.
[0368] It is preferable that the heating cylinder has a system that has a magnetic substance or a heating tube.
[0369] It is preferable that the induction coil is arranged on the side of the heating cylinder while encapsulating at least the semicircle portion and the side is inverse to the contact portion of the heating cylinder and the fixing member (for example, the compression cylinder and the endless belt).
[0370] The process cartridge of the present disclosure includes at least one electrostatic imaging conduction member that carries an electrostatic imaging image, a developing device that reveals the electrostatic imaging born on the electrostatic imaging conduction member with the developing agent. of the present disclosure to obtain a visual image, and other optional devices such as a charger, a radiator, a transfer device, a cleaner, and a discharge device.
[0371] The developing device includes a developer agent container to accommodate the developer agent, a developer agent driving member to load and transfer the developer agent accommodated in the developer agent container, and other optional devices such as a regulator layer thickness to regulate the thickness of the developing agent layer born in the developing agent driving member.
[0372] To be specific, any of the developing devices described in the imaging apparatus can be used appropriately.
[0373] In addition, as for the charger, the radiator, the transfer device, the cleaner and the discharge device, the same devices described in the image forming apparatus can be used appropriately.
[0374] The process cartridge described above is detachable to various image machines, fax machines and printers and preferably detachable to the image device of the present disclosure.
[0375] The process cartridge includes, for example, an electrostatic imaging conduction member 101, a magazine 102, a developing device 104, a transfer device 108, a cleaner 107, and other optional devices.
[0376] In figure 2, reference numbers 103 and 105 represent beams of light through an irradiator and a recording medium, respectively.
[0377] Next, the image formation process is described by the process cartridge illustrated in figure 2.
[0378] The latent electrostatic imaging member 101 is charged by the charging device 102 and irradiated with the light beams 103 by an irradiator while rotating in the direction indicated by an arrow to form a latent electrostatic image on the surface of the imaging member latent electrostatic 101 corresponding to the irradiation image.
[0379] The latent electrostatic image is developed with toner by the developing device 104 and the developed toner image is transferred by the transfer device 108 to the recording medium 105 and printed.
[0380] The surface of the latent electrostatic imaging member 101 after image transfer is cleaned by cleaner 107 and discharged by a discharge device to be ready for the next imaging process.
[0381] Having generally described the preferred embodiments of this invention, another understanding can be obtained by reference to certain specific examples that are provided herein for the purpose of illustration only and are not intended to be limiting. In the descriptions in the following examples, the numbers represent weight ratios in parts, unless otherwise specified. EXAMPLES
[0382] In the following, the present disclosure is described in detail with reference to the Examples and Comparative Examples, but not limited to them. EXAMPLE 1 Example of manufacturing crystalline resin A1
[0383] Place 241 parts of sebacic acid, 31 parts of adipic acid, 164 parts of 1,4-butane diol and 0.75 part of titanium dihydroxybis (triethanol aminate) as a condensation catalyst in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube to conduct the reaction for eight hours at 180 ° C in a nitrogen atmosphere while distilling the produced water.
[0384] The reaction was then carried out for four hours while gradually heating the system to 225 ° C and distilling the produced water and 1,4-butane diol in a nitrogen atmosphere and continuing the reaction with a reduced pressure of 5 mmHg to 20 mmHg until the average molecular weight Mw of the resultant reaches about 6,000.
[0385] Transfer 218 parts of the crystalline resin thus obtained to a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introducing tube and add 250 parts of ethyl acetate and 82 parts of hexamethylene diisocinate (HDI) to this to conduct the reaction at 80 ° C in a nitrogen atmosphere for five hours.
[0386] Then, distill ethyl acetate under reduced pressure to obtain crystalline resin 1 (polyester / polyurethane resin) having an Mw of about 22,000 and a maximum peak heat of fusion heat of 60 ° C. Example of manufacturing non-crystalline resin C1
[0387] Place 240 parts of 1,2-propane diol, 226 parts of terephthalic acid, and 0.64 parts of tetrabutoxy titanate as a condensation catalyst in a reaction vessel equipped with a condenser, a stirrer, and an inlet tube. nitrogen to conduct the reaction at 180 ° C in a nitrogen atmosphere for eight hours while distilling the produced methanol.
[0388] Then, conduct the reaction for four hours while heating the system to 230 ° C and distilling the produced water and 1,2-propane diol in a nitrogen atmosphere and continue the reaction for one hour with a reduced pressure of 5 mmHg to 20 mmHg cooling to 180 ° C.
[0389] From now on, place 8 parts of trimellitic anhydride and 0.5 parts of tetrabutoxy titanate in the reaction vessel to conduct the reaction for one hour and continue the reaction at a reduced pressure of 5 mmHg to 20 mxnHg until Mw reaches about 7,500 to obtain the non-crystalline resin C1 (polyester resin) having a glass transition temperature of 61 ° C and a maximum peak heat temperature of melting of 65 ° C. Example of manufacturing the master batch of coloring agent P1
[0390] Mix 100 parts of the A1 crystalline resin, 100 parts of a cyan pigment (Pigment CI blue 15: 3), and 30 parts of deionized water followed by mixing and kneading in an open cylinder type mixing and kneading machine (Kneadex, manufactured by NIPPON COKE & ENGINEERING CO., LTD.).
[0391] Start mixing and kneading at 90 ° C followed by gradual cooling to 50 ° C to manufacture the master batch of coloring agent P1 having a 1: 1 ratio of resin and pigment. Wax liquid dispersion fabrication example
[0392] Place and sufficiently dissolve 20 parts of microcrystalline wax (Hi-Mic-1090) manufactured by Nippon Seiro Co., Ltd.) having a maximum endothermic peak temperature Wp (melting point) of 69 ° C melting heat, a temperature melting initiation Ws of 57 ° C, and a needle penetration degree of 5 to 25 ° C and 80 parts of ethyl acetate in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introducing tube for heating at 78 ° C.
[0393] After cooling the system to 30 ° C in one hour while stirring, spray the resulting wet in an Ultra Visco mill manufactured by AIMEX CO., LTD.) Under the condition of a liquid feed speed of 1.0 kg / h , a disk peripheral speed of 10 m / s, 0.5 mm of zirconia bead fill amount of 80% by volume, and a pass number of 6 to obtain liquid dispersion of wax W1. Toner manufacturing example 1
[0394] Place 39 parts of A1 crystalline resin and 39 parts of ethyl acetate in a container equipped with a thermometer and stirrer and dissolve them by heating to the resin melting point or higher.
[0395] Add 90 parts of 50% ethyl acetate solution by weight of non-crystalline resin C1, 20 parts of liquid dispersion of wax W1, 12 parts of the master batch of coloring agent P1 and 50 parts of ethyl acetate to the container followed by agitation by a TOM HOMOMIXER (manufactured by PRIMIX Corporation) at a rotation number of 10,000 rpm at 50 ° C for uniform dissolution and dispersion to obtain oil phase 1.
[0396] Maintain the temperature of oil phase 1 in the container at 50 ° C and use it within five hours of manufacture before it is crystallized.
[0397] Then add 90 parts of deionized water, 3 parts of 5% by weight of aqueous solution of nonionic surface active agent of the polyoxyethylene lauryl ether type (NL450, manufactured by DAI-ICHI KOGYO SEIYAKU CO., LTD., 10 parts of ethyl acetate in a container equipped with a stirrer and a thermometer and mix and shake at 40 ° C to prepare an aqueous phase solution Add 50 parts of oil phase 1 kept at 50 ° C to the container and mix the for one minute at 40 ° C to 50 ° C by a TOM HOMOMIXER (manufactured by PRIMIX Corporation) at a rotation number of 13,000 rpm to obtain the emulsified suspension 1.
[0398] Place the emulsified suspension 1 in a container equipped with a stirrer and a thermometer followed by the removal of the solvent at 60 ° C for six hours to obtain the suspension 1.
