WO2010041677A1 - トナー - Google Patents
トナー Download PDFInfo
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- WO2010041677A1 WO2010041677A1 PCT/JP2009/067473 JP2009067473W WO2010041677A1 WO 2010041677 A1 WO2010041677 A1 WO 2010041677A1 JP 2009067473 W JP2009067473 W JP 2009067473W WO 2010041677 A1 WO2010041677 A1 WO 2010041677A1
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- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08742—Binders for toner particles comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- G03G9/08771—Polymers having sulfur in the main chain, with or without oxygen, nitrogen or carbon only
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
- G03G9/08795—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by their chemical properties, e.g. acidity, molecular weight, sensitivity to reactants
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
- G03G9/08797—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by their physical properties, e.g. viscosity, solubility, melting temperature, softening temperature, glass transition temperature
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/093—Encapsulated toner particles
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/093—Encapsulated toner particles
- G03G9/09307—Encapsulated toner particles specified by the shell material
- G03G9/09314—Macromolecular compounds
- G03G9/09321—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
Definitions
- the present invention relates to a toner used in an electrophotographic method or a toner jet method.
- the electrophotographic method has received various requests such as higher image quality, smaller and lighter apparatus, higher speed, and energy saving. For this purpose, it is required to improve toner fixing performance. In particular, there is a demand for improvement in performance (hereinafter referred to as low-temperature fixing performance) capable of fixing toner onto a transfer material at a lower temperature.
- the performance for suppressing the occurrence of image defects (hereinafter referred to as durability stability performance) in continuous printing tends to decrease after long-term storage in a high-temperature and high-humidity environment.
- durability stability performance the performance for suppressing the occurrence of image defects
- the toner on the transfer material adheres to the fixing member, the toner suppresses offset, which is a phenomenon that stains the transfer material by transferring to the transfer material again (hereinafter referred to as offset resistance performance). Tends to decrease.
- gloss performance performance to improve the color developability of the image
- anti-smudge performance performance to suppress unevenness in image gloss
- Patent Documents 1 and 2 disclose that the core particles having a low glass transition point (Tg) are coated with a shell layer having a high Tg, thereby preventing the core particles from oozing out to the toner surface during storage, and the low-temperature fixing performance of the toner. And an improvement in stability in continuous printing.
- Tg glass transition point
- Patent Document 3 describes the ratio of storage elastic modulus G ′ measured at different frequencies by measuring the dynamic viscoelasticity of a toner at a temperature of Tg + 35 ° C. as a rheological characteristic of the binder resin contained in the toner. By controlling this value, it is aimed to achieve both low-temperature fixing performance of toner and improvement of stability in continuous printing.
- An object of the present invention is to provide a toner capable of solving the above-described problems. That is, the object of the present invention is a toner containing wax, which has good durability and stability even when the low-temperature fixing performance is improved, and is excellent in anti-offset performance, gloss performance, and penetration resistance. An object of the present invention is to provide a toner capable of forming a high-quality image.
- the present invention is a toner containing toner particles having at least a binder resin, a colorant, and wax, and inorganic fine particles, wherein the toner has a storage elastic modulus (G′1) at a frequency of 1 Hz on the y-axis.
- the ratio (G′10 / G′1) to the storage elastic modulus (G′10) at a frequency of 10 Hz was created by plotting the measurement temperature (° C.) of the storage elastic modulus on the x-axis (temperature ⁇ G ′ 10 / G′1) In the curve, a temperature having a maximum value A at a temperature of 60.0 to 135.0 ° C., a maximum value B at a temperature of 35.0 to 85.0 ° C.
- the toner containing wax has good durability and stability even when the low-temperature fixing performance is improved, and is excellent in offset resistance performance, gloss performance, and penetration resistance performance, A high-quality image can be formed.
- FIG. 4 is a conceptual diagram showing a positional relationship when toner pellets are set in a dynamic viscoelasticity measuring device in the present invention.
- FIG. 6 is a diagram illustrating an example of a (temperature-G′10 / G′1) curve of toners according to examples and comparative examples of the present invention.
- the toner of the present invention has the following physical properties in order to improve the low-temperature fixing performance of the toner, suppress the decrease in durability stability performance, and form a high-quality image. I found it important. That is, the toner of the present invention has a temperature-storage when the dynamic viscoelasticity measurement of the toner is performed at a high frequency with respect to a temperature-storage elastic modulus curve when the dynamic viscoelasticity measurement of the toner is performed at a low frequency.
- the elastic modulus curve is characterized by a characteristic change in behavior in a specific temperature range.
- a sample formed by pressure molding using a tablet molding machine in an environment of a temperature of 25 ° C. and a humidity of 60% RH is used.
- the true density of the toner is ⁇ (g / cm 3 )
- the toner is weighed 0.20 ⁇ ⁇ (g)
- a 20 kN load is applied for 2 minutes, and a cylindrical pellet having a diameter of 8 mm and a thickness of about 4 mm is obtained. Mold.
- the following measurements are performed using this pellet.
- ARES Rivometric Scientific F.E. Co., Ltd.
- measurement is performed under the following measurement conditions in accordance with the operation manual of the measuring instrument.
- FIG. 2 is a conceptual diagram of the surface shape of a serrated parallel plate used for measuring the dynamic viscoelasticity of toner in the present invention.
- FIG. 3 is a conceptual diagram showing the positional relationship when the toner pellets are set in the dynamic viscoelasticity measuring apparatus.
- the measurement operation is as follows. ⁇ Previous operation> The sample chamber of the measuring apparatus is held at 25.0 ° C. in advance, the pellet is set so that the load (Axial Force) is 30, and the hold switch is turned on.
- the hold switch has a function to hold the load applied to the pellet at the value of the load when the switch is turned on by adjusting the distance between the plates sandwiching the pellet (Gap; distance between the convex portions of both plates).
- TgT glass transition point of the toner measured by a differential scanning calorimeter (DSC) described later
- DSC differential scanning calorimeter
- the temperature of the sample chamber is heated to TgT + 2 (° C.).
- the hold switch is removed, the distance (Gap) between the plates is adjusted so that the load applied to the pellet (Axial Force) is 1500, and the hold switch is turned on again. Then, since the convex portion of the serrated plate is gradually embedded in the surface of the pellet due to the load, the distance (Gap) between the plates gradually decreases.
- the hold switch is removed when the distance (Gap) between the plates becomes 10% smaller than the distance (Gap) between the plates when the hold switch is turned on as the load 1500. Further, the distance between the plates is increased so that the load (Axial Force) applied to the pellet is 150. At this time, care should be taken to move the plate slowly and gradually. Also, the load should not be less than 150.
- the hold switch is turned on again, and the temperature of the sample chamber is set to the measurement start temperature.
- the measurement start temperature is TgT-10 (° C.).
- TgT-10 ° C.
- FIG. 4 shows an example of a (temperature-G′10 / G′1) curve of toners according to examples and comparative examples of the present invention.
- the rate of temperature increase is 2.0 ° C./min and the measurement interval is 30 seconds, so that storage modulus data in increments of 1.0 ° C. can be obtained.
- the temperature in both the measurement at 1 Hz and 10 Hz may slightly shift. In that case, the average value of the measured temperature at the frequency of 1 Hz and the measured temperature at the frequency of 10 Hz is plotted as the measured temperature. Further, a fine sharp peak may appear in the obtained (temperature-G′10 / G′1) curve due to the influence of measurement error, but the maximum value defined in the present invention is a certain temperature range. It is a local maximum at a large peak having
- the toner of the present invention is a toner containing toner particles having at least a binder resin, a colorant, and a wax, and inorganic fine particles, and has a temperature of 60 in the (temperature ⁇ G′10 / G′1) curve. 0.0 to 135.0 ° C. has a maximum value A, a temperature 35.0 to 85.0 ° C.
- the temperature indicating the maximum value A is Ta (° C.)
- the maximum value B is When the temperature shown is Tb (° C.), Ta is larger than Tb, the difference between Ta and Tb (Ta ⁇ Tb) (° C.) is 15.0 to 90.0 ° C., and G ′ in Ta When the value of 10 / G′1 (G′a) is 5.0 or more, the above-described object can be achieved.
- thermoplastic resin when dynamic viscoelasticity measurement of a thermoplastic resin is performed, there is a correlation between temperature and frequency. Measuring at a high frequency, that is, increasing the deformation rate of the sample to be measured corresponds to measuring at a low temperature, and measuring at a low frequency, that is, reducing the deformation rate of the sample to be measured Corresponding to measuring at high temperature. For this reason, when a general dynamic viscoelasticity measurement of toner is performed at a frequency of 1 Hz and a frequency of 10 Hz, the (temperature-G′1) curve and the (temperature-G′10) curve have almost the same shape.
- the temperature-G′10) curve is a state in which the (temperature-G′1) curve is shifted parallel to the high temperature side by about 5 to 10 ° C.
- G′10 / G′1 is 5.0 or more in the high temperature side region of 60.0 to 135.0 ° C. Such a local maximum does not appear.
- the toner of the present invention has a curve shape in a temperature range on the high temperature side such as a temperature of 60.0 to 135.0 ° C. It has the feature of being different. That is, in the temperature range on the high temperature side such as the temperature of 60.0 to 135.0 ° C., there is a portion where the value of G′10 is particularly large compared to G′1, and thus (temperature ⁇ G′10 / G '1) A maximum value A (temperature indicating maximum value A: Ta (° C.)) is detected in the curve. Further, when the behavior change of the (temperature-G′10) curve in the temperature region on the high temperature side such as the temperature of 60.0 to 135.0 ° C. has an intensity exceeding a certain range, the effect of the present invention is exhibited well.
- the effects of the present invention cannot be obtained.
- G′10 (Pa) is too small as compared with G′1 (Pa) at Ta (° C.)
- the durability stability performance, anti-offset performance, and penetration resistance of the toner are lowered.
- G′1 (Pa) is too large compared with G′10 (Pa) at Ta (° C.)
- the low-temperature fixing performance and gloss performance of the toner are deteriorated.
- the G′a is preferably 6.0 or more, more preferably 8.0 or more.
- the reason why the above-mentioned characteristics are observed is considered that the toner of the present invention has a thermodynamically hard part and a soft part.
- G′a is preferably 5.0 to 20.0, more preferably 5.0 to 15.0, and further preferably 6.0 to 14.0. preferable. A particularly preferable range of G′a is 8.0 to 14.0.
- the Ta showing the maximum value A is less than 60.0 ° C.
- the offset resistance performance, the penetration resistance performance, and the durability stability performance of the toner are deteriorated.
- the Ta exceeds 135.0 ° C.
- the low-temperature fixing performance and gloss performance of the toner deteriorate.
- the toner has a portion that is too hard thermally, the toner tends to become brittle, and the durability stability performance of the toner may be reduced.
- the Ta is 60.0 to 135.0 ° C, preferably 65.0 to 135.0 ° C, and more preferably 70.0 to 130.0 ° C.
- the particularly preferable range of Ta is 80.0 to 125.0 ° C.
- the Tb showing the maximum value B is less than 35.0 ° C.
- the toner is too soft, so that the impregnation performance and durability stability performance of the toner cannot be sufficiently obtained.
- the Tb exceeds 85.0 ° C., it becomes too hard, and the low-temperature fixing performance and gloss performance of the toner cannot be sufficiently obtained.
- the Tb is 35.0 to 85.0 ° C, preferably 45.0 to 80.0 ° C, and more preferably 50.0 to 80.0 ° C.
- the particularly preferable range of Tb is 50.0 to 75.0 ° C.
- the (Ta—Tb) is 15.0 to 90.0 ° C., preferably 15.0 to 85.0 ° C., more preferably 20.0 to 82.0 ° C.
- a particularly preferable range of (Ta—Tb) is 30.0 to 82.0 ° C.
- a resin having properties different from those of the binder resin is added in addition to the type and amount of the binder resin and wax contained in the toner particles. And the uniformity of the content of these materials in the toner and the uniformity of the state of presence in the toner.
- the toner As a method for causing the toner to exhibit the characteristic properties as described above, there may be considered a method of coating the soft core phase with the hard shell phase and a method of coating the hard core phase with the soft shell phase as the constitution of the toner particles. Of these, the former is preferred. However, when dynamic viscoelasticity measurement is performed by mixing a resin b having a certain glass transition point (Tg) and a resin a having a higher Tg than the resin b, the resin a and the resin b are In a compatible state, a behavior change corresponding to Tg of the resin a or the resin b is generally not detected.
- Tg glass transition point
- the toner of the present invention is in a state in which a part of the core phase and a part of the shell phase are compatible, and the core phase, and the phase in which the core component covering the core phase and the shell component are compatible. It is presumed that this has a two-layer structure or a three-layer structure with a shell phase covering the two-layer structure.
- the shell phase is synchronized with the behavior of the core phase under the measurement condition of a relatively low frequency such as 1 Hz, that is, low-speed distortion, and the property of the shell phase is not noticeable. Accordingly, in the (temperature-G′1) curve, only the physical properties of the core phase that is the main component of the toner are detected.
- G′a has a large value of 5.0 or more is considered to be because the coating state of the shell phase with respect to the core phase is uniform among the toner particles. That is, as the material contained in the toner particles, the content of the binder resin as the main component of the core phase and the content of the shell resin covering the core phase are uniform among the toner particles, and the toner particles This is probably because the compatibility between the binder resin and the shell resin is uniform.
- G′a is considered to be an index of uniformity with respect to the entire toner when the formation state of the core-shell structure is compared for each toner particle.
- the Tb (° C.) is considered to be a value corresponding to the glass transition point (Tg) of the binder resin that the toner has.
- the Ta (° C.) is considered to be a value corresponding to the Tg of the shell resin, the addition amount, and the compatible state of the shell resin and the binder resin.
- the difference (G′a ⁇ G′b) between the G′10 / G′1 value (G′b) and the G′a at the Tb (° C.) is 1.0 to 15. 0 is preferred.
- the (G′a ⁇ G′b) indicates the difference in the magnitude of the thermal behavior change between the core phase and the shell phase.
- the (G′a ⁇ G′b) is less than 1.0, the change in the thermal behavior of the core phase is more remarkable than that of the shell phase. In some cases, the durability stability performance and the penetration resistance performance of the toner may decrease. Further, when aiming to improve the durability and stability performance of the toner, the low-temperature fixing performance and gloss performance of the toner may deteriorate.
- the (G′a ⁇ G′b) exceeds 15.0, the difference in the thermal behavior between the core phase and the shell phase is significant, so that the low-temperature fixing performance, durability stability performance, and gloss performance of the toner decrease. There is a case. Therefore, the (G′a ⁇ G′b) is more preferably from 1.5 to 10.0, and even more preferably from 4.0 to 8.0.
- the above (G′a-G′b) is the addition and addition of a resin having properties different from those of the binder resin, in addition to the type and addition amount of the binder resin and wax contained in the toner particles, and It can be controlled by the uniformity of the content of these materials in the toner and the uniformity of the state of presence in the toner.
- the toner of the present invention preferably has a G′1 value (G′1Ta) in the Ta (° C.) of 1,000 to 300,000 Pa.
- G′1Ta G′1 value
- the toner having G′a of 5.0 or more when G′1Ta is in the above range, the toner has better low-temperature fixing performance, development stability performance, gloss performance and penetration resistance performance. .
- the G′1Ta is less than 1000 Pa, the development stability performance, anti-offset performance, and penetration resistance of the toner may be reduced.
- the G′1Ta exceeds 300000 Pa, the low-temperature fixing performance and gloss performance of the toner may be deteriorated.
- the G′1Ta is more preferably 2000 to 100000 Pa, and further preferably 2000 to 50000 Pa.
- the above G′1Ta is not limited to the type and amount of binder resin, wax, etc. contained in the toner particles, but also to the addition of a resin having properties different from those of the binder resin, and those materials in the toner. It can be controlled by the uniformity of the content rate and the uniformity of the state of presence in the toner.
- the molecular weight distribution in terms of polystyrene (PSt) calculated by gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble component of the toner has a molecular weight of 5000 to 30000 with a peak molecular weight [maximum molecular weight] (Mp).
- the weight average molecular weight (Mw) is 6,000 to 200,000, and the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 3.0 to 20.0. Is preferred.
- the low temperature fixing performance, gloss performance and anti-smudge performance are further improved while maintaining the durability and stability performance of the toner.
- the Mp is more preferably 7000 to 25000, and further preferably 7000 to 20000.
- the particularly preferable range of Mp is 8000 to 16000.
- the Mw is more preferably 10,000 to 150,000, and further preferably 10,000 to 120,000.
- the particularly preferable range of Mw is 30,000 to 100,000.
- the Mw / Mn is more preferably 5.0 to 20.0, and further preferably 5.0 to 12.0.
- the Mp, Mw, and Mw / Mn can be controlled by the type and amount of additives such as binder resin and wax contained in the toner particles, and shell resin.
- the toner of the present invention is based on a polymerization method, it depends on the type and amount of polymerization initiator, the polymerization temperature, particularly the temperature at the start of polymerization relative to the 10-hour half-life temperature of the polymerization initiator, the type and amount of crosslinking agent, etc. It can be controlled.
- the toner of the present invention contains a THF-insoluble component obtained by the Soxhlet extraction method, and the content of the THF-insoluble component obtained by the Soxhlet extraction method is preferably 5.0 to 35.0% by mass with respect to the toner.
- the low temperature fixing performance, gloss performance and anti-smudge performance are further improved while maintaining the durability and stability performance of the toner.
- the content of the THF-insoluble component is more preferably 5.0 to 20.0, and further preferably 5.0 to 12.0.
- the particularly preferable range of the content of the THF-insoluble component is 6.0 to 10.0.
- the content of the THF-insoluble component can be controlled by the type and amount of additives such as a binder resin and wax contained in the toner particles and a shell resin.
- additives such as a binder resin and wax contained in the toner particles and a shell resin.
- the toner of the present invention depends on the type and amount of polymerization initiator, the polymerization temperature, particularly the temperature at the start of polymerization relative to the 10-hour half-life temperature of the polymerization initiator, the type and amount of crosslinking agent, etc. It can be controlled.