[0399] (1) : Adicionar 100 partes de água desionizada ao bolo filtrado e misturar a mistura por um HOMOMIXER TK a 6.000 rpm durante cinco minutos seguido por filtração; (2) : Adicionar 100 partes de 10% de hidróxido de sódio a 10% ao bolo filtrado obtido em (1) e misturar o resultante por um HOMOMIXER TK a 6.000 rpm durante dez minutos seguido por filtração com uma pressão reduzida; (3) : Adicionar 100 partes de ácido clorídrico a 10% em peso ao bolo filtrado obtido em (2) e misturar o resultante por um HOMOMIXER TK a 6.000 rpm durante cinco minutos seguido por filtração; (4) : Adicionar 300 partes de água desionizada ao bolo filtrado obtido em (3) e misturar o resultante por um HOMOMIXER TK a um número de rotação de 6.000 rpm durante cinco minutos seguido por filtração duas vezes para obter o bolo filtrado 1. Filter 100 parts of the suspension 1 obtained from the mother toner particles with reduced pressure followed by the following washing treatment: (1): Add 100 parts of deionized water to the filtered cake and mix the mixture with a HOMOMIXER TK at 6,000 rpm for five minutes followed by filtration; (2): Add 100 parts of 10% 10% sodium hydroxide to the filter cake obtained in (1) and mix the resultant with a HOMOMIXER TK at 6,000 rpm for ten minutes followed by filtration with reduced pressure; (3): Add 100 parts of 10% by weight hydrochloric acid to the filter cake obtained in (2) and mix the resultant with a HOMOMIXER TK at 6,000 rpm for five minutes followed by filtration; (4): Add 300 parts of deionized water to the filter cake obtained in (3) and mix the resulting by a HOMOMIXER TK at a rotation number of 6,000 rpm for five minutes followed by filtration twice to obtain the filtered cake 1.
[0400] Dry the filter cake 1 by a circulating dryer at 45 ° C for 48 hours.
[0401] Sieve the resultant with a mesh having an opening of 75 µm to obtain the toner mother particle 1.
[0402] Mix 1.0 part of hydrophobic silica (HDK-2000, manufactured by Wacker Chemie AG) with 100 parts of the toner mother particle 1 thus obtained by a HENSCHEL mixer to prepare toner 1 having a volume average particle diameter of 5, 6 µm.
[0403] Evaluate the toner 1 thus obtained and the results are shown in table 4. Carrier manufacturing example
[0404] The carrier for use in the two component developing agent of this disclosure is manufactured as follows: Prepare a liquid application by dispersing 450 parts of toluene, 450 parts of silicone resin (SR2400, non-volatile component: 50%, manufactured by DOW CORNING TORAY CO., LTD.), 10 parts of aminosilane (SH6020, manufactured by DOW CORNING TORAY CO., LTD.) And 10 parts of carbon black as a coating material with a stirrer for ten minutes.
[0405] Place 5,000 parts of Mn ferrite particles (weight average particle diameter: 35 pm) as core material and the coating liquid in a coating device that conducts the coating while swirling through a rotating base plate disc and a flapping wing on the flowing ceiling to apply liquid application to the core material.
[0406] Cook the coated material thus obtained in an electric oven at 250 ° C for two hours to obtain carrier A. Two-part developer agent manufacturing example
[0407] Evenly mix 7 parts of the toner manufactured as described above with 100 parts of carrier A using a turbulent mixer (manufactured by Willy A. Bachofen (WAB) AG) that tip the container while stirring at 48 rpm for three minutes to load them.
[0408] In the present disclosure, place and mix 200 g of carrier A and 14 g of toner in a stainless steel container having an internal 50 ml volume.
[0409] Fill with the two-component agent thus manufactured a cyan development unit of a tandem-type imaging apparatus (imaging apparatus A) employing an indirect transfer system in which a contact charge system, a two-component developing system, a secondary transfer system, a blade cleaning system, and a cylinder fixing system using an external heating system; and forming images followed by the evaluation of toner and developer performance.
[0410] The imaging apparatus A for use in performance testing in the present disclosure is described in detail.
[0411] An imaging apparatus 100 shown in Figure 3 is a tandem type colored imaging apparatus.
[0412] A tandem developing device 120 includes a main portion 150 of the image forming apparatus, a sheet feeder table 200, a scanner 300 and an automatic document feeder (ADF) 400.
[0413] The main portion 150 of the imaging apparatus has an intermediate transfer body 50 that has an endless shape in the center thereof.
[0414] The intermediate transfer 50 is suspended on support cylinders 14, 15 and 16 and rotates clockwise in figure 3.
[0415] An intermediate transfer body cleaner 17 to remove the remaining residual untransfered toner on the intermediate transfer body 50 is arranged around the support cylinder 15.
[0416] The tandem developing device 120, which has four yellow, cyan, magenta and black image forming units 18, is arranged facing the intermediate transfer body 50 suspended on the support cylinders 14 and 15 along the direction of transfer.
[0417] An irradiator 21 is arranged close to the tandem developing device 120.
[0418] A secondary transfer device 22 is arranged facing the tandem developing device 120 with the intermediate transfer body 50 between them.
[0419] In the secondary transfer device 22, a secondary transfer belt 24 having an endless shape is suspended on a pair of cylinders 23 and a recording medium transferred to the secondary transfer belt 24 is possible to contact the intermediate transfer body 50 together.
[0420] A clamping device 25 is arranged close to the secondary transfer device 22.
[0421] In addition, the tandem image forming apparatus 100, a sheet reversing device 28 for forming images on both sides of the recording medium by inverting the recording medium is arranged close to the secondary transfer device 22 and a fixing device 25.
[0422] In the following, the formation of a full color image using the tandem developing device 120 is described.
[0423] First, place an (original) document on a document table 130 on the automatic document feeder 400 or open the automatic document feeder 400, place a document on contact glass 32 for the scanner 300, and close the document feeder automatic 400.
[0424] After the document is moved to the contact glass 32, press a start button in a case where the document is placed on the automatic document feeder 400, or immediately in a case where the document is placed on the contact glass 32 , the scanner is triggered to start scanning with a first scanning unit 33 and a second scanning unit 34.
[0425] Thus, the document is irradiated with the light emitted from a light source by the first scanning unit 33 and the reflection light from the document is redirected to the mirror of the second scanning unit 34. The light redirected to the mirror of the second scanning unit 34 passes through an image focusing lens 35 and is received at a reading sensor 36 to read the document (color image) thereby obtaining black, yellow, magenta and cyan image data.
[0426] Each image data for black, yellow, magenta and cyan is transmitted to each image forming unit 18 (image forming units for black, yellow, magenta and cyan) on the tandem imaging device 120 to form each toner image. colored black, yellow, magenta and cyan in each imaging unit.
[0427] As shown in Figure 4, each imaging unit 18 (imaging units for black, yellow, magenta and cyan) in the tandem developing device 120 includes a latent electrostatic imaging member 10 (a conducting member 10K electrostatic imaging unit for black, a 10Y electrostatic imaging unit for yellow, a 10M electrostatic imaging unit for magenta, and a 10C electrostatic imaging unit for cyan), a 60 charger that uniformly charges the electrostatic imaging conduction member 10, an irradiator that radiates the electrostatic imaging conduction member 10 with L light beams according to each color image data to form a latent electrostatic image corresponding to each color image in the latent electrostatic imaging member 10, a developing unit 61 that forms a toner image with each color toner re screening each latent electrostatic image with each color toner (black toner, yellow toner, magenta toner and cyan toner), a transfer charger 62 that transfers the toner image to the intermediate transfer body 50, a cleaner 63 and a discharge device 64. Therefore, each single color image (black image, yellow image, magenta image and cyan image) can be formed based on each color image data.
[0428] The black image, the yellow image, the magenta image and the cyan image formed on the 10K imaging conduction member for black; the imaging conduction member 10Y for yellow, the imaging conduction member 10M for magenta and the imaging conduction member for cyan, respectively, are first transferred sequentially to the intermediate transfer body 50 rotated by the support cylinders 14 , 15 and 16.
[0429] Then, the black image, the yellow image, the magenta image and the cyan image are superimposed on the intermediate transfer body 50 to form a synthesized color image (color transfer image).
[0430] On the sheet feeder table 200, one of the sheet feeder rollers 142 is selectively rotated to create the recording medium (sheets) of one of multiple sheet cassettes 144 stacked in a sheet bank 143. A separator cylinder 145 separates the medium one by one to feed it to a sheet path 146. Transfer rollers 147 transfer and guide the recording medium to a sheet path 148 in the main portion 150 of the imaging apparatus 100 and the recording medium is retained in a registration cylinder 49.
[0431] Alternatively, the recording media (sheets) on a hand tray 54 are acquired by rotating a cylinder and separated one by one by a separating cylinder 52, transferred to a manual sheet path 53, and also held on the recording cylinder 49.
[0432] The registration cylinder 49 is typically grounded, but a tilt can be applied to it to remove paper dust in the recording medium.
[0433] The registration cylinder 49 is rotated in synchronization with the synthesized color image (color transfer image) on the intermediate transfer body 50 to send the recording medium (sheet) between the intermediate transfer body 50 and the primary transfer device 22. The color synthesized image (color transfer image) is transferred secondarily to the recording medium to form a color synthesized image on it.
[0434] The residual toner remaining in the intermediate transfer body 50 after image transfer is removed by cleaner 17 from the intermediate transfer body.
[0435] The recording medium to which the color image is transferred is sent to the fixture 25 by the secondary transfer device 22 and the synthesized color image (color transfer image) is fixed on the heat and pressure recording medium in the device clamp 25. Reference numbers 26 and 27 represent a clamping belt and a compression cylinder, respectively.
[0436] Then, the recording medium is switched to a switch claw 55, discharged outside by a discharge cylinder 56, and stacked on a discharge tray 57.
[0437] Alternatively, the recording medium is switched by the switch claw 55 and guided to the transfer position again by the sheet reversing device 28 to record another image on the reverse side of the recording medium. Then, the recording medium is discharged by the discharge cylinder 56 and stacked on the discharge tray 57.
[0438] The method of assessing toner performance and the developing agent for use in the present disclosure is described in detail. Low temperature fixing property (lowest fixing temperature)
[0439] Form a single color solid image (image size: 3 cm x 8 cm) of cyan having a toner fixing amount of 0.75 mg / cm2 to 0.95 mg / cm2 after transferring the image onto the reference sheet (photocopying paper <70>, manufactured by NBS RICOH CO., LTD.) use the imaging device A and conduct the fixation while changing the fixing belt temperature. Draw a photograph on the surface of the still image obtained with a drawing tester (AD-401, manufactured by UESHIMA SEISAKUSHO CO., LTD.) With a ruby needle having a tip diameter of 260 µmR to 320 µmR with a 60 degree tip angle Under a load of 50 g and rub the surface of the photo drawn with a fiber (HONECOTTO # 440, manufactured by SAKATA INX ENG CO., LTD.) Five times. The temperature of the fixing belt at which almost no image scraping occurs is determined as the lowest fixing temperature.
[0440] In addition, form the solid image at a position 3.0 cm from the conductive end of the transfer sheet with respect to the transfer direction.
[0441] The speed of the transfer sheet passing through the gripper portion of the fixture is 280 mm / s.
[0442] The lower the lower fixing temperature, the better the low temperature fixing property. Hot offset resistance (fixable temperature range)
[0443] Form a single color solid image (image size: 3 cm x 8 cm) of cyan having a toner fixing amount of 0.75 mg / cm2 to 0.95 mg / cm2 after transferring the image onto a transfer sheet ( TYPE 6200, manufactured by RICOH CO., LTD.) Using the imaging device A and conducting the fixation while changing the temperature of the fixing belt.
[0444] Evaluate the fixed image by observing with the eyes on hot offset and determine the temperature range between the upper limit temperature above which the hot offset occurs and the low fixing temperature as the fixable temperature range.
[0445] In addition, form the solid image at a position 3.0 cm from the conductive end of the transfer sheet with respect to the transfer direction.
[0446] The speed of the transfer sheet passing through the gripper portion of the fixture is 280 mm / s.
[0447] The wider the fixable temperature range, the better the resistance to hot offset.
[0448] The typical average color toner temperature range is around 50 ° C.
[0449] The results are shown in Table 3. Abrasion Resistance
[0450] Form a single color solid image (image size: 3 cm x 8 cm) of cyan having a toner fixing amount of 0.75 mg / cm2 to 0.95 mg / cm2 after transferring the image onto a full transfer sheet (photocopying paper <70>, manufactured by NBS RICOH CO., LTD.) using an A forming device and conducting the fixation at a temperature of 20 ° C higher than the lowest toner fixing temperature. Rub the surface of the output image with a type S scrub tester (SUTHERLAND 2000 RUBTESTER, manufactured by Danilee Co.) using recycled paper (Recycle Paper Resource type A, manufactured by NBS RICOH CO., LTD.) Under a 800 g weight 50 times and evaluate the level of damage by rubbing on the image surface, comparing with the sample.
[0451] Scale the image from 1.0 to 5.0 with a range of 0.5. A level closer to 5 is better. The level of 4.0 or higher is on par with the typical output level.
[0452] The speed of the transfer sheet passing through the gripper portion of the fixture is 280 mm / s, which is driven to A4 size in the landscape direction. Rating criteria
[0453] 5.0: Slight change of brightness observed, but almost no rubbing damage seen with the naked eye. 4.0: Change of brightness observed with slight damage by rubbing. 3.0: Significant brightness change observed with apparent rubbing damage. 2.0: Apparent rubbing damage and slightly seen bottom transfer sheet. 1.0: Most part of the scraped image and background transfer sheet seen. High temperature stability (Storage)
[0454] Fill a glass container with the toner and leave it in a constant bath at 50 ° C for 24 hours. After cooling to 24 ° C, measure the level of penetration of the toner needle by a needle penetration test (according to JIS K2235-1991) to assess high temperature storage by the following criteria: A large needle penetration value represents excellent storage at high temperature. Toner having a needle penetration level less than 150 is likely to cause a problem. Rating criteria
[0455] E (Excellent): The needle penetration level is 250 or higher G (Good): The needle penetration level is 200 to less than 250 F (OK): The needle penetration level is 150 to less than 250 B (Bad): The needle protection level is less than 150 VB (very bad): The needle penetration level is less than 100 EXAMPLE 2 Example of manufacturing toner 2
[0456] Place 84 parts of A1 crystalline resin and 84 parts of ethyl acetate in a container equipped with a thermometer and stirrer and dissolve them by heating to the resin melting point or higher. Add 20 parts of the liquid dispersion of W1 wax, 12 parts of the master batch of coloring agent P1 and 50 parts of ethyl acetate to the container followed by stirring with a HOMOMIXER type TK (manufactured by PRIMIX Corporation) at a rotation number of 10,000 rpm at 50 ° C for uniform dissolution and dispersion to obtain oil phase 2.
[0457] Toner 2 having a volume average particle diameter of 5.6 µm is manufactured in the same way as in example 1 except that oil phase 2 is used instead of oil phase 1 to evaluate the performance of the toner and agent of revelation. EXAMPLE 3 Crystalline resin manufacturing example A2
[0458] Place 283 parts of stearic acid, 215 parts of 1,6-hexane diol, and 1 part of titanium dihydroxybis (triethanol aminate) as a condensation catalyst in a reaction vessel equipped with a condenser, stirrer and introduction tube nitrogen to conduct the reaction for eight hours at 180 ° C in a nitrogen atmosphere while distilling the produced water.
[0459] Then, conduct the reaction for four hours while gradually heating the system to 220 ° C and distilling the produced water and 1,6-hexane diol in a nitrogen atmosphere and continuing the reaction with a reduced pressure of 5 mmHg to 20 mmHg until the Mw reach about 6,000.
[0460] Transfer 249 parts by weight of the crystalline resin thus obtained to a reaction vessel equipped with a condenser, stirrer and nitrogen introducing tube and add 250 parts of ethyl acetate and 82 parts of hexamethylene diisocyanate (HDI) to it conduct the reaction at 80 ° C in a nitrogen atmosphere for five hours.