- the content of the THF-insoluble component is in the above range, and the addition amount of the crosslinking agent with respect to 100 parts by mass of the polymerizable monomer that is a raw material of the binder resin that the toner has Is preferably 0.40 to 3.00 parts by mass.
- the addition amount of the cross-linking agent is in the above range, the content of the THF insoluble component of the toner generally tends to increase, but when the content of the THF insoluble component is within the above range, the low temperature fixing performance and durability stability of the toner are increased. Performance is even better.
- the amount of the THF-insoluble component contained in the toner is small even though the amount of the crosslinking agent added is large, it is considered that the binder resin contained in the toner has many branched molecular chains but few crosslinked bonds.
- a shell resin is used because of a large amount of a crosslinking agent.
- the content of the THF-insoluble component which is cross-linked and has in the toner tends to increase particularly.
- the addition amount of the crosslinking agent is more preferably 0.50 to 2.00 parts by mass, and further preferably 0.70 to 1.40 parts by mass.
- Tg glass transition point of the binder resin contained in the toner particles
- Tg glass transition point of the binder resin contained in the toner particles
- a method in which the polymerization temperature at the start of polymerization is set higher by 15.0 to 50.0 ° C. than the 10-hour half-life temperature of the polymerization initiator is preferable because the radical concentration at the initial stage of polymerization can be increased. Since the radical concentration at the initial stage of polymerization is high, a large number of polymer chains having a uniform molecular weight can be produced from an early stage of the polymerization process.
- the content of the THF-insoluble component can be controlled less than usual. Also, by increasing the polymerization temperature relative to the Tg of the binder resin, the movement of the molecular chain during the polymerization becomes intense, the cross-linking is suppressed, and as a result, the content of the THF-insoluble component of the toner is controlled to be small. it is conceivable that. Moreover, it is controllable also with the kind and addition amount of additives, such as resin for shells.
- the toner of the present invention contains a THF-soluble component by a Soxhlet extraction method, and the content of sulfur element derived from a sulfonic acid group by fluorescence X-ray measurement of the THF-soluble component is the content of the THF-soluble component.
- the content is preferably 0.005 to 0.300% by mass. This point will be described later.
- the toner of the present invention contains a 2-propanol (IPA) soluble component obtained by a Soxhlet extraction method, and the content of the 2-propanol (IPA) soluble component is 10.0 to 50.0% by mass based on the toner. It is preferable that The IPA-soluble component is considered to be a component that improves the thermoplasticity of the toner, such as a component having a relatively low molecular weight, a component having a low Tg, and a wax contained in the binder resin of the toner.
- IPA 2-propanol
- the content of the IPA-soluble component within the above range indicates that in the case of a toner by a polymerization method, the molecular weight and composition of the binder resin and the like are not all uniform in the polymerization process and have some variation. .
- the content of the IPA-soluble component is large.
- the durability stability performance and the penetration resistance performance of the toner. May decrease.
- the content of the IPA-soluble component is particularly preferably in the above range.
- the THF-insoluble component is advantageous for improving the offset resistance performance of the toner, when a large amount of the THF-insoluble component is contained, the compatibility between the core phase and the shell phase may be lowered.
- the amount of the THF-insoluble component is limited to a relatively small amount, and a certain amount of the component insoluble in IPA is contained to improve the compatibility between the core phase and the shell phase, and the offset resistance performance of the toner is also expressed well.
- the content of the IPA-soluble component is more preferably 10.0 to 40.0% by mass, and further preferably 10.0 to 35.0% by mass. preferable.
- the content of the IPA-soluble component is particularly preferably 10.0 to 30.0% by mass.
- the content of the IPA-soluble component can be controlled by the polymerization temperature with respect to the glass transition point (Tg) of the binder resin contained in the toner particles, the type and addition amount of the polymerization initiator, the type and addition amount of the crosslinking agent, and the like. It is.
- a method in which the polymerization temperature at the start of polymerization is set higher by 15.0 to 50.0 ° C. than the 10-hour half-life temperature of the polymerization initiator is preferable because the radical concentration at the initial stage of polymerization can be increased. Since the radical concentration at the initial stage of polymerization is high, a large number of molecular chains with high molecular weight can be produced from the early stage of the polymerization process.
- the content of the IPA-soluble component can be suitably controlled.
- the polymerization temperature relative to the Tg of the binder resin the movement of molecular chains during polymerization becomes intense, and the binding reaction between molecular chains in the middle of growth is suppressed.
- the toner has an IPA soluble property.
- the content of the components can be increased.
- it is controllable also with the kind and addition amount of additives, such as resin for shells.
- a styrene acrylic resin having acrylic acid or methacrylic acid as a copolymerization component is added to 100 parts by mass of the binder resin. It is preferable to contain 3.0 to 40.0 parts by mass.
- the styrene acrylic resin preferably has an acid value of 3.0 to 30.0 mgKOH / g.
- the toner particles according to the present invention preferably have a core-shell structure, and the styrene acrylic resin is preferably present as a resin constituting the shell phase.
- the styrene acrylic resin can be efficiently localized near the surface of the toner by the action of acrylic acid or methacrylic acid. Since the styrene acrylic resin has styrene and acrylic acid or methacrylic acid as a copolymerization component, the resin and the binder resin of the toner are partially compatible so that the interface between the two does not exist clearly. become. Further, when the acid value of the styrene acrylic resin is 3.0 to 30.0 mg KOH / g, the resin is localized in the vicinity of the surface of the toner particles, and the resin is compatible with the binder resin. The balance with action becomes better.
- the acid value of the resin is more preferably 5.0 to 20.0 mgKOH / g, and still more preferably 6.0 to 15.0 mgKOH / g.
- the content of the resin is more preferably 5.0 to 30.0 parts by mass, and further preferably 10.0 to 25.0 parts by mass.
- the styrene acrylic resin preferably contains 85.0% by mass or more of a tetrahydrofuran (THF) soluble component and 90.0% by mass or more of a methanol-insoluble component.
- THF tetrahydrofuran
- the content of the THF soluble component in the styrene acrylic resin is within the above range, the uniformity of the content of the styrene acrylic resin in each toner particle is further improved. Further, in the case of a toner manufacturing method in which particles are formed in water, the toner particle size distribution can be made sharper.
- the content of the THF-soluble component contained in the styrene acrylic resin is more preferably 90.0% by mass or more, and particularly preferably 96.0% by mass or more.
- the styrene acrylic resin when the acid value is 3.0 to 30.0 mg KOH / g, a component that dissolves in methanol tends to be by-produced.
- the uniformity of the content of the styrene acrylic resin in each toner particle is further increased.
- the uniformity of the existence state in which the styrene acrylic resin is localized in each toner particle is increased.
- the content of the methanol insoluble component contained in the styrene acrylic resin is more preferably 95.0% by mass or more, and further preferably 96.0 to 99.5% by mass.
- the styrene acrylic resin has a styrene (PSt) conversion weight average molecular weight (Mw) of 2500 to 150,000 by gel permeation chromatography (GPC), and the weight average molecular weight (Mw) and the number average molecular weight (Mn)
- PSD gel permeation chromatography
- Mw weight average molecular weight
- Mn number average molecular weight
- the ratio (Mw / Mn) is preferably 1.10 to 10.00.
- the Mw of the styrene acrylic resin is more preferably 3000 to 120,000, and still more preferably 3000 to 60000.
- Mw of the styrene acrylic resin is 6000 to 60000.
- Mw / Mn of the styrene acrylic resin is within the above range, the uniformity of the content of the resin contained in each toner particle is increased, and the durability stability performance of the toner is further improved.
- the Mw / Mn of the resin is more preferably 1.50 to 5.00, and further preferably 2.00 to 4.00.
- the styrene acrylic resin preferably has a ratio (Mp / Mw) of the peak molecular weight [maximum molecular weight] (Mp) and the Mw in the molecular weight distribution in terms of styrene by GPC to 0.50 to 3.00.
- Mp peak molecular weight
- Mw peak molecular weight
- Mw the Mw in the molecular weight distribution in terms of styrene by GPC to 0.50 to 3.00.
- a small value of Mp / Mw indicates that the content of a component having a particularly large molecular weight is small relative to the component having a molecular weight as a main component, and the uniformity of the resin contained in each toner particle. It is preferable in terms of improvement. In this case, the durability stability performance of the toner is good.
- the Mp / Mw of the resin is more preferably 0.80 to 2.00, and further preferably 0.90 to 1.50. Particularly preferable Mp / Mw of the
- the styrene acrylic resin preferably has a glass transition point (Tg) measured by a differential scanning calorimeter (DSC) of 55.0 to 95.0 ° C.
- Tg glass transition point measured by a differential scanning calorimeter
- DSC differential scanning calorimeter
- the Tg by DSC of the resin is more preferably 60.0 to 95.0 ° C., and further preferably 65.0 to 95.0.
- the styrene acrylic resin produced by the following method can be used.
- the styrene acrylic resin is preferably produced by (3) a dropping polymerization method.
- the difference in polymerization rate between styrene and an acid monomer such as acrylic acid or methacrylic acid is suppressed, and the content of a THF soluble component and a methanol insoluble component is easily suppressed.
- the polymerization is preferably performed by a pressure polymerization method. The reaction proceeds more uniformly, and the content of THF-soluble components and methanol-insoluble components can be easily suppressed.
- the mixing ratio of acrylic monomers having a monomer Q value smaller than that of styrene is reduced at the initial stage of polymerization relative to the target copolymerization ratio of styrene and acrylic monomers.
- the polymer is produced by a multistage dropping polymerization method in which the blending ratio of the acrylic monomer is increased with progress.
- the content of acrylic acid or methacrylic acid contained in each molecular chain of the styrene acrylic resin can be made more uniform, and the Mw / Mn of the resin can be kept at a small value.
- the Q value is a value unique to the monomer and is a value indicating reactivity in copolymerization.
- the toner of the present invention has a weight average particle diameter (D4) of 3.0 to 8.0 ⁇ m, and a ratio (D4 / D1) of D4 to the number average particle diameter D1 of 1.00 to 1.30. Preferably there is.
- the durability and stability of the toner becomes better.
- (D4 / D1) is within the above range, the content and presence state of the shell phase contained in the toner become more uniform.
- the (D4 / D1) is an index indicating the degree of particle size distribution, and is 1.00 when it is completely monodispersed. The larger the value is than 1.00, the larger the particle size distribution.
- the D4 is more preferably 3.0 to 7.0 ⁇ m, still more preferably 4.0 to 6.0 ⁇ m.
- the (D4 / D1) is more preferably 1.00 to 1.25, and still more preferably 1.00 to 1.20.
- the (D4 / D1) is particularly preferably from 1.00 to 1.15.
- the toner of the present invention has a circularity measured by a flow type particle image measuring apparatus having an image processing resolution of 512 ⁇ 512 pixels (0.37 ⁇ m ⁇ 0.37 ⁇ m per pixel), and a circularity of 0.200 to 1.000.
- the average circularity of the toner analyzed by dividing into 800 ranges is preferably 0.960 to 1.000. When the average circularity is 0.960 to 1.000, the content and presence state of the shell phase contained in the toner becomes more uniform.
- the average circularity is more preferably 0.970 to 1.000, and further preferably 0.980 to 1.000.
- a flow type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation) can be mentioned.
- the measurement principle of the flow-type particle image analyzer “FPIA-3000” is to capture flowing particles as a still image and perform image analysis.
- the sample added to the sample chamber is fed into the flat sheath flow cell by a sample suction syringe.
- the sample fed into the flat sheath flow cell is sandwiched between sheath liquids to form a flat flow.
- the sample passing through the flat sheath flow cell is irradiated with strobe light at 1/60 second intervals, and the flowing particles can be photographed as a still image. Further, since the flow is flat, the image is taken in a focused state.
- the particle image is captured by a CCD camera, and the captured image is subjected to image processing at an image processing resolution of 512 ⁇ 512 (0.37 ⁇ m ⁇ 0.37 ⁇ m per pixel), and the contour of each particle image is extracted,
- the projected area S, the peripheral length L, and the like are measured. Next, the equivalent circle diameter and the circularity are obtained using the area S and the peripheral length L.
- the equivalent circle diameter is the diameter of a circle having the same area as the projected area of the particle image
- the circularity is 1.000, and as the degree of irregularities on the outer periphery of the particle image increases, the circularity decreases.
- the range of the circularity of 0.200 to 1.000 is divided into 800, the arithmetic average value of the obtained circularity is calculated, and the value is defined as the average circularity.
- the toner of the present invention preferably has a standard deviation SD of circularity obtained by the above method of 0.050 or less.
- SD exceeds 0.050, the content and presence state of the shell phase contained in the toner may become uneven, and the durability stability performance of the toner may deteriorate.
- the SD is more preferably 0.030 or less, and further preferably 0.020 or less.
- D4, D4 / D1, average circularity, and SD of the toner described above are the physical properties of the resin, such as the molecular weight, acid value, THF-soluble content and methanol-insoluble content of the styrene-acrylic resin in the toner, Control is possible by the production conditions such as the addition amount and the temperature at which the toner particles are produced and the addition amount of the dispersion stabilizer.
- a styrene acrylic resin is preferable.
- the vinyl monomer for producing the styrene acrylic resin and the styrene acrylic resin used as the shell phase include the following compounds.
- Styrene o-methylstyrene, m-methylstyrene, p-methylstyrene, ⁇ -methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert- Butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-chloro styrene, 3, Derivatives of styrene such as 4-dichlorostyrene, m-nitrostyrene, o-nitrosty
- Unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid
- unsaturated such as maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride Dibasic acid anhydride
- maleic acid methyl half ester maleic acid ethyl half ester, butyl maleic acid half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl half ester
- alkenyl succinic acid Half-esters of unsaturated dibasic acids such as acid methyl half esters, fumaric acid methyl half esters, mesaconic acid methyl half esters
- dimethyl maleic acids, unsaturated dibasic acid esters such as dimethyl fumaric acid
- acrylic acid methacrylate
- acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1-hydroxy-1 And monomers having a hydroxy group such as (methylhexyl) styrene.
- the styrene acrylic resin used as the binder resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups.
- the crosslinking agent used in this case include divinylbenzene and divinylnaphthalene as aromatic divinyl compounds.
- diacrylate compounds linked by an alkyl chain include the following compounds. Ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate and the above compounds The acrylate was replaced with methacrylate.
- diacrylate compounds linked by an alkyl chain containing an ether bond include the following compounds. Diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and acrylates of the above compounds are replaced with methacrylate.
- diacrylate compounds linked by a chain containing an aromatic group and an ether bond include polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane diacrylate and polyoxyethylene (4) -2. , 2-bis (4-hydroxyphenyl) propane diacrylate and those obtained by replacing the acrylate of the above compounds with methacrylate.
- polyfunctional crosslinking agent examples include the following compounds. Pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and acrylates of the above compounds are replaced by methacrylate; triallyl cyanurate, triallyl trimellitate.
- Examples of the polymerization initiator used when producing the styrene acrylic resin that the toner of the present invention has as the binder resin and the styrene acrylic resin used as the resin for the shell include the following compounds.
- Examples of the azo polymerization initiator include the following compounds.
- 2,2'-azobisisobutyronitrile 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (-2,4-dimethylvaleronitrile), 2 , 2′-azobis (-2methylbutyronitrile), dimethyl-2,2′-azobisisobutyrate, 1,1′-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyro Nitriles, 2,2′-azobis (2,4,4-trimethylpentane), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2′-azobis (2-methyl-propane) and the like.
- peroxide polymerization initiators include the following compounds. 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane (molecular weight: 561, theoretical active oxygen content: 11.4%, 10 hour half-life temperature: 94.7 ° C.), 1,1 Di (t-hexylperoxy) cyclohexane (molecular weight: 316, theoretical active oxygen content: 10.1%, 10 hour half-life temperature: 87.1 ° C.), 1,1-di (t-butylperoxy) cyclohexane (Molecular weight: 260, theoretical active oxygen content: 12.3%, 10 hour half-life temperature: 90.7 ° C.), n-butyl 4,4-di (t-butylperoxy) valerate (molecular weight: 334, theoretical activity Oxygen amount: 9.6%, 10 hour half-life temperature: 104.5 ° C., 2,2-di (t-butylperoxy) butane (molecular weight: 234, theoretical active oxygen amount
- t-butyl hydroperoxide (molecular weight: 90, theoretical active oxygen content: 17.8%, 10-hour half-life temperature: 166.5 ° C.), cumene hydroperoxide (molecular weight: 152, theoretical active oxygen content: 10.5) %, 10-hour half-life temperature: 157.9 ° C.), diisopropylbenzene hydroperoxide (molecular weight: 194, theoretical active oxygen content: 8.2%, 10-hour half-life temperature: 145.1 ° C.), p-menthane hydro Peroxide (molecular weight: 172, theoretical active oxygen content: 9.3%, 10 hour half-life temperature: 128.0 ° C.), 1,1,3,3-tetramethylbutyl hydroperoxide (molecular weight: 146, theoretical activity) Hydroperoxides such as oxygen content: 10.9%, 10 hour half-life temperature: 152.9 ° C).
- t-butylcumyl peroxide (molecular weight: 208, theoretical active oxygen content: 7.7%, 10 hour half-life temperature: 119.5 ° C.), di-t-butyl peroxide (molecular weight: 146, theoretical active oxygen content: 10.9%, 10-hour half-life temperature: 123.7 ° C.), di-t-hexyl peroxide (molecular weight: 202, theoretical active oxygen content: 7.9%, 10-hour half-life temperature: 116.4 ° C.) Dialkyl peroxides such as Diisobutyl peroxide (molecular weight: 174, theoretical active oxygen content: 9.2%, 10 hour half-life temperature: 32.7 ° C.), di (3,5,5-trimethylhexanoyl) peroxide (molecular weight: 314, theoretical Active oxygen content: 5.1%, 10-hour half-life temperature: 59.4 ° C., dilauroyl peroxide (molecular weight: 399, theoretical active oxygen content: 4.0%, 10-hour
- Disuccinic acid peroxide (molecular weight: 234, theoretical active oxygen content: 6.8%, 10 hour half-life temperature: 65.9 ° C.), benzoyl peroxide (molecular weight: 242, theoretical active oxygen content: 6.6) %, 10 hour half-life temperature: 73.6 ° C.), benzoyl m-methylbenzoyl peroxide or m-toluoyl peroxide (10 hour half-life temperature: 73.1 ° C.) Diacyl peroxides such.