[0461] Then, distill ethyl acetate with reduced pressure to obtain crystalline resin A2 (polyester / polyurethane resin) having an Mw of about 20,000 and a maximum peak heat temperature of melting of 65 ° C. Example of manufacturing the master batch P2 of the coloring agent
[0462] Fabricate master batch P2 of the coloring agent in the same manner as in master batch P2 of the coloring agent of example 1 except that crystalline resin A2 is used instead of crystalline resin A1. Toner manufacturing example 3
[0463] Place 39 parts of crystalline resin A2 and 39 parts of ethyl acetate in a container equipped with a thermometer and stirrer and dissolve them by heating to the resin melting point or higher.
[0464] Add 90 parts of 50% ethyl acetate solution by weight of non-crystalline resin C1, 20 parts of the liquid dispersion of wax W1, 12 parts of the master batch P2 of the coloring agent, and 50 parts of ethyl acetate to the followed container by agitation by a HOMOMIXER type TK (manufactured by PRIMIX Corporation) at a rotation number of 10,000 rpm at 50 ° C for dissolution and uniform dispersion to obtain oil phase 3.
[0465] Manufacture toner 3 having a volume average particle diameter of 5.5 µm in the same way as in example 1 except that oil phase 3 is used instead of oil phase 1 to evaluate the performance of the toner and the cleaning agent. revelation. EXAMPLE 4 Manufacturing example of A3 crystalline resin
[0466] Place 322 parts of dodecanedioic acid, 215 parts of 1,6-hexane diol and 1 part of titanium dihydroxybis (triethanol aminate) as a condensation catalyst in a reaction vessel equipped with a condenser, a stirrer and an inlet tube. nitrogen to conduct the reaction for eight hours at 180 ° C in a nitrogen atmosphere while distilling the produced water.
[0467] Then, conduct the reaction for four hours while gradually heating the system to 220 ° C and distill the water produced and 1,6-hexane diol in a nitrogen atmosphere and continue the reaction with a reduced pressure of 5 mmHg to 20 ° C. mmHg until the Mw reaches about 6,000.
[0468] Transfer 269 parts of the crystalline resin thus obtained to a reaction vessel equipped with a condenser, stirrer and nitrogen introducing tube and add 280 parts of ethyl acetate and 85 parts of tolylene diisocyanate (TDI) to conduct the reaction at 80 ° C in a nitrogen atmosphere for five hours.
[0469] Then, distill ethyl acetate with reduced pressure to obtain crystalline resin A3 (polyester / polyurethane resin) having an Mw of about 18,000 and a maximum peak heat temperature of fusion of 68 ° C. Manufacturing example of master batch P3 of the coloring agent
[0470] Fabricate master batch P3 of the coloring agent in the same manner as in master batch P1 of the coloring agent of example 1 except that crystalline resin A3 is used instead of crystalline resin A1. Toner fabrication example 4
[0471] Place 39 parts of A3 crystalline resin and 39 parts of ethyl acetate in a container equipped with a thermometer and stirrer and dissolve them by heating to the resin melting point or higher. Add 90 parts of 50% ethyl acetate solution by weight of non-crystalline resin C1, 20 parts of the liquid dispersion of wax W1, 12 parts of the master batch P3 of the coloring agent and 50 parts of ethyl acetate to the container followed by agitation by a HOMOMIXER type TK (manufactured by PRIMIX Corporation) at a rotation number of 10,000 rpm at 50 ° C for uniform dissolution and dispersion to obtain oil phase 4.
[0472] Manufacture toner 4 having a volume average particle diameter of 5.6 µm in the same way as in example 1 except that oil phase 4 is used instead of oil phase 1 to evaluate the performance of the toner and the cleaning agent. revelation. EXAMPLE 5 Example of A4 crystalline resin manufacturing
[0473] Place 142 parts of sebacic acid, 136 parts of dimethyl terephthalic acid, 215 parts of 1,6-hexane diol and 1 part of hydroxybis titanate (triethanol aminate) as a condensation catalyst in a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introducing tube to conduct the reaction at 180 ° C in a nitrogen atmosphere while distilling the produced water.
[0474] Then, conduct the reaction for four hours while gradually heating the system to 220 ° C and distilling the produced water and 1,6-hexane diol in a nitrogen atmosphere and continue the reaction with a reduced pressure of 5 mmHg to 20 mmHg until the Mw reach about 6,000.
[0475] Transfer 247 parts of the crystalline resin thus obtained to a reaction vessel equipped with a condenser, a stirrer and a nitrogen introducing tube and add 270 parts of ethyl acetate and 123 parts of 4,4'-diphenyl methane diisocyanate (MDI ) to conduct the reaction at 80 ° C in a nitrogen atmosphere for five hours.
[0476] Then, distill ethyl acetate with reduced pressure to obtain crystalline resin A4 (polyester / polyurethane resin) having an Mw of about 11,000 and a maximum peak heat temperature of fusion of 52 ° C. Manufacturing example of the master batch P4 of the coloring agent
[0477] Fabricate master batch P4 of the coloring agent in the same manner as in master batch P1 of the coloring agent of example 1 except that crystalline resin 4 is used instead of crystalline resin A1. Toner manufacturing example 5
[0478] Place 39 parts of the A4 crystalline resin and 39 parts of ethyl acetate in a container equipped with a thermometer and a stirrer and dissolve them by heating to the resin melting point or higher. Add 90 parts of 50% ethyl acetate solution by weight of non-crystalline resin C1, 20 parts of the liquid dispersion of wax W1, 12 parts of the master batch P4 of the coloring agent, and 50 parts of ethyl acetate to the followed container by agitation by a HOMOMIXER type TK (manufactured by PRIMIX Corporation) at a rotation number of 10,000 rpm at 50 ° C for uniform dissolution and dispersion to obtain the oil phase 5.
[0479] Manufacture toner 5 having a volume average particle diameter of 5.6 µm in the same way as in example 1 except that oil phase 5 is used instead of oil phase 1 to evaluate the performance of the toner and the cleaning agent. revelation. EXAMPLE 6 Manufacturing example of non-crystalline resin C2
[0480] Place 215 parts of a bisphenol A adduct with 2 moles of propylene oxide, 132 parts of a bisphenol A adduct with 2 moles of ethylene oxide, 100 parts of terephthalic acid, 26 parts of adipic acid, and 1.8 parts tetrabutoxide titanate as a condensation catalyst in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introducing tube to conduct the reaction for six hours at 230 ° C in a nitrogen atmosphere while distilling the produced water.
[0481] Then, conduct the reaction for one hour with a reduced pressure from 5 mmHg to 20 mmHg.
[0482] Then cool to 180 ° C, add 5 parts of trimellitic anhydride and continue the reaction with a reduced pressure from 5 mmHg to 20 mmHg until the Mw reaches about 6,000. Toner manufacturing example 6
[0483] Place 39 parts of the crystalline resin Al and 39 parts of ethyl acetate in a container equipped with a thermometer and a stirrer and dissolve them by heating to the melting point of the resin or higher.
[0484] Add 90 parts of the 50% ethyl acetate solution by weight of the non-crystalline resin C2, 20 parts of the liquid wax dispersion W, 12 parts of the master batch P1 of the coloring agent, and 50 parts of ethyl acetate to the followed container by agitation by a HOMOMIXER type TK (manufactured by PRIMIX Corporation) at a rotation number of 10,000 rpm at 50 ° C for dissolution and uniform dispersion to obtain the oil phase 6.
[0485] Manufacture toner 6 having a volume average particle diameter of 5.7 µm in the same way as in example 1 except that oil phase 6 is used instead of oil phase 1 to evaluate the performance of the toner and the cleaning agent. revelation. EXAMPLE 7 Manufacturing example of crystalline resin A5
[0486] Place 126 parts of 1,4-butane diol, 215 parts of 1,6-hexane diol and 100 parts of methyl ethyl ketone (MEK) in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introducing tube followed by stirring and add 341 parts of hexamethylene diisocyanate (HDI) to them to conduct the reaction at 80 ° C in a nitrogen atmosphere for eight hours.
[0487] Then, distill the methyl ethyl ketone to obtain the crystalline resin A5 (polyurethane resin) having an Mw of about 18,000 and a maximum peak temperature of the melting heat of 59 ° C. Manufacturing example of master batch P5 of the coloring agent
[0488] Fabricate master batch P5 of the coloring agent in the same manner as in master batch P1 of the coloring agent of Example 1 except that crystalline resin A5 is used instead of crystalline resin A1. Toner manufacturing example 7
[0489] Place 39 parts of the crystalline resin A5 and 39 parts of ethyl acetate in a container equipped with a thermometer and a stirrer and dissolve them by heating to the melting point of the resin or higher.