- Diisopropyl peroxydicarbonate (molecular weight: 206, theoretical active oxygen content: 7.8%, 10 hour half-life temperature: 40.5 ° C.), di-n-propyl peroxydicarbonate (molecular weight: 206, theoretical active oxygen content) : 7.8%, 10-hour half-life temperature: 40.3 ° C), bis (4-t-butylcyclohexyl) peroxydicarbonate (molecular weight: 399, theoretical active oxygen content: 4.0%, 10-hour half-life) Temperature: 40.8 ° C.), di-2-ethylhexyl peroxydicarbonate (molecular weight: 346, theoretical active oxygen content: 4.6%, 10 hour half-life temperature: 43.6 ° C.), di-sec-butyl percarbonate Peroxydicarbonates such as oxydicarbonates (molecular weight: 234, theoretical active oxygen content: 6.8%, 10 hour half-life temperature: 40.5 ° C.).
- Cumylperoxyneodecanoate (molecular weight: 306, theoretical active oxygen content: 5.2%, 10 hour half-life temperature: 36.5 ° C), 1,1,3,3-tetramethylbutylperoxyneodecano Ate (molecular weight: 300, theoretical active oxygen content: 5.3%, 10 hour half-life temperature: 40.7 ° C.), t-hexylperoxydecanoate (molecular weight: 272, theoretical active oxygen content: 5.9%) 10-hour half-life temperature: 44.5 ° C.), t-butylperoxyneodecanoate (molecular weight: 244, theoretical active oxygen content: 6.6%, 10-hour half-life temperature: 46.4 ° C.), t -Butylperoxyneoheptanoate (molecular weight: 202, theoretical active oxygen content: 7.9%, 10 hour half-life temperature: 50.6 ° C), t-hexylperoxypivalate (molecular weight: 202, theoretical active oxygen Amount
- a peroxide polymerization initiator is preferable as a polymerization initiator used for polymerization of the styrene acrylic resin. Since the peroxide-based polymerization initiator tends to proceed more uniformly than the azo-based polymerization initiator, the content of the THF-insoluble component contained in each toner particle and the IPA-soluble component The content tends to be uniform. For this reason, even when aiming at further improvement of the low-temperature fixing performance of the toner, the durability stability performance of the toner is easily maintained well.
- a peroxide polymerization initiator when a polymerizable monomer for a binder resin is polymerized in the presence of a resin component such as a shell resin, a peroxide polymerization initiator is preferable.
- the peroxide-based initiator easily causes a hydrogen abstraction reaction of a resin component such as a shell resin, and a branched resin in which the resin component and a part of the binder resin are graft-bonded can be produced.
- the content of the shell resin contained in each toner particle tends to be uniform, and the presence of the shell resin tends to be uniform even when the toner is formed.
- peroxide-based polymerization initiators peroxyesters, peroxyketals, and diacyl peroxides are preferable from the viewpoint of achieving both low-temperature fixing performance and durability stability performance of the toner.
- Peroxyesters are particularly preferred peroxide polymerization initiators from the viewpoint of low-temperature fixing performance of the toner.
- a peroxide polymerization initiator having a 10-hour half-life temperature of 30.0 to 130.0 ° C. is preferable. It is preferable to use a polymerization initiator having a low 10-hour half-life temperature because the radical concentration at the initial stage of polymerization can be increased. Since the radical concentration at the initial stage of polymerization is high, it is possible to generate many molecular chains having a uniform molecular weight from the early stage of the polymerization process.
- the toner has The content of the THF-insoluble component can be reduced, and the content of the IPA-soluble component can be well controlled.
- the 10-hour half-life temperature of the peroxide polymerization initiator is more preferably 30.0 to 100.0 ° C, and further preferably 40.0 to 90.0 ° C.
- the particularly preferable range of the 10-hour half-life temperature of the peroxide polymerization initiator is 40.0 to 70.0 ° C.
- the peroxide polymerization initiator used in the toner of the present invention includes a peroxide polymerization having a branched alkyl group such as t-butyl group, t-hexyl group, 1,1,3,3-tetramethylbutyl group. Initiators are preferred.
- the branched alkyl group can be introduced at the end of the molecular chain of the binder resin of the toner, and the molecular chain can be efficiently branched.
- a peroxide polymerization initiator having a t-butyl group and a t-hexyl group as a branched alkyl group is preferable, and a t-butyl group is particularly preferable as a peroxide polymerization initiator. It is a peroxide-based polymerization initiator.
- the peroxide polymerization initiator used in the toner of the present invention is preferably a peroxide polymerization initiator having a molecular weight of 140 to 400 and a theoretical active oxygen content of 5.00 to 12.00%.
- the carbon number of the functional group introduced at the end of the molecular chain of the binder resin and the balance between the polymerization reaction and the hydrogen abstraction reaction become better, and the low-temperature fixing performance and durability stability performance of the toner tend to be better.
- the molecular weight of the peroxide polymerization initiator is more preferably 140 to 350, and even more preferably 150 to 300.
- the molecular weight of a particularly preferred peroxide polymerization initiator is 160 to 250.
- the theoretical active oxygen content of the peroxide polymerization initiator is more preferably 6.00 to 11.00%, and even more preferably 6.80 to 11.00%.
- the toner of the present invention contains one kind or two or more kinds of waxes.
- the wax that can be used in the present invention include the following compounds.
- saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid
- unsaturated fatty acids such as brassic acid, eleostearic acid, and valinalic acid
- stearyl alcohol, aralkyl alcohol behenyl alcohol, carnauvyl alcohol, and seryl alcohol Saturated alcohols such as melyl alcohol
- polyhydric alcohols such as sorbitol
- fatty acids such as palmitic acid, stearic acid, behenic acid, and montanic acid
- stearyl alcohol, aralkyl alcohol behenyl alcohol, carnauvir alcohol, seryl alcohol
- Esters of alcohols such as merisyl alcohol
- fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide
- methylene bis stearic acid amide, ethylene biscapric acid amide Saturated fatty acid bisamides such as ethylene bislauric acid
- Examples of the wax preferably used in the present invention include aliphatic hydrocarbon waxes and ester waxes that are esters of fatty acids and alcohols.
- aliphatic hydrocarbon waxes and ester waxes that are esters of fatty acids and alcohols.
- low molecular weight alkylene polymer obtained by radical polymerization of alkylene under high pressure with Ziegler catalyst or metallocene catalyst under low pressure; alkylene polymer obtained by thermally decomposing high molecular weight alkylene polymer; synthesis containing carbon monoxide and hydrogen Synthetic hydrocarbon waxes obtained from the distillation residue of hydrocarbons obtained by gas from the gas or by hydrogenation of these are preferred.
- what carried out the fractionation of the hydrocarbon wax by the use of the press perspiration method, the solvent method, the vacuum distillation, or the fractional crystallization method is more preferably used.
- the hydrocarbon as a base is synthesized by the reaction of carbon monoxide and hydrogen using a metal oxide catalyst (mostly two or more multi-component systems) [for example, the Jintol method, the Hydrocol method (the fluidized catalyst bed Hydrocarbon compounds synthesized by use); hydrocarbons with up to several hundred carbon atoms obtained by the age method (using the identified catalyst bed) in which a large amount of wax-like hydrocarbons can be obtained; alkylene such as ethylene by Ziegler catalyst Polymerized hydrocarbons are preferred because they are linear hydrocarbons with little branching, small and long saturation.
- a wax synthesized by a method that does not rely on polymerization of alkylene is also preferred from its molecular weight distribution.
- a wax having a melting point of 55 to 140 ° C. is preferable.
- a low melting point wax of 55 to 120 ° C., more preferably 55 to 100 ° C. is more preferable.
- the low melting point wax dissolves quickly at the time of fixing, works effectively between the fixing roller and the toner interface, and has a high effect on high temperature offset.
- aliphatic hydrocarbon waxes and ester waxes having a melting point of 55 to 100 ° C. can improve both the low-temperature fixing performance and the durability stability performance of the toner, and the color development after fixing.
- Aliphatic hydrocarbon waxes effectively interact with the colorant because the aromatic ring of the pigment and the ester bond of the ester wax are close in polarity to the carbonyl group of the pigment to improve the color development performance of the colorant.
- Particularly preferably used waxes are aliphatic hydrocarbon waxes such as paraffin wax, polyethylene and Fischer-Tropsch wax which have a short molecular chain and little steric hindrance and excellent mobility.
- the main peak is preferably in the region of molecular weight 350 to 2400, and more preferably in the region of molecular weight 400 to 2000 from the viewpoint of improving the low-temperature fixability performance of the toner.
- the content of the wax is preferably 3 to 30 parts by mass with respect to 100 parts by mass of the binder resin in terms of achieving both low temperature fixing performance, anti-offset performance, and durability stability performance of the toner.
- the wax content of the toner of the present invention is more preferably 5 to 20 parts by mass, and particularly preferably 6 to 14 parts by mass.
- the extraction method is not particularly limited, and any method can be used.
- a predetermined amount of toner is Soxhlet extracted with toluene, and after removing the solvent from the obtained toluene-soluble component, a chloroform-insoluble component is obtained. Thereafter, identification analysis is performed by IR method or the like. In addition, quantitative analysis is performed by DSC.
- the toner of the present invention has a maximum endothermic peak measured by a differential scanning calorimeter (DSC) at 60.0 to 95.0 ° C., and the endothermic amount of the endothermic peak is 3.0 to 30.0 J / g. preferable.
- the endothermic peak is considered to be a peak due to melting of the wax contained in the toner in a crystalline state among the waxes that the toner has. It is preferable that the endothermic amount be in the above range from the viewpoint of achieving both low temperature fixing performance, offset resistance performance, and durability stability performance of the toner.
- a part of the wax contained in the toner is compatible with the binder resin at the time of toner production, a part is used as a plasticizer for the binder resin, and a part is used as a release agent for the toner.
- a part of the wax contained in the toner in a crystalline state is further mixed with the binder resin in the fixing step and used as a plasticizer. For this reason, since all the wax which toner has does not act as a mold release agent, it is preferable to contain more wax than usual.
- the endothermic amount of the endothermic peak is more preferably 5.0 to 20.0 J / g, and even more preferably 6.0 to 15.0 J / g.
- the toner of the present invention may use a charge control agent.
- the charge control agent for controlling the toner particles to be negatively charged include the following. Organometallic compound, chelate compound, monoazo metal compound, acetylacetone metal compound, urea derivative, metal-containing salicylic acid compound, metal-containing naphthoic acid compound, quaternary ammonium salt, calixarene, silicon compound, nonmetal carboxylic acid compound and derivatives thereof Is mentioned.
- a sulfonic acid resin having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group can be preferably used.
- the charge control agent for controlling the toner particles to be positively charged for example, the following charge control agents can be used. Modified products with nigrosine and fatty acid metal salts, quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and onium salts such as phosphonium salts which are analogs thereof And these lake pigments, triphenylmethane dyes and these lake pigments (as rake agents, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide) ), Metal salts of higher fatty acids; These can be used alone or in combination of two or more.
- quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosul
- the charge control agent is contained in an amount of 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the binder resin in the toner particles. Good in terms of.
- the toner of the present invention preferably contains a resin containing a sulfonic acid functional group having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group (hereinafter referred to as a sulfonic acid resin).
- a resin containing a sulfonic acid functional group having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group hereinafter referred to as a sulfonic acid resin.
- Styrene acrylic resin, polyester, polyurethane, polyurea, polyamide, or the like can be used as the resin that is the main component of the sulfonic acid resin.
- the main component of the sulfonic acid resin is preferably a styrene acrylic resin.
- the sulfonic acid resin is likely to be localized in the vicinity of the surface of the toner particles, and the durability stability performance of the toner is likely to be improved.
- a part of the polar group of the shell resin interacts with a sulfonic acid group of the sulfonic acid resin, thereby further improving the durability and stability of the toner. It becomes easy to improve.
- the main component of the sulfonic acid resin is a styrene acrylic resin
- the content of the sulfonic acid resin between the toner particles tends to be uniform, and the durability stability performance of the toner tends to be better.
- the content of the sulfonic acid resin is too high, or when the content of the sulfonic acid group of the sulfonic acid resin is too high, the low-temperature fixing performance of the toner may be deteriorated.
- the content of the sulfur element derived from the sulfonic acid group by the fluorescent X-ray measurement of the THF soluble component by the Soxhlet extraction method is 0. 0 relative to the content of the THF soluble component. It is preferably 005 to 0.300 mass%.
- the content of the elemental sulfur is less than 0.005% by mass, the durability stability performance and penetration resistance performance of the toner may be deteriorated.
- the sulfur element content exceeds 0.300% by mass, the low-temperature fixing performance and gloss performance of the toner may deteriorate.
- the content of the elemental sulfur is more preferably 0.020 to 0.300% by mass, and further preferably 0.040 to 0.200% by mass.
- the content of the sulfur element can be controlled by the content of the sulfonic acid group of the sulfonic acid resin and the amount of the sulfonic acid resin added.
- sulfonic acid group As the sulfonic acid group, sulfonic acid group, or sulfonic acid ester group possessed by the sulfonic acid-based resin, particularly preferred functional groups include those represented by the following formulas (1) to (6).
- the functional group is preferably directly bonded to the main chain of the styrene acrylic resin.
- X represents an amide bond
- R represents a linear or branched alkanediyl group having 1 to 8 carbon atoms
- Y represents hydrogen, an alkali metal, or 1 to 8 carbon atoms
- 6 represents a straight-chain or branched alkyl group having 6 carbon atoms
- Z represents hydrogen or a straight-chain or branched alkyl group having 1 to 6 carbon atoms.
- a sulfonic acid resin having a repeating unit represented by the following chemical formula (7) is preferable from the viewpoint of low-temperature fixing performance and durability stability performance of the toner.
- X represents an amide bond
- Y represents hydrogen, an alkali metal, a linear or branched alkyl group having 1 to 6 carbon atoms
- R 2 represents hydrogen or a methyl group.
- a sulfonic acid resin having a repeating unit represented by the following chemical formula (8) is preferable from the viewpoint of low-temperature fixing performance and durability stability performance of the toner.
- X represents an amide bond
- Y represents hydrogen, an alkali metal, a linear or branched alkyl group having 1 to 6 carbon atoms
- R 2 represents hydrogen or a methyl group.
- a sulfonic acid resin having a repeating unit represented by the following chemical formula (9) is preferable from the viewpoint of low-temperature fixing performance and durability stability performance of the toner.
- X represents an amide bond
- R represents a linear or branched alkanediyl group having 1 to 8 carbon atoms
- Y represents hydrogen, an alkali metal, or a linear chain having 1 to 6 carbon atoms. or it shows a branched alkyl group
- R 2 represents hydrogen or a methyl group.
- the sulfonic acid resin preferably has a glass transition temperature (Tg) of 30.0 to 100.0 ° C.
- Tg glass transition temperature
- the toner exhibits better low-temperature fixing performance and durability stability performance. Further, in a toner having a core-shell structure, if a sulfonic acid resin having an excessively high Tg is localized in the vicinity of the surface of the toner particle, the difference in thermodynamic properties from the vicinity of the center of the toner particle becomes too large. In some cases, the durability stability performance of the toner may be reduced. For this reason, Tg of the sulfonic acid resin is more preferably 35.0 to 80.0 ° C, and further preferably 40.0 to 75.0 ° C.
- the sulfonic acid resin preferably has a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group content of 0.01 to 20.00% by mass relative to the mass of the sulfonic acid resin.
- the content of the sulfonic acid group, sulfonic acid group, or sulfonic acid ester group is within the above range, the content of the sulfonic acid-based resin contained in each toner particle tends to be more uniform. . Thereby, even when aiming at improvement of the low-temperature fixing performance of the toner, the durability stability performance becomes better.
- the content is more preferably 0.01 to 10.00% by mass, and further preferably 0.02 to 5.00% by mass.
- the sulfonic acid resin preferably has an acid value of 1.0 to 80.0 mgKOH / g from the viewpoint of achieving both low temperature fixing performance and durability stability performance of the toner.
- the acid value of the sulfonic acid resin is more preferably 3.0 to 40.0 mgKOH / g, and further preferably 5.0 to 30.0 mgKOH / g.
- the sulfonic acid-based resin is preferably contained in an amount of 0.01 to 15.00 parts by mass with respect to 100 parts by mass of the binder resin from the viewpoint of achieving both low-temperature fixing performance and durability stability performance of the toner.
- the content of the sulfonic acid resin is more preferably 0.50 to 10.00 parts by mass, and further preferably 2.00 to 5.00 parts by mass.
- the sulfonic acid resin preferably has a weight average molecular weight (Mw) of 500 to 100,000 from the viewpoint of achieving both low-temperature fixing performance and durable stability performance of the toner. More preferably, it is 1000-70000, More preferably, it is 5000-50000.
- the sulfonic acid resin has a ratio (Mw / Mn) of the Mw to the number average molecular weight (Mn) of 1.50 to 20.00. To preferred. More preferably, it is 2.00 to 10.00, More preferably, it is 2.00 to 5.00.
- the toner particles of the present invention contain a colorant.
- a colorant carbon black, a magnetic material, or a color toned to black using a yellow / magenta / cyan colorant shown below is used.
- the colorant for cyan toner, magenta toner, and yellow toner for example, the following colorants can be used.
- the yellow colorant compounds represented by monoazo compounds, disazo compounds, condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complex methine compounds, and allylamide compounds are used as pigments. Specifically, the following pigments are preferably used.
- the dye system include C.I. l. Solvent Yellow 33, 56, 79, 82, 93, 112, 162, 163, C.I. I. Disperse Yellow 42, 64, 201, 211 may be mentioned.
- magenta colorant monoazo compounds, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds are used. Specific examples include the following colorants.
- cyan colorant copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, and basic dye lake compounds can be used. Specifically, C.I. I. Pigment blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66.
- colorants can be used alone or mixed and further used in the form of a solid solution.
- the colorant used in the present invention is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP transparency, and dispersibility in the toner.
- the colorant is added in an amount of 0.4 to 20 parts by mass with respect to 100 parts by mass of the binder resin.
- the toner of the present invention contains a magnetic material and can be used as a magnetic toner.
- the magnetic material can also serve as a colorant.
- the magnetic material include iron oxides such as magnetite, hematite, and ferrite; metals such as iron, cobalt, and nickel. Or alloys of these metals with metals such as aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium and mixtures thereof.
- These magnetic materials preferably have a number average particle size of 2 ⁇ m or less, more preferably 0.1 to 0.5 ⁇ m, from the viewpoint of low-temperature fixing performance and durability stability performance of the toner.
- the amount to be contained in the toner is preferably 20 to 200 parts by mass, more preferably 40 to 150 parts by mass with respect to 100 parts by mass of the binder resin.
- the magnetic material has a coercive force (Hc) of 1.59 to 23.9 kA / m (20 to 300 Oersted) and a saturation magnetization ( ⁇ s) of 50 to 200 Am in terms of magnetic characteristics when 796 kA / m (10 kOersted) is applied. 2 / kg and the remanent magnetization ( ⁇ r) are preferably 2 to 20 Am 2 / kg.
- the toner of the present invention has inorganic fine particles.
- the inorganic fine particles are preferably externally added to the toner particles and mixed as a fluidity improver.
- titanium oxide fine particles, silica fine particles, or alumina fine particles are preferably exemplified, and silica fine particles are more preferable.
- the surface of these inorganic fine particles is hydrophobized.
- the inorganic fine particles are preferably used in an amount of 0.1 to 5 parts by weight, more preferably 0.5 to 3.5 parts by weight, based on 100 parts by weight of the toner particles.
- the inorganic fine particles used in the toner of the present invention those having a specific surface area of 30 m 2 / g or more by nitrogen adsorption measured by the BET method, particularly those in the range of 50 to 400 m 2 / g can give good results. This is preferable because it is possible.
- the toner of the present invention may be further externally added to and mixed with an external additive for the purpose other than the above improvement of fluidity, for example, for the purpose of improving cleaning properties.
- an external additive for the purpose of improving the cleaning property for example, fine particles having a primary particle size of more than 30 nm (preferably a specific surface area of less than 50 m 2 / g), more preferably a primary particle size of 50 nm or more (preferably a ratio)
- examples thereof include inorganic fine particles or organic fine particles having a surface area of less than 30 m 2 / g and a nearly spherical shape.
- spherical silica fine particles, spherical polymethylsilsesquioxane fine particles, or spherical resin fine particles are preferable.
- Lubricant powder such as fluororesin powder, zinc stearate powder, polyvinylidene fluoride powder; abrasive such as cerium oxide powder, silicon carbide powder, strontium titanate powder; anti-caking agent; carbon black powder, zinc oxide powder, tin oxide powder
- Conductivity-imparting agents such as: organic particles having opposite polarity, or inorganic particles.
- the external additive as described above is preferably used in an amount of 0.1 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the toner particles.
- the toner of the present invention is a method of atomizing a molten mixture into air using a disk or a multi-fluid nozzle to obtain substantially spherical toner particles, or an aqueous system that is soluble in a polymerizable monomer and insoluble in the resulting polymer. It can be produced by a method using a dispersion polymerization method in which toner particles are directly generated using an organic solvent.
- a method for producing toner particles using an emulsion polymerization method typified by a soap-free polymerization method in which toner particles are produced by direct polymerization in the presence of a water-soluble polar polymerization initiator, a dissolution suspension method, an emulsification It can also be produced by agglomeration or suspension polymerization.
- the toner of the present invention is preferably produced by a production method having a step of forming toner particles in water. Specifically, the following methods are mentioned.
- a step of forming an aqueous dispersion of a monomer composition having at least a shell resin, a polymerizable monomer, a wax, and a colorant in water, and the polymerizable monomer of the aqueous dispersion A so-called suspension polymerization method in which toner particles are formed through a polymerization step.
- a method by a so-called emulsion aggregation method wherein resin particles having a shell resin are added to the dispersion, and the toner particles are formed through a step of coating the colored particles.
- a so-called solution suspension method in which toner particles are formed through a step of forming a liquid and a step of removing the solvent from the aqueous dispersion.
- the method for producing the toner of the present invention it is particularly preferable to use the production method by the suspension polymerization method (1).
- the suspension polymerization method By using the suspension polymerization method, the shell resin and the binder resin are partially graft-bonded in the polymerization process, and the content of the shell resin is uniform among the toner particles. Is thought to be better expressed.
- a specific method for producing toner particles by the suspension polymerization method is as follows. Polymerizing monomer, resin for shell, colorant, wax, and other additives such as charge control agent and cross-linking agent as required are uniformly distributed by a disperser such as a homogenizer, ball mill, colloid mill, or ultrasonic disperser.
- the monomer composition thus obtained is suspended in an aqueous medium containing a dispersion stabilizer.
- a high-speed disperser such as a high-speed stirrer or an ultrasonic disperser
- the toner particle size distribution obtained is sharpened by setting the desired toner particle size at a stretch.
- the polymerization initiator may be added in advance to the monomer composition, or may be added after the monomer composition is suspended in an aqueous medium. After the suspension, stirring may be performed using an ordinary stirrer to such an extent that the particle state is maintained and the floating / sedimentation of the particles is prevented.
- the pH is preferably 4 to 10.5 when suspended, from the viewpoint of uniformity of toner shape. When the pH is less than 4, the toner particle size distribution tends to be large. On the other hand, if the pH exceeds 10.5, the charging performance of the toner may deteriorate.
- inorganic dispersants can be preferably used because their stability is not easily lost even when the reaction temperature is changed.
- examples of such inorganic dispersants include the following compounds. Polyvalent metal phosphates such as tricalcium phosphate, magnesium phosphate, aluminum phosphate and zinc phosphate; carbonates such as calcium carbonate and magnesium carbonate; inorganic salts such as calcium metasuccinate, calcium sulfate and barium sulfate; Inorganic oxides such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, silica, bentonite and alumina.
- inorganic dispersants are preferably used alone or in combination of two or more, with respect to 100 parts by weight of the polymerizable monomer.
- a surfactant may be used in combination with 100 parts by mass of the polymerizable monomer.
- the surfactant include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, sodium stearate, and potassium stearate.
- these inorganic dispersants When these inorganic dispersants are used, they may be used as they are, but it is preferable to produce the inorganic dispersant in an aqueous medium in order to obtain finer particles.
- aqueous medium in order to obtain finer particles.
- tricalcium phosphate it is possible to produce a poorly water-soluble tricalcium phosphate by mixing an aqueous solution of sodium phosphate and an aqueous solution of calcium chloride under high-speed stirring. Dispersion is possible.
- the inorganic dispersant can be almost completely removed by dissolving with an acid or alkali after completion of the polymerization.
- the polymerization is performed at a polymerization temperature of 40 ° C. or higher, generally 50 to 100 ° C.
- a polymerization temperature of 40 ° C. or higher, generally 50 to 100 ° C.
- the binder resin and the wax are phase-separated with the progress of the polymerization, and toner particles in which the wax is encapsulated are obtained.
- the temperature at the start of polymerization is higher by 15.0 to 50.0 ° C. than the 10-hour half-life temperature (° C.) of the polymerization initiator.
- Polymerization is preferred as the temperature. Since the radical concentration in the initial stage of polymerization can be increased, a large number of molecular chains having a uniform molecular weight can be generated from the early stage of the polymerization process. Thereby, a cross-linking is easily suppressed and the content of the THF-insoluble component and the IPA-soluble component can be suitably controlled. Further, when the above-described shell resin is used, the shell resin and a part of the binder resin are easily graft-bonded, and the adhesion between the shell resin and the binder resin is easily improved.
- the temperature at the start of polymerization relative to the 10 hour half-life temperature (° C.) of the polymerization initiator is more preferably 25.0 to 50.0 ° C., and further preferably 30.0 to 50.0 ° C. preferable.
- the temperature at the start of the polymerization is 30.0 to the glass transition point (Tg) (° C.) of the binder resin produced by the polymerization.
- Polymerization is preferably performed at a temperature as high as 70.0 ° C.
- the temperature at the start of polymerization with respect to the glass transition point (Tg) (° C.) of the binder resin is more preferably 35.0 to 60.0 ° C., and more preferably 35.0 to 50.0 ° C. Further preferred.
- the toner of the present invention can be used as a one-component developer, and can also be used as a two-component developer having a toner and a carrier.
- a carrier may be any known one. Examples thereof include a carrier made of an element selected from iron, copper, zinc, nickel, cobalt, manganese, and a chromium element, and a ferrite carrier made of a composite oxide of iron and other elements.
- it may be a magnetic material-containing resin carrier in which a magnetic material is dispersed in a resin or a resin-filled carrier in which pores of a porous magnetic material are filled with a resin.
- the carrier As the shape of the carrier, there are a sphere or a substantially spherical shape, a flat shape or an indeterminate shape, any of which can be used.
- the carrier is preferably a magnetic carrier having a resin component on the surface and a true density of 2.5 to 4.2 g / cm 3 .
- the carrier used as the two-component developer preferably has a volume distribution standard 50% particle size (D50) of 15 to 70 ⁇ m. More preferably, it is 20-70 micrometers, More preferably, it is 25-60 micrometers.
- D50 volume distribution standard 50% particle size
- the 50% particle size (D50) based on the volume distribution of the magnetic carrier is within this range, an image with good dot reproducibility can be obtained over a long period of time without fogging.
- the 50% particle size (D50) based on the volume distribution of the carrier is less than 15 ⁇ m, the fluidity of the carrier is lowered, and the durability stability performance of the toner may be lowered.
- the particle size of the carrier can be within the above range by classifying with a wind classifier (Elbow Jet Lab EJ-L3, manufactured by Nippon Steel Mining Co., Ltd.). A method for measuring the 50% particle size (D50) based on the volume distribution will be described later.
- the true density of the carrier is preferably 2.5 to 4.2 g / cm 3 , more preferably 2.7 to 4.1 g / cm 3 , and still more preferably 3.0 to 4.0 g / cm 3. 3 . Since the true density of the carrier is small, the phenomenon that the toner and the carrier deteriorate in the developing machine is suppressed. A method for measuring the true density of the carrier will be described later.
- the magnetization strength of the carrier is preferably 40 to 70 Am 2 / kg under a magnetic field of 1000 / 4 ⁇ (kA / m). When the carrier is within this range, an image with good dot reproducibility can be obtained over a long period of time. A method of measuring the magnetization intensity will be described later.
- the carrier preferably has an average circularity of 0.85 to 0.95, and preferably contains 90% by number or more of particles having a circularity of 0.80 or more.
- the average circularity is more preferably 0.87 to 0.93, and still more preferably 0.88 to 0.92.
- the average circularity is a coefficient representing the shape of the roundness of the particle, and is obtained from the maximum diameter of the particle and the measured particle projected area. An average circularity of 1.00 indicates a perfect sphere (perfect circle), and a smaller numerical value indicates an elongated or irregular shape.
- the average circularity of the carrier is 0.85 to 0.95, the carrier has sufficient carrier strength, excellent chargeability to the toner, and hardly adheres to the toner and toner components, and has excellent durability. . A method for measuring the average circularity of the carrier will be described later.
- the mixing ratio of toner and carrier should be 0.02 to 0.35 parts by mass with respect to 1 part by mass of carrier. It is preferable to use at 0.04 to 0.25 parts by mass, and it is particularly preferable to use at 0.05 to 0.20 parts by mass.
- the true density of the toner and carrier can be measured by a method using a gas displacement pycnometer.
- the measurement principle is that a shutoff valve is provided between a sample chamber (volume V 1 ) having a constant volume and a comparison chamber (volume V 2 ), and after measuring the mass (M 0 (g)), the sample is put into the sample chamber. .
- the sample chamber and the comparison chamber is filled with an inert gas such as helium, the pressure at that time and P 1. Close the shut-off valve and add inert gas only to the sample chamber. The pressure at that time and P 2. Open the shutoff valve, the pressure in the system when connecting the comparison chamber and the sample chamber and P 3.
- the volume (V 0 (cm 3 )) of the sample can be obtained by the following formula A.
- the true density ⁇ (g / cm 3 ) of the toner and carrier can be obtained.
- V 0 V 1 ⁇ [V 2 / ⁇ (P 2 ⁇ P 1 ) / (P 3 ⁇ P 1 ) ⁇ 1 ⁇ ] (Formula A)
- ⁇ M 0 / V 0 (Formula B)
- measurement was performed using a dry automatic densitometer Accupic 1330 (manufactured by Shimadzu Corporation).
- a 10 cm 3 sample container is used, and as a sample pretreatment, helium gas purge is performed 10 times at a maximum pressure of 19.5 psig (134.4 kPa).
- the pressure fluctuation in the sample chamber is set to 0.0050 psig / min as a guide. Start and automatically measure true density. The measurement is performed 5 times, and the average value is obtained to obtain the true density (g / cm 3 ).
- the weight average molecular weight (Mw), number average molecular weight (Mn), and peak molecular weight (Mp) of molecular weight distribution by GPC are values determined by the following methods. 30 mg of the sample to be measured is placed in 5 ml of tetrahydrofuran (THF) and left at room temperature for 24 hours. This is filtered with a disposable filter for high performance liquid chromatograph (HPLC) “Mysholy disk H-25-5” (manufactured by Tosoh Corporation) to obtain a sample solution. Using this sample solution, measurement is performed under the following conditions.
- HPLC high performance liquid chromatograph
- HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation) Column: Seven columns of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko) Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 ml / min Oven temperature: 40.0 ° C Sample injection volume: 0.10 ml In calculating the molecular weight of the sample, a molecular weight calibration curve prepared using the following standard sample is used.
- An RI (refractive index) detector is used as the detector.
- the cylindrical filter paper is gently taken out and vacuum-dried at a temperature of 40 ° C. for 24 hours. After leaving this in an environment adjusted to a temperature of 25 ° C. and a humidity of 60% RH for 3 days, the amount of solid content remaining on the cylindrical filter paper is weighed, and this is defined as W2 (g).
- W2 g
- the content of the THF soluble component or insoluble component, the content of the IPA soluble component, and the content of the methanol insoluble component are calculated from the following formulas.
- Sample THF or methanol insoluble component content (W2 / W1) ⁇ 100
- Sample content of THF or IPA soluble component (% by mass) 100 ⁇ (W2 / W1) ⁇ 100
- a sample for measuring X-ray fluorescence of a THF-soluble component a solution obtained by distilling off THF in a solution extracted by the Soxhlet extractor to recover a resin component, followed by vacuum drying at a temperature of 40 ° C. for 24 hours is used.
- the glass transition point (Tg), melting point (Tm), maximum endothermic peak temperature, and endothermic amount are measured using a differential scanning calorimeter (DSC).
- DSC differential scanning calorimeter
- Q1000 manufactured by TA Instruments
- 4 mg of a sample is precisely weighed in an aluminum pan, an empty aluminum pan is used as a reference pan, and measurement is performed in a nitrogen atmosphere with a modulation amplitude of 0.5 ° C. and a frequency of 1 / min. The measurement temperature was held at 10 ° C.
- the glass transition point determined by the midpoint method is the glass transition point at the intersection of the baseline before the endothermic peak and the baseline after the endothermic peak in the DSC curve at elevated temperature and the rising curve. (See FIG. 1).
- the measurement of the maximum endothermic peak temperature and endothermic amount of the toner is based on the fact that the endothermic peak deviates from the extrapolation line of the baseline before the endothermic peak in the reversing heat flow curve obtained by the same measurement as above.
- the maximum endothermic peak temperature In the region surrounded by the endothermic peak and the straight line connecting the extrapolated baseline after the end of the endothermic peak and the endothermic peak, the maximum endothermic peak temperature And When two or more maximum values exist in the peak, the temperature at the maximum value where the length between the connected straight line and the maximum value is long in the enclosed region is set as the temperature of the maximum endothermic peak. Even when two or more of the enclosed regions exist independently, the temperature at the maximum value where the length between the straight line and the maximum value connected in the same manner as described above is long is set as the temperature of the maximum endothermic peak.
- the endothermic amount is the point where the endothermic peak departs from the extrapolation line of the baseline before the endothermic peak, the extrapolation line of the baseline after the end of the endothermic peak, and the The endothermic amount (J / g) is determined from the area (integrated value of the melting peak) of the region surrounded by the straight line connecting the points where the endothermic peak contacts and the endothermic peak. In the case where two or more of the enclosed regions are present independently, they are summed to obtain an endothermic amount.
- the melting point of the wax is the temperature of the maximum endothermic peak measured in the same manner as the method for measuring the temperature of the maximum endothermic peak of the toner.
- the acid value of the resin is determined as follows.
- the basic operation conforms to JIS-K0070.
- the number of mg of potassium hydroxide required to neutralize free fatty acids, resin acid groups and the like contained in 1 g of a sample is referred to as an acid value, and is measured by the following method.
- a) Solvent As a solvent for the sample, an ethyl ether-ethyl alcohol mixture (1 + 1 or 2 + 1) or a benzene-ethyl alcohol mixture (1 + 1 or 2 + 1) is used.
- A B ⁇ f ⁇ 5.661 / S
- f 0.1 mol / liter-factor of potassium hydroxide ethyl alcohol solution
- the hydroxyl value of the resin is determined as follows.
- the basic operation conforms to JIS-K0070.
- a hydroxyl value is measured by the following method.
- (1) Preparation of Reagent (a) Acetylation Reagent 25 ml of acetic anhydride is placed in a 100 ml volumetric flask, pyridine is added to make a total volume of 100 ml, and shaken sufficiently. (In some cases, pyridine may be added).
- the acetylating reagent should be kept in brown bottles away from moisture, carbon dioxide and acid vapors.
- B Preparation of phenolphthalein solution 1 g of phenolphthalein is dissolved in 100 ml of ethyl alcohol (95 v / v%).