[0490] Add 90 parts of 50% ethyl acetate solution by weight of non-crystalline resin C1, 20 parts of the liquid dispersion of wax W1, 12 parts of the master batch P5 of the coloring agent, and 50 parts of ethyl acetate to the followed container by agitation by a HOMOMIXER type TK manufactured by PRIMIX Corporation) at a rotation number of 10,000 rpm at 50 ° C for uniform dissolution and dispersion to obtain the oil phase 7.
[0491] Manufacture toner 7 having a volume average particle diameter of 5.6 µm in the same way as in example 1 except that oil phase 7 is used instead of oil phase 1 to evaluate the performance of the toner and the cleaning agent. revelation. EXAMPLE 8 Toner manufacturing example 8
[0492] Place 53 parts of crystalline resin A2 and 53 parts of ethyl acetate in a container equipped with a thermometer and stirrer and dissolve them by heating to the resin melting point or higher.
[0493] Add 62 parts of 50% ethyl acetate solution by weight of the non-crystalline resin C1, 20 parts of the liquid dispersion of wax W1, 12 parts of the master batch P2 of the coloring agent, and 50 parts of ethyl acetate to the followed container by agitation by a HOMOMIXER type TK manufactured by PRIMIX Corporation) at a rotation number of 10,000 rpm at 50 ° C for uniform dissolution and dispersion to obtain the oil phase 8.
[0494] Manufacture toner 8 having a volume average particle diameter of 5.6 µm in the same way as in example 1 except that oil phase 8 is used instead of oil phase 1 to evaluate the performance of the toner and the cleaning agent. revelation. EXAMPLE 9 Toner manufacturing example 9
[0495] Place 66 parts of A2 crystalline resin and 66 parts of ethyl acetate in a container equipped with a thermometer and stirrer and dissolve them by heating to the resin melting point or higher.
[0496] Add 36 parts of 50% ethyl acetate solution by weight of the non-crystalline resin C1, 20 parts of the liquid dispersion of wax W1, 12 parts of the master batch P2 of the coloring agent, and 50 parts of ethyl acetate to the followed container by agitation by a HOMOMIXER type TK manufactured by PRIMIX Corporation) at a rotation number of 10,000 rpm at 50 ° C for uniform dissolution and dispersion to obtain the oil phase 9.
[0497] Manufacture toner 9 having a volume average particle diameter of 5.5 µm in the same way as in example 1 except that oil phase 9 is used instead of oil phase 1 to evaluate the performance of the toner and the cleaning agent. revelation. EXAMPLE 10 Example of manufacturing toner 10
[0498] Place 84 parts of A2 crystalline resin and 84 parts of ethyl acetate in a container equipped with a thermometer and a stirrer and dissolve them by heating to the resin melting point or higher.
[0499] Add 20 parts of the liquid dispersion of the W1 wax, 12 parts of the master batch P2 of the coloring agent, and 50 parts of ethyl acetate to the container followed by stirring with a TK HOMOMIXER manufactured by (PRIMIX Corporation) at a rotation number of 10,000 rpm at 50 ° C for uniform dissolution and dispersion to obtain oil phase 10.
[0500] Manufacture toner 10 having a volume average particle diameter of 5.6 µm in the same way as in example 1 except that oil phase 10 is used instead of oil phase 1 to evaluate the performance of the toner and the cleaning agent. revelation. EXAMPLE 11 Crystalline resin manufacturing example B2
[0501] Place 247 parts of hexamethylene diamine (HDI) and 247 parts of ethyl acetate in a reaction vessel equipped with a condenser, stirrer and nitrogen introducing tube and add a resin solution in which 249 parts of A2 crystalline resin are dissolved in 249 parts of ethyl acetate therefor to conduct the reaction at 80 ° C for five hours in a nitrogen atmosphere to obtain 50% by weight ethyl acetate solution of the precursor of crystalline resins B2 having an isocyanate group in one far end. Example of manufacturing toner 11
[0502] Place 39 parts of crystalline resin A2 and 39 parts of ethyl acetate in a container equipped with a thermometer and stirrer and dissolve them by heating to the resin melting point or higher. Add 20 parts of the liquid dispersion of the W1 wax, 12 parts of the master batch P2 of the coloring agent, and 50 parts of ethyl acetate to the container followed by stirring by a TK HOMOMIXER manufactured by (PRIMIX Corporation) at a rotation number of 10,000 rpm at 50 ° C.
[0503] Add 90 parts of the 50% by weight ethyl acetate solution of crystalline resin precursor B2 to the container followed by a HOMOMIXER type TK (manufactured by PRIMIX Corporation) at a speed of 10,000 rpm for uniform dissolution and dispersion to obtain uniform oil phase 11.
[0504] Maintain the temperature of the oil phase 11 in the container to be 50 ° C and use it within five hours of manufacture before being crystallized.
[0505] Then add 90 parts of deionized water, 3 parts of 25% by weight of the liquid dispersion of the organic resin particles (styrene copolymer, methacrylic acid, butyl acrylate and a sodium salt of a sulfuric ester adduct with oxide methacrylate) of ethylene, manufactured by SANYO CHEMICALS INDUSTRIES LTD.) to stabilize the dispersion, 1 part of sodium carboxy methyl cellulose 16 parts of 48.3% by weight aqueous solution of sodium dodecyl sulfate diphenyl ether (EREMINOR MON-7, manufactured by SANYO CHEMICALS INDUSTRIES LTD.) and 5 parts of ethyl acetate in a container equipped with a stirrer and a thermometer and mix and shake them at 40 ° C to prepare a water phase solution. Add 80 parts of oil phase 11 maintained at 50 ° C and 7 parts of isophorone diamine to the water phase solution followed by mixing for one minute at 40 ° C to 50 ° C by a TK HOMOMIXER (manufactured by PRIMIX Corporation ) at a rotation number of 11,000 rpm to obtain the emulsion suspension 11.
[0506] Then, place the suspension in emulsion 11 in a reaction vessel equipped with a stirrer and a thermometer followed by removal of the solvent at 60 ° C for six hours. After aging for 10 hours (reaction) of the precursor of the unreacted crystalline resin at 45 ° C, suspension 11 is obtained.
[0507] Manufacture toner 11 having a volume average particle diameter of 5.6 µm in the same way as in example 1 except that suspension 11 is used instead of suspension 1 to evaluate the performance of the toner and developing agent. EXAMPLE 12 Toner manufacturing example 12
[0508] Initially mix 39 parts of crystalline resin A1, 45 parts of non-crystalline resin C1, 4 parts of microcrystalline wax (HI-Mic-1090, manufactured by NIPPON SEIRO CO., LTD.) Having a maximum endothermic peak temperature Wp melting heat) of 69 ° C, a start temperature of melting Ws of 57 ° C and a needle penetration degree of 5 to 25 ° C, and 12 parts of the master batch P1 of the coloring agent by a mixer HENSCHEL (manufactured by NIPPON COKE & ENGINEERING CO., LTD.) Followed by melting and mixing and kneading by a double wheel mixer (PCM-30, manufactured by IKEGAI CORPORATION) from 80 ° C to 120 ° C.
[0509] Cool the mixture obtained at room temperature followed by coarse spraying with a hammer mill to 200 µm to 300 µm.
[0510] Finely spray the resultant by a supersonic jet mill (Labojet, manufactured by NIPPON PNEUMATIC MFG. CO., LTD.) In order to obtain a weight average particle diameter of 5.2 µm to 5.8 µm while adjusting the pressure of spray air and classify the resultant by an airflow classifier (MDS-1, manufactured by NIPPON PNEUMATIC MFG. CO., LTD.) so that the weight average particle diameter is 5.9 µm to 6, 3 µm and the amount of fine powder having a weight average particle diameter of 4 µm or less is 10% by number or less while adjusting the blind opening to obtain the toner parent particle 12.
[0511] Manufacture toner 12 having a volume average particle diameter of 6.1 μπι in the same way as in example 1 except that the toner parent particle 12 is used instead of the toner parent particle 1 to evaluate the performance of the toner and the developing agent. EXAMPLE 13 Toner manufacturing example 13
[0512] Add 100 parts of oil phase 1 to an aqueous phase in which 100 parts of water, 5 parts of 48.3% by weight aqueous solution of sodium dodecyl disulfonate ester (EREMINOR MON-7, manufactured by SANYO & Co . KG) followed by emulsification by MANTON GAULIN in high pressure HOMOGENIZER (manufactured by GAULIN CO.) To obtain the emulsified suspension 13.
[0513] Place the emulsified suspension 13 in a container equipped with a stirrer and a thermometer followed by the removal of the solvent at 60 ° C for four hours to obtain a suspension.
[0514] The volume average particle diameter of the obtained suspension is measured by a particle size distribution analyzer (LA-920, manufactured by HORIBA LTD.) And found to be 0.15 µm.
[0515] Place 1,000 parts of water, 5 parts of 48.3% by weight aqueous solution of sodium dodecyl disulfonate ether (EREMINOR MON-7, manufactured by SANYO CHEMICALS INDUSTRIES, LTD.) And 800 parts of the suspension in a container equipped with a stirrer and a thermometer, adjust their pH to 10 by 2% by weight aqueous sodium hydroxide solution, and heat the system to 80 ° C while adding liquid in which 40 parts of magnesium chloride hexahydrate are dissolved in 40 parts of deionized water the resulting little by little while stirring.
[0516] Maintain the temperature at 80 ° C until the agglomerated particles grow to 5.6 µm to obtain the suspension 13.
[0517] Manufacture toner 13 having a volume average particle diameter of 5.6 µm in the same way as in example 1 except that suspension 13 is used instead of suspension 1 to evaluate the performance of the toner and developing agent. EXAMPLE 14 Manufacturing example of liquid dispersion of wax W2
[0518] Place and sufficiently dissolve 20 parts of microcrystalline wax (Hi-Mic-1070, manufactured by Nippon Seiro Co., Ltd.) having a maximum endothermic peak temperature Wp (melting point) of the melting heat of 60 ° C, a temperature of fusion initiation Ws of 42 ° C and a needle penetration degree of 20 to 25 ° C and 80 parts of ethyl acetate in a reaction vessel equipped with a condenser, stirrer and nitrogen introducing tube by heating the 78 ° C.
[0519] After cooling the system to 30 ° C in one hour while stirring, spray the resulting wet in an Ultra Visco mill manufactured by AIMEX Co., Ltd.) under the condition of a liquid feed speed of 1.0 kg / h, a peripheral disk speed of 10 m / s, 0.5 mm of zirconia bead fill quantity of 80% and a number of passes of 6 to obtain the liquid dispersion of wax W2. Toner manufacturing example 14
[0520] Place 39 parts of A2 crystalline resin and 39 parts of ethyl acetate in a container equipped with a thermometer and stirrer and dissolve them by heating to the resin melting point or higher. Add 20 parts of the liquid dispersion of W2 wax, 12 parts of the master batch of P2 coloring agent and 50 parts of ethyl acetate to the container followed by stirring with a TK HOMOMIXER (manufactured by PRIMIX Corporation) at a rotation number of 10,000 rpm at 50 ° C. Add 90 parts of 50% ethyl acetate solution by weight of crystalline resin precursor B2 to the container followed by a TOM HOMOMIXER (manufactured by PROMIX Corporation) at a speed of 10,000 rpm for uniform dissolution and dispersion to obtain uniform the oil phase 14.
[0521] Manufacture toner 14 having a volume average particle diameter of 5.5 µm in the same way as in example 11 except that oil phase 14 is used instead of oil phase 11 to evaluate the performance of the toner and the cleaning agent. revelation. EXAMPLE 15 Manufacturing example of liquid dispersion of wax W3
[0522] Place and dissolve sufficiently 8 parts of the microcrystalline wax (Hi-Mic-2095, manufactured by Nippon Seiro Co., Ltd.) having a maximum endothermic peak temperature Wp (melting point) of the melting heat of 82 ° C, a temperature of fusion initiation Ws of 64 ° C, and a degree of needle penetration of 20 to 25 ° C and 80 parts of ethyl acetate in a reaction vessel equipped with a condenser, stirrer and a nitrogen introducing tube by heating at 78 ° C. After cooling the system to 30 ° C in one hour while stirring, spray the resulting wet in an Ultra Visco mill manufactured by AIMEX Co., Ltd.) under the condition of a liquid feed speed of 1.0 kg / h , a peripheral disk speed of 10 m / s, 0.5 mm of the zirconia bead fill amount of 80%, and a number of passes of 6 to obtain the liquid dispersion of the W3 wax. Toner manufacturing example 15
[0523] Place 39 parts of crystalline resin A1 and 39 parts of ethyl acetate in a container equipped with a thermometer and a stirrer and dissolve them by heating to the resin melting point or higher. Add 20 parts of the liquid dispersion of the W3 wax, 12 parts of the master batch of coloring agent P1 and 50 parts of ethyl acetate to the container followed by stirring with a TK HOMOMIXER (manufactured by PRIMIX Corporation) at a rotation number of 10,000 rpm at 50 ° C. Add 90 parts of 50% ethyl acetate solution by weight of crystalline resin precursor B2 to the container followed by a TOM HOMOMIXER (manufactured by PROMIX Corporation) at a speed of 10,000 rpm for uniform dissolution and dispersion to obtain uniform the oil phase 15.
[0524] Manufacture toner 15 having a volume average particle diameter of 5.6 μπι in the same way as in example 11 except that oil phase 15 is used instead of oil phase 11 to evaluate the performance of the toner and the cleaning agent. revelation. EXAMPLE 16 Manufacturing example of liquid dispersion of wax W4
[0525] Place and dissolve sufficiently 20 parts of the microcrystalline wax (Hi-Mic-2065, manufactured by Nippon Seiro Co., Ltd.) having a maximum endothermic peak temperature Wp (melting point) of the melting heat of 58 ° C, a temperature melting initiation Ws of 39 ° C, and a needle penetration degree of 13 to 25 ° C and 80 parts of ethyl acetate in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introducing tube for heating at 78 ° C.
[0526] After cooling the system to 30 ° C in one hour while stirring, spray the resulting wet in an Ultra Visco mill manufactured by AIMEX Co., Ltd.) under the condition of a liquid feed speed of 1.0 kg / h , a peripheral disk speed of 10 m / s, 0.5 mm of the zirconia bead fill amount of 80%, and a number of passes of 6 to obtain the liquid dispersion of the W4 wax. Toner manufacturing example 16
[0527] Place 39 parts of A2 crystalline resin and 39 parts of ethyl acetate in a container equipped with a thermometer and stirrer and dissolve them by heating to the resin melting point or higher. Add 20 parts of the liquid dispersion of the wax. W4, 12 parts of the master batch of coloring agent P2 and 50 parts of ethyl acetate to the vessel followed by stirring by a TOM HOMOMIXER (manufactured by PRIMIX Corporation) at a speed of 10,000 rpm at 50 ° C.
[0528] Add 90 parts of 50% ethyl acetate solution by weight of crystalline resin precursor B2 to the container followed by a TOM HOMOMIXER (manufactured by PROMIX Corporation) at a speed of 10,000 rpm for uniform dissolution and dispersion to obtain uniform the oil phase 16.
[0529] Manufacture toner 16 having a volume average particle diameter of 5.7 µm in the same way as in example 11 except that oil phase 16 is used instead of oil phase 11 to evaluate the performance of the toner and the cleaning agent. revelation. EXAMPLE 17 Toner manufacturing example 17
[0530] Place 36 parts of A2 crystalline resin and 36 parts of ethyl acetate in a container equipped with a thermometer and stirrer and dissolve them by heating to the resin melting point or higher.
[0531] Add 50 parts of the liquid dispersion of wax W1, 12 parts of the master batch of coloring agent P2 and 32 parts of. ethyl acetate to the vessel followed by stirring by a TOM HOMOMIXER (manufactured by PRIMIX Corporation) at a rotation number of 10,000 rpm at 50 ° C. Add 84 parts of 50% ethyl acetate solution by weight of B2 crystalline resin precursor to the container followed by a TK HOMOMIXER (manufactured by PROMIX Corporation) at 10,000 rpm for uniform dissolution and dispersion to obtain uniform the oil phase 17.