- C Preparation of 0.2 mol / liter potassium hydroxide-ethyl alcohol solution Dissolve 35 g of potassium hydroxide in as little water as possible and add ethyl alcohol (95 v / v%) to 1 liter to make 2 to 3 days. Filter after standing. The orientation is performed according to JISK 8006.
- the flask was heated again in a glycerin bath for 10 minutes, allowed to cool, and then the funnel and the flask wall were washed with 5 ml of ethyl alcohol, and 0.2 mol / liter of phenolphthalein solution was used as an indicator. Titrate with potassium hydroxide ethyl alcohol solution. A blank test is performed in parallel with this test. In some cases, a KOH-THF solution may be used as an indicator. (3) Calculation formula The hydroxyl value is calculated by the following formula.
- A ⁇ (BC) ⁇ f ⁇ 28.05 / S ⁇ + D
- A Hydroxyl value (mgKOH / g)
- B 0.5 mol / liter of blank test-amount of potassium hydroxide ethyl alcohol solution used (ml)
- C Amount used of 0.5 mol / liter-potassium hydroxide ethyl alcohol solution in this test (ml)
- f Factor of 0.5 mol / liter-potassium hydroxide ethyl alcohol solution
- S Sample (g)
- D Acid value (mgKOH / g)
- the average circularity of the toner particles is measured using a flow type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation) under the measurement and analysis conditions during calibration.
- FPIA-3000 flow type particle image analyzer
- a specific measuring method is as follows. First, about 20 ml of ion-exchanged water from which impure solids are removed in advance is put in a glass container. In this, “Contaminone N” (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd.
- a desktop type ultrasonic cleaner disperser for example, “VS-150” (manufactured by Vervocrea) having an oscillation frequency of 50 kHz and an electric output of 150 W is used.
- Ion exchange water is added, and about 2 ml of the above-mentioned Contaminone N is added to this water tank.
- the flow type particle image analyzer equipped with “UPlanApro” (magnification: 10 ⁇ , numerical aperture: 0.40) as an objective lens is used, and the particle sheath “PSE-900A” (manufactured by Sysmex Corporation) is used as the sheath liquid. Is used.
- the dispersion prepared in accordance with the above procedure is introduced into the flow type particle image analyzer, and 3000 toner particles are measured in the HPF measurement mode and in the total count mode.
- the binarization threshold at the time of particle analysis is set to 85%, the analysis particle diameter is limited to the equivalent circle diameter of 1.985 ⁇ m or more and less than 39.69 ⁇ m, and the average circularity of the toner particles is obtained.
- automatic focus adjustment is performed using standard latex particles (for example, “RESEARCH AND TEST PARTICLES Latex Microsphere Suspensions 5200A” manufactured by Duke Scientific) diluted with ion-exchanged water before starting the measurement. Thereafter, it is preferable to perform focus adjustment every two hours from the start of measurement.
- a flow type particle image analyzer which has been issued a calibration certificate issued by Sysmex Corporation, which has been calibrated by Sysmex Corporation, is used. The measurement is performed under the measurement and analysis conditions when the calibration certificate is received, except that the analysis particle diameter is limited to a circle equivalent diameter of 1.985 ⁇ m or more and less than 39.69 ⁇ m.
- the weight average particle diameter D4 ( ⁇ m) and the number average particle diameter D1 ( ⁇ m) of the toner can be measured by the following methods.
- a precision particle size distribution measuring apparatus “Coulter Counter Multisizer 3” registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method equipped with an aperture tube of 100 ⁇ m is used.
- attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. Note that the measurement is performed with 25,000 effective measurement channels.
- the electrolytic aqueous solution used for the measurement special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.
- the dedicated software Prior to measurement and analysis, the dedicated software is set as follows. On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50000 particles, set the number of measurements once, and the Kd value is “standard particles 10.0 ⁇ m” (Beckman Coulter, Inc.) Set the value obtained using By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set.
- SOM Change Standard Measurement Method
- the current is set to 1600 ⁇ A
- the gain is set to 2
- the electrolyte is set to ISOTON II
- the “aperture tube flush after measurement” is checked.
- the bin interval is set to logarithmic particle size
- the particle size bin is set to 256 particle size bin
- the particle size range is set to 2 ⁇ m to 60 ⁇ m.
- the specific measurement method is as follows. (1) About 200 ml of the electrolytic solution is placed in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm.
- the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
- (5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is adjusted as appropriate so that the water temperature is 10 ° C. or higher and 40 ° C. or lower.
- the electrolyte solution of (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . Measurement is performed until the number of measured particles reaches 50,000.
- the measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) and the number average particle diameter (D1) are calculated.
- the “average diameter” on the “analysis / volume statistics (arithmetic average)” screen is the weight average particle diameter (D4)
- the graph / number% is set.
- the “average diameter” on the “analysis / number statistics (arithmetic average)” screen is the number average particle diameter (D1).
- Measurement is performed using wavelength-dispersed fluorescent X-ray “Axios advanced” (manufactured by PANalytical). About 3 g of the sample is put into a ring made of vinyl chloride for measuring 27 mm, and pressed at 200 kN to mold the sample. The amount of sample used and the thickness of the molded sample are measured, and the content of sulfur element derived from the sulfonic acid group is determined as an input value for content calculation. The analysis conditions and analysis method are shown below.
- the 50% particle size (D50) and average circularity based on the volume distribution of the carrier are measured as follows using a multi-image analyzer (manufactured by Beckman Coulter).
- a solution obtained by mixing about 1% NaCl aqueous solution and glycerin at 50% by volume: 50% by volume is used as the electrolytic solution.
- the NaCl aqueous solution may be prepared using primary sodium chloride, and may be, for example, ISOTON (registered trademark) -II (manufactured by Coulter Scientific Japan).
- Glycerin may be a special grade or first grade reagent.
- a surfactant preferably alkylbenzenesulfone hydrochloric acid
- 2 to 20 mg of a measurement sample is further added.
- the electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 minute to obtain a dispersion.
- a 200 ⁇ m aperture and a 20 ⁇ lens as the aperture, the equivalent circle diameter and circularity are calculated under the following measurement conditions.
- Average luminance within measurement frame 220 to 230 Measurement frame setting: 300 SH (threshold): 50 Binarization level: 180
- the electrolytic solution and the dispersion liquid are put into a glass measuring container, and the concentration of carrier particles in the measuring container is set to 5 to 10% by volume. Stir the contents of the glass container at the maximum stirring speed.
- the sample suction pressure is 10 kPa. If the carrier specific gravity is large and sedimentation tends to occur, the measurement time is 15 to 30 minutes. In addition, the measurement is interrupted every 5 to 10 minutes to replenish the sample solution and the electrolytic solution-glycerin mixed solution. The number of measurements is 2000.
- the main body software removes a defocused image, aggregated particles (multiple simultaneous measurements), etc. on the particle image screen.
- “Area” is the projected area of the binarized carrier particle image
- “MaxLength” is defined as the maximum diameter of the carrier particle image.
- the equivalent circle diameter is represented by the diameter of a perfect circle when “Area” is the area of the perfect circle.
- the equivalent circle diameter is divided into 256 parts of 4 to 100 ⁇ m, and is used logarithmically on a volume basis. Using this, the 50% particle size (D50) based on volume distribution is obtained. The average circularity is obtained by adding the circularity of each particle and dividing by the total number of particles.
- the strength of the magnetization of the carrier can be obtained by a vibrating magnetic field type magnetic characteristic device VSM (Vibrating sample magnetometer), a direct current magnetization characteristic recording device (BH tracer) or the like. Preferably, it can measure with an oscillating magnetic field type magnetic property apparatus.
- the oscillating magnetic field type magnetic property device include an oscillating magnetic field type magnetic property automatic recording device BHV-30 manufactured by Riken Denshi Co., Ltd. Using this, it can be measured by the following procedure.
- the cylindrical plastic container is filled with the carrier sufficiently densely, while an external magnetic field of 1000 / 4 ⁇ (kA / m) (1000 oersted) is created, and the magnetization moment of the carrier filled in the container is measured in this state. . Further, the actual mass of the carrier filled in the container is measured to determine the magnetization strength (Am 2 / kg) of the carrier.
- the container D having a flow rate adjusting function was kept at ⁇ 10 ° C., and the following materials were put therein.
- PBD Di-t-butyl peroxide
- Tol3 7.6 parts by mass Toluene
- the flow rate when charging from the container B to the container A was set to 25 parts by mass / hour.
- the flow rate when charging from the container C into the container A was started from 8 parts by mass / hour, and was set to 12 parts by mass / hour after 4 hours by increasing the flow rate at a constant acceleration.
- the flow rate when charging the container A from the container D was set to 10 parts by mass / hour.
- the inside of the container A was stirred at 200 rpm and heated to 140 ° C.
- the charging of each material was started simultaneously from the container B, the container C, and the container D.
- the mixture was further stirred for 3 hours from the end of all the charging.
- the solvent was distilled off to obtain styrene acrylic resin 1.
- Table 2 shows the physical properties of the styrene acrylic resin 1.
- Styrene acrylic resins 2, 3, and 6 were obtained in the same manner as in Production Example 1 of styrene acrylic resin except that the conditions were changed to those shown in Table 1.
- Table 2 shows the physical properties of styrene acrylic resins 2, 3, and 6.
- a container D connected to the container A and equipped with a flow rate adjusting function was kept at ⁇ 10 ° C., and the following materials were put in it.
- PBD Di-t-butyl peroxide
- Tol3 Toluene
- the flow rate when charging from the container C to the container A was 10 parts by mass / hour, and the flow rate when charging from the container D to the container A was set to 10 parts by mass / hour.
- the inside of the container A was stirred at 200 rpm and heated to 140 ° C.
- the introduction of each material from the container B, the container C, and the container D was started simultaneously.
- the mixture was further stirred for 3 hours from the end of all the charging.
- the solvent was distilled off to obtain styrene acrylic resin 4.
- Table 2 shows the physical properties of the styrene acrylic resin 4.
- Styrene acrylic resins 5 and 9 were obtained in the same manner as in Production Example 4 of styrene acrylic resin except that the conditions were changed to those shown in Table 1.
- Table 2 shows the physical properties of styrene acrylic resins 5 and 9.
- reaction solution was added to 700 parts by mass of methanol stirred at 200 rpm, and the precipitate was collected.
- the obtained precipitate was washed with 1 mol / liter-hydrochloric acid and washed with deionized water three times. It dried with the 40 degreeC vacuum dryer, and obtained the sulfonic acid group containing styrene acrylic resin.
- the following materials were placed in a reaction vessel equipped with a reflux condenser, a stirrer, and a nitrogen inlet tube under a nitrogen atmosphere and heated in an oil bath at 80 ° C.
- Trimethyl orthoformate 400 parts by mass
- the inside of the container was stirred at 200 rpm, and the sulfonic acid group-containing styrene acrylic resin obtained above: 100 parts by mass was added over 30 minutes, and further 12 hours. Stir.
- the reaction solution was added to 5000 parts by mass of methanol stirred at 200 revolutions per minute to collect the precipitate. Methanol washing and deionized water washing were repeated three times, and then dried under reduced pressure. Thereby, a sulfonic acid-based resin 1 having a sulfonic acid methyl ester group was obtained.
- the physical properties of the sulfonic acid resin 1 are shown in Table 3-1, and the structure of the sulfonic acid resin 1 is shown in Table 3-2.
- a solution obtained by diluting 1 part by mass of t-butylperoxy-2-ethylhexanoate as a polymerization initiator with 30 parts by mass of 2-butanone was added dropwise over 30 minutes, and stirring was continued for 5 hours. Further, t-butylperoxy was further added.
- a solution prepared by diluting 1 part by weight of -2-ethylhexanoate with 30 parts by weight of 2-butanone was added dropwise over 30 minutes, and the mixture was further stirred for 5 hours for polymerization. While maintaining the temperature, 500 parts by mass of deionized water was gently added, and the mixture was stirred at 80 rpm for 2 hours so as not to disturb the interface between the organic layer and the aqueous layer.
- HNP-10 Nippon Seiki Wax Co.
- Toner particles 1 100 parts by mass Hydrophobic titanium oxide treated with nC 4 H 9 Si (OCH 3 ) 3 (BET specific surface area: 120 m 2 / g): 0.8 parts by mass Hexamethyldisilazane Hydrophobic silica treated with silicone oil after treatment (BET specific surface area 180 m 2 / g): physical properties of 0.8 part by weight of toner 1 are shown in Tables 6-1 and 6-2. The performance evaluation of the toner 1 described later was performed. Table 7 shows the results of performance evaluation of toner 1.
- Example 1 ⁇ Examples 2 to 6 and Comparative Examples 2, 4, 6 to 8, 10 and 11>
- toners 2 to 6, 10, 12, 14 to 16, 18 and 19 were added in the same manner as in Example 1 except that the types and amounts of raw materials used and the reaction temperature were changed to the conditions shown in Table 5. Obtained.
- Tables 6-1 and 6-2 show the physical properties of the toners 2 to 6, 10, 12, 14 to 16, 18 and 19.
- performance evaluation of toners 2 to 6, 10, 12, 14 to 16, 18 and 19 was performed.
- Table 7 shows the results of performance evaluation of toners 2 to 6, 10, 12, 14 to 16, 18 and 19.
- Example 7 In Example 1, the type and amount of raw materials used, the timing of charging the initiator, and the reaction temperature were changed to the conditions shown in Table 5, and the monomer composition was charged in the granulation step of the monomer composition. At the same time, a toner 7 was obtained in the same manner as in Example 1 except that the polymerization initiator was added. The physical properties of Toner 7 are shown in Tables 6-1 and 6-2. The performance of the toner 7 was evaluated in the same manner as in Example 1. Table 7 shows the results of performance evaluation of the toner 7.
- Example 8 and Comparative Examples 1, 3 and 9> In Example 7, toners 8, 9, 11 and 17 were obtained in the same manner as in Example 7 except that the types and amounts of raw materials used and the reaction temperature were changed to the conditions shown in Table 5. Tables 6-1 and 6-2 show the physical properties of Toners 8, 9, 11 and 17. In the same manner as in Example 1, performance evaluation of the toners 8, 9, 11 and 17 was performed. Table 7 shows the results of performance evaluation of the toners 8, 9, 11, and 17.
- Example 5 the core composition was formed in the same manner as in Example 1 except that the styrene acrylic resin 1 was not added in the monomer composition formation step, and the polymerization step was held at 90 ° C. without cooling after the completion of the polymerization. A dispersion of particles was obtained.
- Example 13 (Manufactured by Kojun Pharmaceutical Co., Ltd.): 0.35 parts by mass were added dropwise simultaneously over 30 minutes, and polymerization was continued for 5 hours as it was, followed by cooling to room temperature.
- a toner 13 was obtained in the same manner as in the washing / drying step and the external addition step in Example 1.
- the physical properties of Toner 13 are shown in Tables 6-1 and 6-2.
- Table 7 shows the results of performance evaluation of the toner 13.
- the fixing unit removed from the commercially available color printer (LBP-5400, manufactured by Canon) was remodeled so that the fixing temperature and process speed could be adjusted, and a fixing test for unfixed images was performed using this.
- the process speed was set to 240 mm / second, and the toner image was fixed at each temperature while changing the set temperature every 5 ° C. within the range of 110 ° C. to 240 ° C.
- the low-temperature fixing performance was evaluated based on the temperature at which the low-temperature offset was not generated after changing from the low temperature side to the high temperature.
- the anti-offset performance, the gloss performance, and the penetration resistance were evaluated.
- B The rate of change in glossiness is 5% or more and less than 10% (excellent penetration resistance)
- C The change rate of the glossiness is 10% or more and less than 15% (the level of impregnation resistance is not a problem)
- D The change rate of glossiness is 15% or more and less than 20% (smear resistance is slightly inferior)
- E The rate of change in glossiness is 20% or more (impregnation performance is poor)
- the cartridge was mounted on a cyan station, and continuous printing with a printing rate of 1% was performed on image receiving paper (Canon Office Planner 64 g / m 2 ), and a solid image was formed once every 500 sheets.
- image receiving paper Canon Office Planner 64 g / m 2
- the durability stability performance was evaluated according to the following evaluation criteria. (Evaluation criteria for durability and stability) A: The solid image density becomes less than 1.5 after the added amount of toner is added four times. (Excellent durability and stability) B: After adding the toner three times, the solid image density becomes less than 1.5.
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Abstract
Description
定着工程においては、転写材上のトナーが定着部材に付着した後、該トナーが再度転写材に移行することによって転写材を汚す現象であるオフセットを抑制する性能(以下、耐オフセット性能と称する)が低下しやすくなる。また、高光沢の画像を形成することによって、画像の発色性を向上させる性能(以下、グロス性能と称する)や、画像の光沢にムラが生じることを抑制する性能(以下、耐しみ込み性能と称する)が低下しやすくなる。
特許文献1及び2は、ガラス転移点(Tg)の低いコア粒子をTgの高いシェル層で被覆することにより、保存中にコア粒子がトナー表面へしみ出すことを抑制し、トナーの低温定着性能と連続印字における安定性の向上とを両立しようとするものである。
本発明の目的は、前述の如き課題を解決し得るトナーを提供することにある。
即ち、本発明の目的は、ワックスを含有するトナーにおいて、低温定着性能を向上させた場合においても良好な耐久安定性能を有し、耐オフセット性能、グロス性能、及び、耐しみ込み性能に優れ、高品位な画像の形成を可能とするトナーを提供することにある。
すなわち、本発明のトナーは、低周波数でトナーの動的粘弾性測定を行った場合の温度-貯蔵弾性率曲線に対し、高周波数でトナーの動的粘弾性測定を行った場合の温度-貯蔵弾性率曲線が、ある特定の温度領域で、特徴的な挙動変化を示すことを特徴とする。
測定試料としては、温度25℃湿度60%RHの環境下で、錠剤成型器を用いて加圧成形した試料を用いる。トナーの真密度をρ(g/cm3)としたとき、トナーを0.20×ρ(g)秤量し、20kNの荷重を2分間加え、直径8mm、厚さ約4mmの円柱状のペレットを成形する。このペレットを用いて以下の測定を行う。
測定装置として、ARES(レオメトリック・サイエンティフィック・エフ・イー株式会社製)を用い、当該計測機器の操作マニュアルに従い、以下の測定条件で測定する。
・ 配列(Geometry Type):パラレルプレート(Parallel Plates)
・ パラレルプレート:セレイテッド(serrated)型パラレルプレートを使用
・ 測定開始温度(Initial Temp):後述(TgT-10(℃))
・ 測定終了温度(Final Temp):180(℃)
・ ギャップ調整(Change Gap to Match Tool Thermal Expansion):on
・ 膨張係数(Tool Thermal Expansion Coefficient):0.0(μm/℃)
・ 密度(Fluid Density):1.0(g/cm3)
・ 装置弾性(Fixture Compliance):0.83(μrad/g・cm)
・ 試験モード(Test Type):Dynamic Temperature Ramp
・ 周波数(Frequency)
1Hz:6.2832(rad・s)
10Hz:62.832(rad・s)
・ 昇温速度(Ramp Rate):2.0(℃/min)
・ 浸透時間(Soak Time After Ramp):1.0(s)
・ 測定間隔(Time Per Measure):30.0(s)
・ 歪み(Strain):0.02(%)
・ テンション調整(Auto Tension Adjustment):on
・ モード(Mode):Apply Constant Static Force
・ テンション方向(AutoTension Direction):Compression
・ 初期スタティックフォース(Initial Static Force):10.0(g)
・ 自動テンションセンシティビティ(Auto Tension Sensitivity):40.0(g)
・ 自動テンションの作動条件(When Sample Modulus <):1.00×108(dyn/cm2)
・ 自動テンションリミット(AutoTension Limits):Default
・ 最大自動テンションレート(Max AutoTension Rate):0.01(mm/s)
・ 自動歪み調整(AutoStrain):on
・ 最大歪(Max Applied Strain):40.0(%)
・ 最大トルク(Max Allowed Torque):150.0(g・cm)
・ 最小トルク(Min Allowed Torque):1.0(g・cm)
・ 歪み調整(Strain Adjustment):20.0(%)
・ 歪み幅調整(Strain Amplitude Control):Default Behavior
・ オプション(Measurement Option):Default Delay Settings
Cycles:0.5
Time:3.0(s)
・ トランスデューサー(Transducer):Transducer1
測定操作は以下のとおりとする。
<前操作>
測定装置の試料室を予め25.0℃に保持しておき、荷重(Axial Force)が30になるように前記ペレットをセットしてホールドスイッチを入れる。ホールドスイッチは、ペレットを挟んでいるプレート間の距離(Gap;両プレートにおける凸部間距離)を調節することにより、ペレットにかかる荷重を、該スイッチが入った時の荷重の値に保持する機能を有する。後述する示差走査熱量計(DSC)により測定したトナーのガラス転移点(Tg)をTgT(℃)としたとき、試料室の温度をTgT+2(℃)に加熱する。試料室内が該温度で安定したらホールドスイッチを外し、ペレットにかかる荷重(Axial Force)が1500になるようにプレート間の距離(Gap)を調節し、再度ホールドスイッチを入れる。すると、荷重により、セレイテッド型プレートの凸部がペレットの表面に徐々に埋め込まれていくため、プレート間の距離(Gap)が徐々に小さい値になる。荷重1500としてホールドスイッチを入れた時点でのプレート間の距離(Gap)に対し、プレート間の距離(Gap)が10%小さくなった時点でホールドスイッチを外す。さらにプレート間の距離を広げて、ペレットにかかる荷重(Axial Force)が150になるようにする。この際、プレートの移動速度をなるべくゆっくりとし、少しずつ移動させるように注意する。また、荷重が150よりも小さくなりすぎないようにする。荷重が150になった時点で再度ホールドスイッチを入れ、試料室の温度を測定開始温度にセットする。測定開始温度は、TgT-10(℃)とする。
上記の操作において、TgT+2(℃)の温度でペレットを固定化する目的は、トナーに熱を加えすぎないようにするためである。これにより、トナーに含有される結着樹脂、ワックス、その他の添加剤の存在状態が、測定を開始する前に熱によって変化することを抑制でき、トナーの物性をより正確に測定することができる。
<測定>
測定開始温度に達して試料室の温度が安定したら、ホールドスイッチを外し、その時のプレート間の距離(Gap)を入力する。そして、測定を開始する。測定は、2個のペレットを用い、測定周波数が1Hzの場合と10Hzの場合とで二回測定を行う。
測定周波数が1Hzの場合に得られた貯蔵弾性率をG’1(Pa)とし、測定周波数10Hzの場合に得られた貯蔵弾性率をG’10(Pa)とする。それぞれの測定温度をx軸とし、そのときのG’1をy軸とした(温度-G’1曲線)、及び、G’10をy軸とした(温度-G’10)曲線をそれぞれ得る。
得られた曲線より、G’1とG’10との比(G’10/G’1)をy軸、測定温度をx軸として、(温度-G’10/G’1)曲線を作成する。この曲線より、本発明で規定する物性値を読みとる。図4として、本発明の実施例及び比較例に係るトナーの(温度-G’10/G’1)曲線の一例を示す。
尚、G’1及びG’10のいずれの測定においても、昇温速度2.0℃/min、測定間隔を30秒としているため、1.0℃刻みの貯蔵弾性率のデータが得られるが、1Hzと10Hzとの両測定における温度が若干ずれることがある。その場合には、周波数1Hzのときの測定温度と周波数10Hzの測定温度との平均値を測定温度としてプロットする。また、測定誤差の影響によって、得られた(温度-G’10/G’1)曲線に細かなシャープなピークが出現することがあるが、本願発明において規定される極大値はある程度の温度幅を有する大きなピークにおける極大値である。
さらに、温度60.0乃至135.0℃といった高温側の温度領域における(温度-G’10)曲線の挙動変化が一定の範囲を超える強度を有する場合に、本発明の効果が良好に発現される。
一方で、上述のような特徴がみられるのは、本発明のトナーが熱力学的に硬い部分と軟らかい部分とを有するためと考えられるが、トナーの低温定着性能、及び、耐久安定性能のさらなる向上の観点からは、熱力学的な硬さの違いが大きすぎない方が好ましい。このため、該G’aは5.0乃至20.0であることが好ましく、5.0乃至15.0であることがより好ましく、さらには、6.0乃至14.0であることがさらに好ましい。特に好ましいG’aの範囲は、8.0乃至14.0である。
しかし、あるガラス転移点(Tg)を有する樹脂bと、該樹脂bよりも高いTgを有する樹脂aとを混ぜ合わせて動的粘弾性測定を行った場合、該樹脂aと該樹脂bとが相溶した状態では、該樹脂aや該樹脂bのTgに対応した挙動変化は一般に検出されない。動的粘弾性測定の条件が1Hzであっても10Hzであっても、該樹脂aのTgと該樹脂bのTgとの中間のTgに対応した挙動変化が検出される。このため、(温度-G’10/G’1)曲線を作成した場合には、極大値は一つしかみられない。一方、前記樹脂aと前記樹脂bとが完全に相分離した状態では、動的粘弾性測定の条件が1Hzであっても10Hzであっても、該樹脂bのTgに対応した挙動と、該樹脂aのTgに対応した挙動とが検出される。しかし、(温度-G’1)曲線と(温度-G’10)曲線とを比較すると、ほぼ同じ形状のため、(温度-G’10/G’1)曲線を作成した場合には、前記樹脂bのTgに対応した極大値しかみられないのが一般的である。または、樹脂aのTgに対応した極大値がみられたとしても、前記G’aは極めて小さい値になる。
このため、前述のようなコアシェル構造を有するとしても、一般的なコアシェル構造を有するだけでは前述のような特徴ある物性は発現されないと考えられる。
即ち、本発明のトナーは、コア相の一部とシェル相の一部とが相溶した状態にあり、コア相と、該コア相を被覆するコア成分とシェル成分とが相溶した相との二層構造、或いは、該二層構造を被覆するシェル相との三層構造になっていると推測される。
上述のような構成を有する場合、周波数1Hzといった比較的低い周波数の測定条件、即ち低速の歪みに対してはシェル相がコア相の挙動に同調し、シェル相の性質が目立たなくなると考えられる。よって、前記(温度-G’1)曲線においては、トナーの主成分となるコア相の物性だけが検出される。一方、周波数10Hzといった高い周波数の測定条件、即ち高速の歪みに対しては、コア相とシェル相とが同調できなくなるため、コア相、及び、シェル相の物性が検出されると考えられる。
さらに、前記G’aが5.0以上といった大きい値を有するのは、コア相に対するシェル相の被覆状態が、トナー粒子間において均一であるためと考えられる。即ち、トナー粒子に含有される材料として、コア相の主成分となる結着樹脂の含有量、該コア相を被覆するシェル用樹脂の含有量がトナー粒子間において均一であり、且つ、トナー粒子間において該結着樹脂と該シェル用樹脂の相溶状態が均一であるためと考えられる。
トナー粒子の一粒一粒について、シェル用樹脂の含有量を比較した場合、その含有量に偏りが大きい場合には、周波数10Hzにおいてシェル相に対応する物性挙動が検出されにくくなる。このため、前記G’aは小さい値となる。また、トナー粒子の内部におけるコア相とシェル相との相溶状態が粒子間において不均一である場合には、周波数10Hzにおいてシェル相に対応する物性挙動が検出されにくくなり、前記G’aは小さい値になる。一方、シェル相の被覆状態が不均一なままに、シェル相の被覆量を増やした場合には、周波数10Hzにおいてシェル相に対応する物性挙動は検出されやすくなるが、トナー全体が硬くなるため周波数1Hzにおいてもシェル相に対応する物性挙動が検出されやすくなる。このため、やはり前記G’aは小さい値になると考えられる。
即ち、該G’aは、トナー粒子の一粒一粒についてコアシェル構造の形成状態を比較した場合の、トナー全体に対する均一性の指標になると考えられる。
また、前記Tb(℃)は、トナーが有する結着樹脂のガラス転移点(Tg)に対応する値と考えられる。前記Ta(℃)は、シェル用樹脂のTg、添加量、及び、該シェル用樹脂と結着樹脂との相溶状態に対応する値と考えられる。
なお、上記(G’a-G’b)は、トナー粒子に含有される結着樹脂、ワックス等の種類と添加量の他、結着樹脂と異なる性質を有する樹脂を添加すること、及び、それら材料のトナー中における含有率の均一性、トナー中における存在状態の均一性により制御することができる。
なお、上記G’1Taは、トナー粒子に含有される結着樹脂、ワックス等の種類と添加量の他、結着樹脂と異なる性質を有する樹脂を添加すること、及び、それら材料のトナー中における含有率の均一性、トナー中における存在状態の均一性により制御することができる。
上記の効果を更に高めるためには、該Mpは7000乃至25000であることがより好ましく、7000乃至20000であることがさらに好ましい。特に好ましい該Mpの範囲は、8000乃至16000である。また、該Mwは10000乃至150000であることがより好ましく、10000乃至120000であることがさらに好ましい。特に好ましい該Mwの範囲は、30000乃至100000である。更に、該Mw/Mnは5.0乃至20.0であることがより好ましく、5.0乃至12.0であることがさらに好ましい。上記Mp、Mw、Mw/Mnは、トナー粒子に含有される結着樹脂、ワックスの他、シェル用樹脂といった添加剤の種類と添加量により制御することができる。本発明のトナーが重合法による場合には、重合開始剤の種類及び添加量、重合温度、特に重合開始剤の10時間半減期温度に対する重合開始時の温度、架橋剤の種類及び添加量等により制御可能である。
上記THF不溶成分の含有量は、トナー粒子に含有される結着樹脂、ワックスの他、シェル用樹脂といった添加剤の種類と添加量により制御することができる。本発明のトナーが重合法による場合には、重合開始剤の種類及び添加量、重合温度、特に重合開始剤の10時間半減期温度に対する重合開始時の温度、架橋剤の種類及び添加量等により制御可能である。
上記のように架橋剤の添加量が多いにも関わらず、トナーが有するTHF不溶成分の含有量を少なく制御する方法としては、トナー粒子に含有される結着樹脂のガラス転移点(Tg)に対する重合温度、重合開始剤の種類及び添加量、架橋剤の種類及び添加量等により制御可能である。重合開始剤の10時間半減期温度に対して、重合開始時の重合温度を15.0乃至50.0℃高く設定する方法は、重合初期のラジカル濃度を高くすることができて好ましい。重合初期のラジカル濃度が高いことで、重合工程の早い段階から分子量が揃った高分子鎖を多く生成することが可能となる。高分子鎖の形成が早いほど、高分子鎖同士の架橋反応がしにくくなるため、通常よりもTHF不溶成分の含有量を少なく制御できると考えられる。また、結着樹脂のTgに対し重合温度を高くすることで、重合途中の分子鎖の運動が激しくなり、架橋結合が抑制され、結果としてトナーが有するTHF不溶成分の含有量を少なく制御されると考えられる。また、シェル用樹脂といった添加剤の種類及び添加量によっても制御可能である。
トナーが有するTHF不溶成分の含有量が5.0乃至35.0質量%である場合に、IPA可溶成分の含有量が上記範囲であることは特に好ましい。THF不溶成分はトナーの耐オフセット性能を向上するためには有利であるが、THF不溶成分を多く含有すると、コア相とシェル相との相溶性が低下する場合がある。この場合に、THF不溶成分はある程度少ない量に留め、IPAに不溶の成分をある程度多く含有することで、コア相とシェル相との相溶性を向上し、トナーの耐オフセット性能も良好に発現される。上記の効果を更に高めるためには、該IPA可溶成分の含有量は、10.0乃至40.0質量%であることがより好ましく、10.0乃至35.0質量%であることがさらに好ましい。特に好ましい上記IPA可溶成分の含有量は、10.0乃至30.0質量%である。
上記IPA可溶成分の含有量は、トナー粒子に含有される結着樹脂のガラス転移点(Tg)に対する重合温度、重合開始剤の種類及び添加量、架橋剤の種類及び添加量等により制御可能である。重合開始剤の10時間半減期温度に対して、重合開始時の重合温度を15.0乃至50.0℃高く設定する方法は、重合初期のラジカル濃度を高くすることができて好ましい。重合初期のラジカル濃度が高いことで、重合工程の早い段階から高分子量が揃った分子鎖を多く生成することが可能となる。また、高分子鎖を比較的短くそろえることができるため、IPA可溶成分の含有量を好適に制御することができる。また、結着樹脂のTgに対し重合温度を高くすることで、重合途中の分子鎖の運動が激しくなり、成長途中にある分子鎖同士の結合反応が抑制され、結果としてトナーが有するIPA可溶成分の含有量を多くすることができる。また、シェル用樹脂といった添加剤の種類及び添加量によっても制御可能である。
上記に加えて、該スチレンアクリル樹脂が、テトラヒドロフラン(THF)可溶成分を85.0質量%以上含有し、メタノール不溶成分を90.0質量%以上含有することが好ましい。これにより、トナー一粒一粒が有する該スチレンアクリル樹脂の含有量の均一性が増し、且つ、トナー一粒一粒の内部においてスチレンアクリル樹脂が局在化する存在状態の均一性が増す。
(1)実質的に溶媒を有しない状態でモノマーを重合する固相重合法。
(2)重合に使用すべき全てのモノマーと全ての重合開始剤と溶媒とを添加し、一括して重合する溶液重合法。
(3)重合反応中にモノマーを追加しながら重合する滴下重合法。
また、常圧重合法及び加圧重合法により製造されたものを用いることができる。
本発明において、上記スチレンアクリル樹脂は、(3)滴下重合法により製造されたものであることが好ましい。共重合成分としてアクリル酸或いはメタクリル酸といった酸モノマーとスチレンとの重合速度の違いを抑制し、THF可溶成分、及び、メタノール不溶成分の含有量を抑制しやすくなる。また、上記の重合は、加圧重合法により行われることが好ましい。反応がより均一に進行し、THF可溶成分、及び、メタノール不溶成分の含有量を抑制しやすくなる。