[0532] Manufacture toner 17 having a volume average particle diameter of 5.7 μπι in the same way as in example 11 except that oil phase 17 is used instead of oil phase 11 to evaluate the performance of the toner and the cleaning agent. revelation. EXAMPLE 18
[0533] The performance of toner and developer is evaluated in the same way as in example 11 except that a refurbished imaging device B based on imaging device A in a way that the latent electrostatic imaging member, the the charger, the developing device, and the cleaner of the imaging device A are integrated into a detachable process cartridge detachable to the imaging device B is used instead of the imaging device A. COMPARATIVE EXAMPLE 1 Manufacturing example of liquid dispersion of wax W5
[0534] Place and dissolve sufficiently 20 parts of paraffin wax (Be Square 180 White, manufactured by TOYO ADL CORPORATION) having a wide endothermic peak range such as a maximum endothermic peak temperature Wp (melting point) of 67 ° melting heat C, a start temperature of melting Ws of 48 ° C, and a needle penetration degree of 10 to 25 ° C and 80 parts of ethyl acetate in a reaction vessel equipped with a condenser, a stirrer and a introduction of nitrogen heating to 78 ° C.
[0535] After cooling the system to 30 ° C in one hour while stirring, spray the resulting wet in an Ultra Visco mill manufactured by AIMEX CO., LTD.) Under the condition of a liquid feed speed of 1.0 kg / h , a disk peripheral speed of 10 m / s, 0.5 mm of zirconia bead fill amount of 80% by weight, and a pass number of 6 to obtain the liquid dispersion of the W5 wax. Toner Manufacturing Example 18
[0536] Place 39 parts of the crystalline resin Al and 39 parts of ethyl acetate in a container equipped with a thermometer and a stirrer and dissolve them by heating to the melting point of the resin or higher. Add 90 parts of 50% ethyl acetate solution by weight of non-crystalline resin C1, 20 parts of the liquid dispersion of wax W5, 12 parts of the master batch P1 of the coloring agent, and 50 parts of ethyl acetate to the followed container by agitation by a HOMOMIXER type TK (manufactured by PRIMIX Corporation) at a rotation number of 10,000 rpm at 50 ° C for dissolution and uniform dispersion to obtain the oil phase 18.
[0537] Manufacture toner 18 having a volume average particle diameter of 5.6 µm in the same way as in example 1 except that oil phase 18 is used instead of oil phase 1 to evaluate the performance of the toner and the cleaning agent. revelation. COMPARATIVE EXAMPLE 2 Manufacturing example of W6 liquid dispersion
[0538] Place and sufficiently dissolve 20 parts of paraffin wax (HNP-11, manufactured by (Nippon Seiro Co., Ltd.) having a sharp endothermic peak range such as an endothermic peak temperature ima Wp (melting point) of the heat of melting temperature of 68 ° C, a temperature of initiation of melting Ws of 63 ° C, and a needle penetration degree of 9 to 25 ° C and 80 parts of ethyl acetate in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introducing tube heating to 78 ° C.
[0539] After cooling the system to 30 ° C in one hour while stirring, spray the resulting wet in an Ultra Visco mill manufactured by AIMEX CO., LTD.) Under the condition of a liquid feed speed of 1.0 kg / h , a disk peripheral speed of 10 m / s, 0.5 mm of zirconia bead fill amount of 80% by weight, and a pass number of 6 to obtain the liquid dispersion of the W6 wax. Toner manufacturing example 19
[0540] Place 39 parts of the crystalline resin A1 and 39 parts of ethyl acetate in a container equipped with a thermometer and a stirrer and dissolve them by heating to the melting point of the resin or higher.
[0541] Add 90 parts of 50% by weight ethyl acetate solution of non-crystalline resin C1, 20 parts of the liquid dispersion of wax W6, 12 parts of the master batch P1 of the coloring agent, and 50 parts of ethyl acetate to the followed container by agitation by a HOMOMIXER type TK (manufactured by PRIMIX Corporation) at a rotation number of 10,000 rpm at 50 ° C for dissolution and uniform dispersion to obtain oil phase 189.
[0542] Manufacture toner 19 having a volume average particle diameter of 5.6 µm in the same way as in example 1 except that oil phase 19 is used instead of oil phase 1 to evaluate the performance of the toner and the cleaning agent. revelation. COMPARATIVE EXAMPLE 3 Toner manufacturing example 20
[0543] Place 39 parts of crystalline resin A2 and 39 parts of ethyl acetate in a container equipped with a thermometer and stirrer and dissolve them by heating to the resin melting point or higher.
[0544] Add 20 parts liquid dispersion of the W5 wax, 12 parts of the master batch P2 of the coloring agent, and 50 parts of ethyl acetate to the container followed by stirring with a TOM HOMOMIXER (manufactured by PRIMIX Corporation) at a rotation number of 10,000 rpm at 50 ° C.
[0545] Add 90 parts of the 50% by weight ethyl acetate solution of crystalline resin precursor B2 to the container followed by stirring with a TK HOMOMIXER (manufactured by PRIMIX Corporation) at a rotation number of 10,000 rpm for uniform dissolution and dispersion for get oil phase 20.
[0546] Manufacture toner 20 having a volume average particle diameter of 5.6 µm in the same way as in example 11 except that oil phase 20 is used instead of oil phase 11 to evaluate the performance of the toner and the cleaning agent. revelation. COMPARATIVE EXAMPLE 4 Example of manufacturing non-crystalline resin C3
[0547] Place 212 parts of a bisphenol A adduct with 2 moles of propylene oxide, 132 parts of a bisphenol A adduct with 2 moles of ethylene oxide, 100 parts of terephthalic acid, 26 parts of terephthalic acid, and 1.8 parts tetrabutoxide titanate as a condensation catalyst in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introducing tube to conduct the reaction for six hours at 230 ° C in a nitrogen atmosphere while distilling the produced water.
[0548] Then, conduct the reaction for one hour with a reduced pressure from 5 mmHg to 20 mmHg. After cooling to 180 ° C, place 5 parts of trimellitic anhydride and continue the reaction with a reduced pressure from 5 mmHg to 20 mmHg until the Mw reaches about 6,000.
[0549] Transfer 239 parts of the non-crystalline resin thus obtained to a reaction vessel equipped with a condenser, stirrer and nitrogen introducing tube and add 250 parts of ethyl acetate and 47 parts of hexamethylene diisocyanate (HDI) to conduct the reaction at 80 ° C in a nitrogen atmosphere for five hours.
[0550] Then, distill the ethyl acetate under reduced pressure to obtain the non-crystalline resin C3 (polyester / polyurethane resin) having an Mw of about 20,000, a glass transition temperature of 54 ° C and a maximum peak heat temperature melting temperature of 62 ° C. Manufacturing example of non-crystalline resin B3
[0551] Place 142 parts of hexamethylene diamine (HDI) and 150 parts of ethyl acetate in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introducing tube and add a resin solution in which 239 parts of the C3 non-crystalline resin they are dissolved in 239 parts of ethyl acetate to conduct the reaction at 80 ° C for five hours in a nitrogen atmosphere. 50% ethyl acetate solution by weight of the precursor of non-crystalline resins B3 having an isocyanate group at one end is obtained as a result. Manufacturing example of the master batch P6 of the coloring agent
[0552] Fabricate master batch P6 of the coloring agent in the same manner as in master batch P1 of the coloring agent of example 1 except that non-crystalline resin C3 is used instead of crystalline resin A1. Toner manufacturing example 21
[0553] Place 39 parts of C3 non-crystalline resin and 39 parts of ethyl acetate in a container equipped with a thermometer and stirrer and dissolve them by heating to the resin melting point or higher.
[0554] Add 20 parts liquid dispersion of the W1 wax, 12 parts of the master batch P6 of the coloring agent, and 50 parts of ethyl acetate to the container followed by agitation by a HOMOMIXER type TK (manufactured by PRIMIX Corporation) at a rotation number of 10,000 rpm at 50 ° C.
[0555] Add 90 parts of the 50% by weight ethyl acetate solution of the B3 crystalline resin precursor to the container followed by stirring with a TK HOMOMIXER (manufactured by PRIMIX Corporation) at a speed of 10,000 rpm for uniform dissolution and dispersion for obtain oil phase 21.
[0556] Manufacture toner 21 having a volume average particle diameter of 5.8 µm in the same way as in example 11 except that oil phase 21 is used instead of oil phase 11 to evaluate the performance of the toner and the cleaning agent. revelation. COMPARATIVE EXAMPLE 5 Manufacturing example of non-crystalline resin C4
[0557] Place 215 parts of a bisphenol A adduct with 2 moles of propylene oxide, q32 parts of a bisphenol A adduct with 2 moles of ethylene oxide, 100 parts of terephthalic acid, 26 parts of terephthalic acid and 1.8 parts of titanate tetrabutoxide as a condensation catalyst in a reaction vessel equipped with a condenser, a stirrer and a nitrogen introducing tube to conduct the reaction for six hours at 230 ° C in a nitrogen atmosphere while distilling the produced water.
[0558] Then, conduct the reaction for one hour with a reduced pressure from 5 mmHg to 20 mmHg.
[0559] After cooling to 180 ° C, place 5 parts of trimellitic anhydride and continue the reaction with a reduced pressure of 5 mmHg to 20 mmHg until the Mw reaches about 22,000 to obtain the non-crystalline resin C4 (polyester resin) having a temperature of glass transition of 52 ° C and a maximum peak temperature of the heat of fusion of 60 ° C. Manufacturing example of non-crystalline resin B4
[0560] Place 142 parts of hexamethylene diamine (HDI) and 150 parts of ethyl acetate in a reaction vessel equipped with a condenser, stirrer and nitrogen introducing tube and add a resin solution in which 239 parts of non-crystalline resin C4 are dissolved in 239 parts of ethyl acetate therefor to conduct the reaction at 80 ° C for five hours in a nitrogen atmosphere to obtain 50% by weight ethyl acetate solution of the precursor of non-crystalline resins B4 having an isocyanate group at one end. Manufacturing example of the master batch P7 of the coloring agent
[0561] Fabricate master batch P7 of the coloring agent in the same manner as in master batch P1 of the coloring agent of example 1 except that non-crystalline resin C4 is used instead of crystalline resin A1. Toner manufacturing example 22
[0562] Place 39 parts of C4 non-crystalline resin and 39 parts of ethyl acetate in a container equipped with a thermometer and stirrer and dissolve them by heating to the resin melting point or higher.
[0563] Add 20 parts of the liquid dispersion of wax W1, 12 parts of the master batch P7 of the coloring agent, and 50 parts of ethyl acetate to the container followed by stirring with a TOM HOMOMIXER (manufactured by PRIMIX Corporation) at a rotation number of 10,000 rpm at 50 ° C.
[0564] Add 90 parts of 50% ethyl acetate solution by weight of the non-crystalline resin precursor B4 to the container followed by stirring with a TK HOMOMIXER (manufactured by PRIMIX Corporation) at a rotation number of 10,000 rpm at 50 ° C to uniform dissolution and dispersion to obtain the oil phase 22.
[0565] Manufacture toner 22 having a volume average particle diameter of 5.6 µm in the same way as in example 11 except that oil phase 22 is used instead of oil phase 11 to evaluate the performance of the toner and the cleaning agent. revelation. COMPARATIVE EXAMPLE 6 Toner manufacturing example 23
[0566] Place 36 parts of the crystalline resin Al and 36 parts of ethyl acetate in a container equipped with a thermometer and a stirrer and dissolve them by heating to the melting point of the resin or higher. Add 84 parts of 50% by weight of the non-crystalline resin C1, 50 parts of the liquid dispersion of wax W5, 12 parts of the master batch P1 of the coloring agent, and 32 parts of ethyl acetate to the container followed by stirring with a HOMOMIXER type TK (manufactured by PRIMIX Corporation) at a rotation number of 10,000 rpm at 50 ° C for uniform dissolution and dispersion to obtain the oil phase 23.
[0567] Manufacture toner 23 having a volume average particle diameter of 5.6 µm in the same way as in example 1 except that oil phase 23 is used instead of oil phase 1 to evaluate the performance of the toner and the cleaning agent. revelation.
[0568] The C / A ratios for each toner are shown in table 3.


Dis / Sus method: Dissolution suspension method

权利要求:
Claims (11)
[0001]
Toner comprising: a coloring agent; a binder resin comprising a crystalline resin having a urethane skeleton and / or a urea skeleton; and a release agent comprising a microcrystalline wax, characterized by the fact that, in a diffraction spectrum of the toner obtained by X-ray diffraction, a ratio of C / (A + C) is 0.15 or greater, where C represents an integrated intensity of a spectrum deriving from a crystalline structure and A represents an intensity of spectrum integrity derived from a non-crystalline structure.
[0002]
Toner according to claim 1, characterized in that the binder resin comprising a crystalline resin comprises a urethane skeleton and / or a urea skeleton in an amount of 50% by weight or more.
[0003]
Toner according to any one of claims 1 to 2, characterized in that the crystalline resin comprises a polyurethane resin obtained by elongating and / or cross-linking a compound with a high content of diisocyanate and a polyester resin.
[0004]
Toner according to any one of claims 1 to 3, characterized in that the crystalline resin comprises a first crystalline resin and a second crystalline resin having a weight average molecular weight Mw greater than the first crystalline resin.
[0005]
Toner according to claim 4, characterized in that the second crystalline resin is obtained by elongating a modified crystalline resin having an isocyanate group at one end.
[0006]
Toner according to claim 4, characterized by the fact that the second crystalline resin is obtained by elongating a modified crystalline resin that is modified from the first crystalline resin to have a functional group reactive with an active hydrogen group.
[0007]
Toner according to any one of claims 1 to 6, characterized in that it satisfies the following relationship: WS (° C) ≤T (° C) Wp (° C) where T (° C) represents a maximum peak melting heating temperature of the toner measured by a differential scanning calorimeter (DSC), Wp (° C) represents a maximum peak melting heating temperature of the release agent measured by DSC, and Ws (° C) represents a melting start temperature defined as a temperature at an intersection of a tangent to a DSC curve of the release agent measured by DSC at a temperature at which a slope of the curve, which is a negative value, on a lower temperature side of Wp (° C) is maximum and a straight line extrapolating a baseline of the DSC curve of the release agent measured by DSC.
[0008]
Toner according to any one of claims 1 to 7, characterized in that the release agent has a penetration rate of 15 or lower at 25 ° C.
[0009]
Developing agent characterized by the fact that it comprises: a carrier; and the toner as defined in any one of claims 1 to 8.
[0010]
Imaging device characterized by the fact that it comprises: a member conducting an electrostatic latent image; a charger to charge a surface of the member carrying an electrostatic latent image; an irradiator to radiate the surface of the latent electrostatic image with light to form an electrostatic latent image thereon; a developing device for developing the latent electrostatic image with the developing agent as defined in claim 10 to form a visual image; a transfer device for transferring the visual image to a recording medium for forming an image for transfer therein; and a fixing device for fixing the transfer image on the recording medium.
[0011]
Process cartridge characterized by the fact that it comprises: a member conducting an electrostatic imaging to conduct the electrostatic imaging; and a developing device for developing the latent electrostatic image with the developing agent of claim 9 to form a visual image; wherein the process cartridge is detachably attachable to an image forming apparatus.

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同族专利:

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公开号 | 公开日

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EP2573621A1|2013-03-27|

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JP5769016B2|2015-08-26|

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法律状态:
2013-12-17| B03A| Publication of a patent application or of a certificate of addition of invention [chapter 3.1 patent gazette]|

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

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2020-05-19| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-10-27| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-01-12| 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 24/09/2012, 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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JP2011-207195|2011-09-22|

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JP2011207195A|JP5769016B2|2011-09-22|2011-09-22|Toner for electrophotography, developer using the toner, image forming apparatus, and process cartridge|

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