上記Q値はモノマーに固有の値であり、共重合における反応性を示す値である。例えば「POLYMER HANDBOOK Third Edition」(A WILEY-INTERSCIENCE PUBLICATION JOHN WILEY&SONS)(II/268頁)に記載されている値を用いることができる。具体的なモノマーのQ値は、例えば、スチレン:1.00、ブチルアクリレート:0.38、メチルアクリレート:0.45、メチルメタクリレート:0.78、アクリル酸:0.83、メタクリル酸:0.98、2-ヒドロキシエチルメタクリレート:1.78である。
フロー式粒子像分析装置「FPIA-3000」(シスメックス社製)の測定原理は、流れている粒子を静止画像として撮像し、画像解析を行うというものである。試料チャンバーへ加えられた試料は、試料吸引シリンジによって、フラットシースフローセルに送り込まれる。フラットシースフローセルに送り込まれた試料は、シース液に挟まれて扁平な流れを形成する。フラットシースフローセル内を通過する試料に対しては、1/60秒間隔でストロボ光が照射されており、流れている粒子を静止画像として撮影することが可能である。また、扁平な流れであるため、焦点の合った状態で撮像される。粒子像はCCDカメラで撮像され、撮像された画像は512×512の画像処理解像度(一画素あたり0.37μm×0.37μm)で画像処理され、各粒子像の輪郭抽出を行い、粒子像の投影面積Sや周囲長L等が計測される。
次に、上記面積Sと周囲長Lを用いて円相当径と円形度を求める。円相当径とは、粒子像の投影面積と同じ面積を持つ円の直径のことであり、円形度Cは、円相当径から求めた円の周囲長を粒子投影像の周囲長で割った値として定義され、次式で算出される。
円形度C=2×(π×S)1/2/L
粒子像が円形の時に円形度は1.000になり、粒子像の外周の凹凸の程度が大きくなればなるほど円形度は小さい値になる。各粒子の円形度を算出後、円形度0.200~1.000の範囲を800分割し、得られた円形度の相加平均値を算出し、その値を平均円形度とする。
上述したトナーのD4、D4/D1、平均円形度、SDは、トナーが有する前記スチレンアクリル樹脂の分子量、酸価、THF可溶分やメタノール不溶分の含有量といった該樹脂の物性、該樹脂の添加量、及び、トナー粒子製造時の温度や分散安定剤の添加量といった製造条件により制御が可能である。
本発明のトナーに用いられる結着樹脂としてはスチレンアクリル樹脂が好ましい。該スチレンアクリル樹脂、及び、シェル相として使用するスチレンアクリル樹脂を生成するためのビニル系モノマーとしては以下の化合物が挙げられる。
スチレン;o-メチルスチレン、m-メチルスチレン、p-メチルスチレン、α-メチルスチレン、p-フェニルスチレン、p-エチルスチレン、2,4-ジメチルスチレン、p-n-ブチルスチレン、p-tert-ブチルスチレン、p-n-ヘキシルスチレン、p-n-オクチルスチレン、p-n-ノニルスチレン、p-n-デシルスチレン、p-n-ドデシルスチレン、p-メトキシスチレン、p-クロルスチレン、3,4-ジクロルスチレン、m-ニトロスチレン、o-ニトロスチレン、p-ニトロスチレンの如きスチレンの誘導体;エチレン、プロピレン、ブチレン、イソブチレンの如き不飽和モノオレフィン類;ブタジエン、イソプレンの如き不飽和ポリエン類;塩化ビニル、塩化ビニルデン、臭化ビニル、フッ化ビニルの如きハロゲン化ビニル類;酢酸ビニル、プロピオン酸ビニル、安息香酸ビニルの如きビニルエステル類;メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸-n-ブチル、メタクリル酸イソブチル、メタクリル酸-n-オクチル、メタクリル酸ドデシル、メタクリル酸-2-エチルヘキシル、メタクリル酸ステアリル、メタクリル酸フェニル、メタクリル酸ジメチルアミノエチル、メタクリル酸ジエチルアミノエチルの如きα-メチレン脂肪族モノカルボン酸エステル類;アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸-n-ブチル、アクリル酸イソブチル、アクリル酸-n-オクチル、アクリル酸ドデシル、アクリル酸-2-エチルヘキシル、アクリル酸ステアリル、アクリル酸-2-クロルエチル、アクリル酸フェニルの如きアクリル酸エステル類;ビニルメチルエーテル、ビニルエチルエーテル、ビニルイソブチルエーテルの如きビニルエーテル類;ビニルメチルケトン、ビニルヘキシルケトン、メチルイソプロペニルケトンの如きビニルケトン類;N-ビニルピロール、N-ビニルカルバゾール、N-ビニルインドール、N-ビニルピロリドンの如きN-ビニル化合物;ビニルナフタリン類;アクリロニトリル、メタクリロニトリル、アクリルアミドの如きアクリル酸もしくはメタクリル酸誘導体。
マレイン酸、シトラコン酸、イタコン酸、アルケニルコハク酸、フマル酸、メサコン酸の如き不飽和二塩基酸;マレイン酸無水物、シトラコン酸無水物、イタコン酸無水物、アルケニルコハク酸無水物の如き不飽和二塩基酸無水物;マレイン酸メチルハーフエステル、マレイン酸エチルハーフエステル、マレイン酸ブチルハーフエステル、シトラコン酸メチルハーフエステル、シトラコン酸エチルハーフエステル、シトラコン酸ブチルハーフエステル、イタコン酸メチルハーフエステル、アルケニルコハク酸メチルハーフエステル、フマル酸メチルハーフエステル、メサコン酸メチルハーフエステルの如き不飽和二塩基酸のハーフエステル;ジメチルマレイン酸、ジメチルフマル酸の如き不飽和二塩基酸エステル;アクリル酸、メタクリル酸、クロトン酸、ケイヒ酸の如きα,β-不飽和酸;クロトン酸無水物、ケイヒ酸無水物の如きα,β-不飽和酸無水物、前記α,β-不飽和酸と低級脂肪酸との無水物;アルケニルマロン酸、アルケニルグルタル酸、アルケニルアジピン酸、これらの酸無水物及びこれらのモノエステルの如きカルボキシル基を有するモノマー。
ペンタエリスリトールトリアクリレート、トリメチロールエタントリアクリレート、トリメチロールプロパントリアクリレート、テトラメチロールメタンテトラアクリレート、オリゴエステルアクリレート及び以上の化合物のアクリレートをメタクリレートに代えたもの;トリアリルシアヌレート、トリアリルトリメリテート。
アゾ系重合開始剤としては、例えば以下の化合物が挙げられる。
2,2’-アゾビスイソブチロニトリル、2,2’-アゾビス(4-メトキシ-2,4-ジメチルバレロニトリル)、2,2’-アゾビス(-2,4-ジメチルバレロニトリル)、2,2’-アゾビス(-2メチルブチロニトリル)、ジメチル-2,2’-アゾビスイソブチレート、1,1’-アゾビス(1-シクロヘキサンカルボニトリル)、2-(カーバモイルアゾ)-イソブチロニトリル、2,2’-アゾビス(2,4,4-トリメチルペンタン)、2-フェニルアゾ-2,4-ジメチル-4-メトキシバレロニトリル、2,2’-アゾビス(2-メチル-プロパン)等。
過酸化物系重合開始剤としては、例えば以下の化合物が挙げられる。
2,2-ビス(4,4-ジ-t-ブチルパーオキシシクロヘキシル)プロパン(分子量:561、理論活性酸素量:11.4%、10時間半減期温度:94.7℃)、1,1-ジ(t-ヘキシルパーオキシ)シクロヘキサン(分子量:316、理論活性酸素量:10.1%、10時間半減期温度:87.1℃)、1,1-ジ(t-ブチルパーオキシ)シクロヘキサン(分子量:260、理論活性酸素量:12.3%、10時間半減期温度:90.7℃)、n-ブチル4,4-ジ(t-ブチルパーオキシ)バレレート(分子量:334、理論活性酸素量:9.6%、10時間半減期温度:104.5℃)、2,2-ジ(t-ブチルパーオキシ)ブタン(分子量:234、理論活性酸素量:13.7%、10時間半減期温度:103.1℃)、1,1-ジ(t-ブチルパーオキシ)-2-メチルシクロヘキサン(分子量:274、理論活性酸素量:11.7%、10時間半減期温度:83.2℃)等のパーオキシケタール類。
t-ブチルヒドロパーオキサイド(分子量:90、理論活性酸素量:17.8%、10時間半減期温度:166.5℃)、クメンヒドロパーオキサイド(分子量:152、理論活性酸素量:10.5%、10時間半減期温度:157.9℃)、ジイソプロピルベンゼンヒドロパーオキサイド(分子量:194、理論活性酸素量:8.2%、10時間半減期温度:145.1℃)、p-メンタンヒドロパーオキサイド(分子量:172、理論活性酸素量:9.3%、10時間半減期温度:128.0℃)、1,1,3,3-テトラメチルブチルヒドロパーオキサイド(分子量:146、理論活性酸素量:10.9%、10時間半減期温度:152.9℃)等のヒドロパーオキサイド類。
t-ブチルクミルパーオキサイド(分子量:208、理論活性酸素量:7.7%、10時間半減期温度:119.5℃)、ジ-t-ブチルパーオキサイド(分子量:146、理論活性酸素量:10.9%、10時間半減期温度:123.7℃)、ジ-t-ヘキシルパーオキサイド(分子量:202、理論活性酸素量:7.9%、10時間半減期温度:116.4℃)、等のジアルキルパーオキサイド類。
ジイソブチルパーオキサイド(分子量:174、理論活性酸素量:9.2%、10時間半減期温度:32.7℃)、ジ(3,5,5-トリメチルヘキサノイル)パーオキサイド(分子量:314、理論活性酸素量:5.1%、10時間半減期温度:59.4℃)、ジラウロイルパーオキサイド(分子量:399、理論活性酸素量:4.0%、10時間半減期温度:61.6℃)、ジサクシニックアシッドパーオキサイド(分子量:234、理論活性酸素量:6.8%、10時間半減期温度:65.9℃)、ベンゾイルパーオキサイド(分子量:242、理論活性酸素量:6.6%、10時間半減期温度:73.6℃)、ベンゾイルm-メチルベンゾイルパーオキサイド又はm-トルオイルパーオキサイド(10時間半減期温度:73.1℃)等のジアシルパーオキサイド類。
ジイソプロピルパーオキシジカーボネート(分子量:206、理論活性酸素量:7.8%、10時間半減期温度:40.5℃)、ジ-n-プロピルパーオキシジカーボネート(分子量:206、理論活性酸素量:7.8%、10時間半減期温度:40.3℃)、ビス(4-t-ブチルシクロヘキシル)パーオキシジカーボネート(分子量:399、理論活性酸素量:4.0%、10時間半減期温度:40.8℃)、ジ-2-エチルヘキシルパーオキシジカーボネート(分子量:346、理論活性酸素量:4.6%、10時間半減期温度:43.6℃)、ジ-sec-ブチルパーオキシジカーボネート(分子量:234、理論活性酸素量:6.8%、10時間半減期温度:40.5℃)等のパーオキシジカーボネート類。
クミルパーオキシネオデカノエート(分子量:306、理論活性酸素量:5.2%、10時間半減期温度:36.5℃)、1,1,3,3-テトラメチルブチルパーオキシネオデカノエート(分子量:300、理論活性酸素量:5.3%、10時間半減期温度:40.7℃)、t-ヘキシルパーオキシデカノエート(分子量:272、理論活性酸素量:5.9%、10時間半減期温度:44.5℃)、t-ブチルパーオキシネオデカノエート(分子量:244、理論活性酸素量:6.6%、10時間半減期温度:46.4℃)、t-ブチルパーオキシネオヘプタノエート(分子量:202、理論活性酸素量:7.9%、10時間半減期温度:50.6℃)、t-ヘキシルパーオキシピバレート(分子量:202、理論活性酸素量:7.9%、10時間半減期温度:53.2℃)、t-ブチルパーオキシピバレート(分子量:174、理論活性酸素量:9.2%、10時間半減期温度:54.6℃)、2,5-ジメチル-2,5-ジ(2-エチルヘキサノイルパーオキシ)ヘキサン(分子量:431、理論活性酸素量:7.4%、10時間半減期温度:66.2℃)、1,1,3,3-テトラメチルブチルパーオキシ-2-エチルヘキサノエート(分子量:272、理論活性酸素量:5.9%、10時間半減期温度:65.3℃)、t-ヘキシルパーオキシ-2-エチルヘキサノエート(分子量:244、理論活性酸素量:6.6%、10時間半減期温度:69.9℃)、t-ブチルパーオキシ-2-エチルヘキサノエート(分子量:216、理論活性酸素量:7.4%、10時間半減期温度:72.1℃)、t-ブチルパーオキシラウレート(分子量:272、理論活性酸素量:5.9%、10時間半減期温度:98.3℃)、t-ブチルパーオキシ-3,5,5-トリメチルヘキサノエート(分子量:230、理論活性酸素量:7.0%、10時間半減期温度:97.1℃)、t-ヘキシルパーオキシイソプロピルモノカーボネート(分子量:204、理論活性酸素量:7.8%、10時間半減期温度:95.0℃)、t-ブチルパーオキシイソプロピルモノカーボネート(分子量:176、理論活性酸素量:9.1%、10時間半減期温度:98.7℃)、t-ブチルパーオキシ-2-エチルヘキシルモノカーボネート(分子量:246、理論活性酸素量:6.5%、10時間半減期温度:99.0℃)、2,5-ジメチル-2,5-ジ(ベンゾイルパーオキシ)ヘキサン(分子量:386、理論活性酸素量:8.3、10時間半減期温度:99.7℃)、t-ブチルパーオキシアセテート(分子量:132、理論活性酸素量:12.1%、10時間半減期温度:101.9℃)、t-ヘキシルパーオキシベンゾエート(分子量:222、理論活性酸素量:7.2%、10時間半減期温度:99.4℃)、t-ブチルパーオキシ-3-メチルベンゾエート(理論活性酸素量:8.1%)、t-ブチルパーオキシベンゾエート(分子量:194、理論活性酸素量:8.2%、10時間半減期温度:104.3℃)等のパーオキシエステル類。
過酸化物系重合開始剤の中でも、パーオキシエステル類、パーオキシケタール類、及び、ジアシルパーオキサイド類が、トナーの低温定着性能と耐久安定性能との両立の観点から好ましい。トナーの低温定着性能の観点から、特に好ましい過酸化物系重合開始剤としては、パーオキシエステル類である。
本発明のトナーに用いられる過酸化物系重合開始剤としては、分子量が140乃至400であり、理論活性酸素量が5.00乃至12.00%である過酸化物系重合開始剤が好ましい。結着樹脂の分子鎖の末端に導入される官能基の炭素数、及び、重合反応と水素引き抜き反応のバランスがより良好となり、トナーの低温定着性能と耐久安定性能がより良好になりやすい。このため、過酸化物系重合開始剤の分子量としては、140乃至350であることがより好ましく、150乃至300であることがさらに好ましい。特に好ましい過酸化物系重合開始剤の分子量としては、160乃至250である。また、過酸化物系重合開始剤の理論活性酸素量としては、6.00乃至11.00%であることがより好ましく、6.80乃至11.00%であることがさらに好ましい。
低分子量ポリエチレン、低分子量ポリプロピレン、アルキレン共重合体、マイクロクリスタリンワックス、パラフィンワックス、フィッシャートロプシュワックスなどの脂肪族炭化水素系ワックス、また、酸化ポリエチレンワックスなどの脂肪族炭化水素系ワックスの酸化物、又はそれらのブロック共重合物;カルナバワックス、ベヘン酸ベヘニルエステルワックス、モンタン酸エステルワックスなどの脂肪酸エステルを主成分とするワックス類、及び脱酸カルナバワックスなどの脂肪酸エステル類を一部又は全部を脱酸化したものなどが挙げられる。更に、パルミチン酸、ステアリン酸、モンタン酸などの飽和直鎖脂肪酸類;ブラシジン酸、エレオステアリン酸、バリナリン酸などの不飽和脂肪酸類;ステアリルアルコール、アラルキルアルコール、ベヘニルアルコール、カルナウビルアルコール、セリルアルコール、メリシルアルコールなどの飽和アルコール類;ソルビトールなどの多価アルコール類;パルミチン酸、ステアリン酸、ベヘン酸、モンタン酸等の脂肪酸類とステアリルアルコール、アラルキルアルコール、ベヘニルアルコール、カルナウビルアルコール、セリルアルコール、メリシルアルコール等のアルコール類のエステル類;リノール酸アミド、オレイン酸アミド、ラウリン酸アミドなどの脂肪酸アミド類;メチレンビスステアリン酸アミド、エチレンビスカプリン酸アミド、エチレンビスラウリン酸アミド、ヘキサメチレンビスステアリン酸アミドなどの飽和脂肪酸ビスアミド類;エチレンビスオレイン酸アミド、ヘキサメチレンビスオレイン酸アミド、N,N’-ジオレイルアジピン酸アミド、N,N’-ジオレイルセバシン酸アミドなどの不飽和脂肪酸アミド類;m-キシレンビスステアリン酸アミド、N,N’-ジステアリルイソフタル酸アミドなどの芳香族系ビスアミド類;ステアリン酸カルシウム、ラウリン酸カルシウム、ステアリン酸亜鉛、ステアリン酸マグネシウムなどの脂肪族金属塩(一般に金属石けんといわれているもの);脂肪族炭化水素系ワックスにスチレンやアクリル酸などのビニル系モノマーを用いてグラフト化させたワックス類;ベヘニン酸モノグリセリドなどの脂肪酸と多価アルコールの部分エステル化物;植物性油脂の水素添加などによって得られるヒドロキシル基を有するメチルエステル化合物などが挙げられる。
中でも、融点55乃至100℃以下の脂肪族炭化水素系ワックスやエステルワックスは、トナーの低温定着性能と耐久安定性能の両立、及び、定着後の発色性を向上させることができる。脂肪族炭化水素系ワックスは顔料の芳香環と、エステルワックスのエステル結合は顔料のカルボニル基と極性が近いために効果的に着色剤と相互作用し、着色剤の発色性能を良化するためと考えられる。
特に好ましく用いられるワックスとしては、分子鎖が短く、且つ、立体障害が少なくモビリティに優れるパラフィンワックス、ポリエチレン、フィッシャートロプシュワックスの如き脂肪族炭化水素ワックスである。
ワックスの分子量分布では、メインピークが分子量350乃至2400の領域にあることが好ましく、分子量400乃至2000の領域にあることが、トナーの低温定着性性能の向上の点でより好ましい。このような分子量分布を持たせることによりトナーに好ましい熱特性を付与することができる。
上記ワックスの含有量としては、結着樹脂100質量部に対し3乃至30質量部含有すると、トナーの低温定着性能、耐オフセット性能、及び、耐久安定性能の両立の点で好ましい。本発明のトナーが有するワックスの含有量としては、5乃至20質量部であることがより好ましく、6乃至14質量部であることが特に好ましい。
上記の如き物性を求めるにあたって、ワックスをトナーから抽出する場合には、抽出方法は特に制限されるものではなく、任意の方法が可能である。一例を挙げると、所定量のトナーをトルエンにてソックスレー抽出し、得られたトルエン可溶分から溶剤を除去した後、クロロホルム不溶分を得る。その後、IR法などにより同定分析をする。また、定量に関しては、DSCにより定量分析を行う。
トナー粒子を負荷電性に制御する荷電制御剤としては、以下のものが挙げられる。
有機金属化合物、キレート化合物、モノアゾ金属化合物、アセチルアセトン金属化合物、尿素誘導体、含金属サリチル酸系化合物、含金属ナフトエ酸系化合物、4級アンモニウム塩、カリックスアレーン、ケイ素化合物、ノンメタルカルボン酸系化合物及びその誘導体が挙げられる。また、スルホン酸基、スルホン酸塩基、或いは、スルホン酸エステル基を有するスルホン酸樹脂は好ましく用いることができる。
トナー粒子を正荷電性に制御する荷電制御剤としては、例えば、以下に示す荷電制御剤を用いることができる。
ニグロシン及び脂肪酸金属塩による変性物、トリブチルベンジルアンモニウム-1-ヒドロキシ-4-ナフトスルホン酸塩、テトラブチルアンモニウムテトラフルオロボレート等の4級アンモニウム塩、及びこれらの類似体であるホスホニウム塩等のオニウム塩及びこれらのレーキ顔料、トリフェニルメタン染料及びこれらのレーキ顔料(レーキ化剤としては、リンタングステン酸、リンモリブデン酸、リンタングステンモリブデン酸、タンニン酸、ラウリン酸、没食子酸、フェリシアン化物、フェロシアン化物等)、高級脂肪酸の金属塩;。これらを単独或いは2種類以上組み合わせて用いることができる。
上記硫黄元素の含有量は、前記スルホン酸系樹脂が有するスルホン酸基の含有量、及び、該スルホン酸樹脂の添加量により制御することができる。
上記スルホン酸系樹脂は、上記Mwと個数平均分子量(Mn)との比(Mw/Mn)が1.50乃至20.00であることが、トナーの低温定着性能と耐久安定性能の両立の観点から好ましい。より好ましくは2.00乃至10.00であり、さらに好ましくは2.00乃至5.00である。
シアントナー、マゼンタトナー、イエロートナー用の着色剤として、例えば、以下に示す着色剤を用いることができる。
C.I.ピグメントイエロー3,7,10,12~15,17,23,24,60,62,73,74,75,83,93~95,99,100,101,104,108~111,117,120,123,128,129,138,139,147,148,150,151,154,155,166,168~177,179,180,181,183,185,191:1,191,192,193,199、214。
染料系としては、例えば、C.l.ソルベントイエロー33,56,79,82,93,112,162,163、C.I.ディスパースイエロー42,64,201,211が挙げられる。
これらの磁性体は、トナーの低温定着性能及び耐久安定性能の観点より、個数平均粒子径が2μm以下であることが好ましく、より好ましくは0.1~0.5μmである。トナー中に含有させる量としては結着樹脂100質量部に対し20~200質量部であることが好ましく、より好ましくは40~150質量部である。
上記磁性体は、796kA/m(10kエルステッド)印加での磁気特性において、保磁力(Hc)が1.59~23.9kA/m(20~300エルステッド)、飽和磁化(σs)が50~200Am2/kg、残留磁化(σr)が2~20Am2/kgであることが好ましい。
上記クリーニング性を向上させる目的の外部添加剤としては、例えば、一次粒径が30nmを超える(好ましくは比表面積が50m2/g未満)微粒子、より好ましくは一次粒径が50nm以上(好ましくは比表面積が30m2/g未満)で球状に近い無機微粒子又は有機微粒子が挙げられる。これらの内、球状のシリカ微粒子、球状のポリメチルシルセスキオキサン微粒子、又は球状の樹脂微粒子が好ましい。
フッ素樹脂粉末、ステアリン酸亜鉛粉末、ポリフッ化ビニリデン粉末の如き滑剤粉末;酸化セリウム粉末、炭化硅素粉末、チタン酸ストロンチウム粉末の如き研磨剤;ケーキング防止剤;カーボンブラック粉末、酸化亜鉛粉末、酸化スズ粉末の如き導電性付与剤;逆極性の有機微粒子、又は無機微粒子。これらの添加剤も、その表面を疎水化処理して用いることも可能である。
上述の如き外添剤は、トナー粒子100質量部に対して0.1乃至5質量部使用することが好ましく、0.1乃至3質量部使用することがより好ましい。
本発明のトナーは、水中においてトナー粒子を形成する工程を有する製法により製造されることが好ましい。具体的には、以下の方法が挙げられる。
(1)水中において、シェル用樹脂、重合性単量体、ワックス、及び、着色剤を少なくとも有する単量体組成物の水分散液を形成する工程、該水分散液の重合性単量体を重合する工程を経てトナー粒子を形成する、いわゆる懸濁重合法による方法。
(2)水中において、結着樹脂を有する樹脂粒子、ワックス、着色剤を少なくとも有する水分散液を形成する工程、該水分散液において樹脂粒子を凝集させて、着色粒子の分散液を形成する工程、該分散液にシェル用樹脂を有する樹脂粒子を添加し、前記着色粒子を被覆する工程を経てトナー粒子を形成する、いわゆる乳化凝集法による方法。
(3)結着樹脂、該結着樹脂を溶解可能な溶剤、ワックス、着色剤を少なくとも有する樹脂組成物を形成する工程、シェル用樹脂を有する水中において、前記樹脂組成物を分散して水分散液を形成する工程、該水分散液から前記溶剤を除去する工程を経てトナー粒子を形成する、いわゆる溶解懸濁法による方法。
懸濁重合法によるトナー粒子の具体的な製造方法は以下の通りである。
重合性単量体、シェル用樹脂、着色剤、ワックス、その他必要に応じて荷電制御剤、及び架橋剤などの添加剤を、ホモジナイザー、ボールミル、コロイドミル、超音波分散機等の分散機によって均一に溶解又は分散させる。こうして得られた単量体組成物を、分散安定剤を含有する水系媒体中に懸濁する。この時、高速撹拌機もしくは超音波分散機のような高速分散機を使用して一気に所望のトナー粒子のサイズとすることで、得られるトナー粒子の粒度分布がシャープになる。重合開始剤添加の時期としては、予め単量体組成物に加えても良いし、水系媒体中に単量体組成物を懸濁した後に添加しても良い。
懸濁後は、通常の撹拌機を用いて、粒子状態が維持されかつ粒子の浮遊・沈降が防止される程度の撹拌を行えば良い。なお、本発明においては、前記懸濁する際に、pHが4乃至10.5であることが、トナー形状の均一性の点で好ましい。pHが4未満であると、トナーの粒子径分布が大きくなりやすい。またpHが10.5を超えると、トナーの帯電性能が低下する場合がある。
これらの無機分散剤は、重合性単量体100質量部に対して、0.2乃至20質量部を単独で又は2種類以上組み合わせて使用することが好ましい。また、より微粒化されたトナーの製造を目的とする場合には、重合性単量体100質量部に対して0.001乃至0.1質量部の界面活性剤を併用しても良い。界面活性剤としては、例えばドデシルベンゼン硫酸ナトリウム、テトラデシル硫酸ナトリウム、ペンタデシル硫酸ナトリウム、オクチル硫酸ナトリウム、オレイン酸ナトリウム、ラウリル酸ナトリウム、ステアリン酸ナトリウム、ステアリン酸カリウムが挙げられる。
これらの無機分散剤を用いる場合には、そのまま使用しても良いが、より細かい粒子を得るため、水系媒体中にて該無機分散剤を生成させることが好ましい。具体的には、リン酸三カルシウムの場合、高速撹拌下、リン酸ナトリウム水溶液と塩化カルシウム水溶液とを混合して、難水溶性のリン酸三カルシウムを生成させることができ、より均一で細かな分散が可能となる。無機分散剤は、重合終了後酸あるいはアルカリで溶解して、ほぼ完全に取り除くことができる。
本発明において、上記懸濁重合法、及びその他の重合法における重合工程において、重合開始剤の10時間半減期温度(℃)に対し、重合開始時の温度を15.0乃至50.0℃高い温度として重合することが好ましい。重合初期のラジカル濃度を高くすることができることで、重合工程の早い段階から分子量が揃った分子鎖を多く生成することが可能となる。これにより、架橋結合が抑制されやすく、THF不溶性分やIPA可溶成分の含有量を好適に制御できる。また、前述したシェル用樹脂を用いる場合、該シェル用樹脂と結着樹脂の一部とがグラフト結合しやすくなり、シェル用樹脂と結着樹脂との接着性が向上しやすい。尚、重合開始剤の10時間半減期温度(℃)に対する重合開始時の温度は、25.0乃至50.0℃であることがより好ましく、30.0乃至50.0℃であることがさらに好ましい。
本発明において、上記懸濁重合法、及びその他の重合法における重合工程において、重合により生成する結着樹脂のガラス転移点(Tg)(℃)に対し、重合開始時の温度を30.0乃至70.0℃高い温度として重合することが好ましい。重合途中の分子鎖の運動が激しくなるため架橋結合が抑制されやすく、THF不溶性分やIPA可溶成分の含有量を好適に制御できる。また、前述したシェル用樹脂を用いる場合、該シェル用樹脂と結着樹脂の一部とがグラフト結合しやすくなり、シェル用樹脂と結着樹脂との接着性が向上しやすい。尚、結着樹脂のガラス転移点(Tg)(℃)に対する重合開始時の温度は、35.0乃至60.0℃であることがより好ましく、35.0乃至50.0℃であることがさらに好ましい。
二成分系現像剤として用いる場合には、本発明のトナーとキャリアとを混合した現像剤として使用する。該キャリアは、公知のいずれのものであっても良い。例えば、鉄、銅、亜鉛、ニッケル、コバルト、マンガン、及び、クロム元素から選ばれる元素からなるキャリアや鉄とそれ以外の元素の複合酸化物からなるフェライトキャリアが挙げられる。或いは、樹脂中に磁性体を分散させた磁性体含有樹脂キャリアや多孔質磁性体の孔に樹脂を充填した樹脂充填キャリアであってもよい。該キャリアの形状としては、球または略球状、扁平または不定形があり、そのいずれのものも用いることができる。中でも、キャリアは表面に樹脂成分を有し、真密度が2.5乃至4.2g/cm3の磁性キャリアであることが好ましい。
キャリアの粒径は、風力分級機(エルボジェットラボEJ-L3、日鉄鉱業社製)等で分級することで、上記の範囲内にすることができる。
上記体積分布基準の50%粒径(D50)の測定方法は後述する。
トナー、キャリアの真密度は、気体置換型ピクノメータを用いる方法により測定することができる。測定原理は、一定体積の試料室(体積V1)と比較室(体積V2)との間に遮断弁を設け、予め質量(M0(g))を測定したのちサンプルを試料室に入れる。試料室及び比較室内をヘリウムの如き不活性ガスで充満し、そのときの圧力をP1とする。遮断弁を閉じ、試料室のみ不活性ガスを加える。そのときの圧力をP2とする。遮断弁を開き、試料室と比較室とを接続したときの系内の圧力をP3とする。下記式Aにより、サンプルの体積(V0(cm3))を求めることができる。下記式Bにより、トナー、キャリアの真密度ρ(g/cm3)を求めることができる。
V0=V1-[V2/{(P2-P1)/(P3-P1)-1}] (式A)
ρ=M0/V0 (式B)
上記の方法として、本発明では乾式自動密度計アキュピック1330(島津製作所(株)社製)を用いて測定した。この際、10cm3の試料容器を用い、試料前処理としてはヘリウムガスパージを最高圧19.5psig(134.4kPa)で10回行う。この後、容器内圧力が平衡に達したか否かの圧力平衡判定値として、試料室内の圧力の振れが0.0050psig/minを目安とし、この値以下であれば平衡状態とみなして測定を開始し、真密度を自動測定する。測定は5回行い、その平均値を求めて真密度(g/cm3)とする。
本発明において、GPCによる重量平均分子量(Mw)、個数平均分子量(Mn)、分子量分布のピーク分子量(Mp)とは、以下の方法によって求められる値である。
測定するサンプル30mgをテトラヒドロフラン(THF)5mlに入れ、室温にて24時間静置する。これを、高速液体クロマトグラフ(HPLC)用ディスポーザブルフィルター「マイショリディスク H-25-5」(東ソー社製)で濾過してサンプル溶液を得る。このサンプル溶液を用いて、以下の条件で測定する。
装置:HLC8120 GPC(検出器:RI)(東ソー社製)
カラム:Shodex KF-801、802、803、804、805、806、807の7連(昭和電工社製)
溶離液:テトラヒドロフラン(THF)
流速:1.0ml/min
オーブン温度:40.0℃
試料注入量:0.10ml
試料の分子量の算出にあたっては、以下の標準サンプルを用いて作成した分子量校正曲線を使用する。Polymer Laboratories社製 標準ポリスチレンEasical PS-1(分子量7500000、841700、148000、28500、2930の混合物、及び、分子量2560000、320000、59500、9920、580の混合物)及びPS-2(分子量377400、96000、19720、4490、1180の混合物、及び、分子量188700、46500、9920、2360、580の混合物)。検出器にはRI(屈折率)検出器を用いる。
以下に示すソックスレー抽出法により測定される。
円筒濾紙(東洋濾紙製No.86Rを使用)を、温度40℃で24時間真空乾燥した後、25℃、60%RHの温湿度に調整された環境下に3日間放置する。この円筒濾紙に測定する試料約2.0gを秤量し、このときの試料の重さをW1(g)とする。ソックスレー抽出器を用い、溶媒としてTHF、IPA、又はメタノール200mlを用い、温度90℃のオイルバスで24時間抽出する。その後、円筒濾紙を静かに取り出して、温度40℃で24時間真空乾燥する。これを温度25℃、湿度60%RHに調整された環境下に3日間放置した後、円筒濾紙に残存する固形分の量を秤量し、これをW2(g)とする。THF可溶成分、或いは不溶成分の含有量、IPA可溶成分の含有量、メタノール不溶成分の含有量は、下記式から算出される。
試料のTHF又はメタノール不溶成分の含有量(質量%)=(W2/W1)×100
試料のTHF又はIPA可溶成分の含有量(質量%)=100-(W2/W1)×100
THF可溶成分の蛍光X線測定を行うサンプルとしては、上記ソックスレー抽出器により抽出された溶液のTHFを留去させて樹脂成分を回収し、温度40℃で24時間真空乾燥したものを用いる。
本発明において、ガラス転移点(Tg)、融点(Tm)、並びに最大吸熱ピークの温度、吸熱量の測定は、示差走査熱量計(DSC)を用いて測定する。DSCとして、具体的に、Q1000(TAインストルメンツ社製)を使用する。測定方法は、アルミパンに試料4mgを精秤し、リファレンスパンとして空のアルミパンを用い、窒素雰囲気下、モジュレーション振幅0.5℃、周波数1/分で測定する。測定温度は、10℃で10分間保持した後、昇温速度1℃/分で10℃から180℃まで走査して得られたリバーシングヒートフロー曲線をDSC曲線とし、これを用いて中点法によりTgを求める。なお、中点法によって求められたガラス転移点とは、昇温時のDSC曲線において吸熱ピーク前の基線と吸熱ピーク後の基線の中線と、立ち上がり曲線での交点をもってガラス転移点とするものである(図1参照)。
トナーの最大吸熱ピークの温度、吸熱量の測定は、上記と同様に測定して得られたリバーシングヒートフロー曲線において、吸熱ピーク前のベースラインの外挿線から該吸熱ピークが離脱する点と、吸熱ピーク終了後のベースラインの外挿線と該吸熱ピークが接する点とを結んだ直線と吸熱ピークとで囲まれる領域において、該吸熱ピークの極大値となる温度を、最大吸熱ピークの温度とする。該ピークに極大値が2つ以上存在する場合は、前記囲まれる領域において、前記結んだ直線と極大値との長さが長い極大値における温度を、最大吸熱ピークの温度とする。前記囲まれる領域が独立して2つ以上存在する場合にも、前記と同様にして結んだ直線と極大値との長さが長い極大値における温度を、最大吸熱ピークの温度とする。
吸熱量は、上記測定で得られたリバーシングヒートフロー曲線において、吸熱ピーク前のベースラインの外挿線から該吸熱ピークが離脱する点と、吸熱ピーク終了後のベースラインの外挿線と該吸熱ピークが接する点とを結んだ直線と吸熱ピークとで囲まれる領域の面積(融解ピークの積分値)より吸熱量(J/g)を求める。前記囲まれる領域が独立して2つ以上存在する場合には、それらを合計して吸熱量とする。
ワックスの融点は、上記トナーの最大吸熱ピークの温度の測定方法と同様にして測定した最大吸熱ピークの温度である。
樹脂の酸価は以下のように求められる。基本操作は、JIS-K0070に準ずる。
試料1g中に含有されている遊離脂肪酸、樹脂の酸基などを中和するのに要する水酸化カリウムのmg数を酸価といい、以下の方法によって測定される。
(1)試薬
(a)溶剤の調製
試料の溶剤としては、エチルエーテル-エチルアルコール混液(1+1または2+1)またはベンゼン-エチルアルコール混液(1+1または2+1)を用いる。これらの溶液は使用直前にフェノールフタレインを指示薬として0.1モル/リットルの水酸化カリウムエチルアルコール溶液で中和しておく。
(b)フェノールフタレイン溶液の調製
フェノールフタレイン1gをエチルアルコール(95v/v%)100mlに溶かす。
(c)0.1モル/リットルの水酸化カリウム-エチルアルコール溶液の調製
水酸化カリウム7.0gをできるだけ少量の水に溶かしエチルアルコール(95v/v%)を加えて1リットルとし、2~3日放置後ろ過する。標定はJISK 8006(試薬の含量試験中滴定に関する基本事項)に準じて行う。
(2)操作
試料1~20gを正しくはかりとり、これに溶剤100ml及び指示薬としてフェノールフタレイン溶液数滴を加え、試料が完全に溶けるまで十分に振る。固体試料の場合は水浴上で加温して溶かす。冷却後これを0.1モル/リットルの水酸化カリウム-エチルアルコール溶液で滴定し、指示薬の微紅色が30秒間続いたときを中和の終点とする。
(3)計算式
次の式によって酸価を算出する。
A=B×f×5.611/S
A:酸価(mgKOH/g)
B:0.1モル/リットル-水酸化カリウムエチルアルコール溶液の使用量(ml)
f:0.1モル/リットル-水酸化カリウムエチルアルコール溶液のファクター
S:試料(g)
試料1gを規定の方法によってアセチル化するとき水酸基と結合した酢酸を中和するのに要する水酸化カリウムのmg数を水酸基価といい、以下の方法によって測定される。
(1)試薬
(a)アセチル化試薬の調製
無水酢酸25mlをメスフラスコ100mlに入れ、ピリジンを加えて全量を100mlにし、十分に振りまぜる。(場合によっては、ピリジンを追加しても良い)。アセチル化試薬は、湿気、炭酸ガス及び酸の蒸気に触れないようにし、褐色びんに保存する。
(b)フェノールフタレイン溶液の調製
フェノールフタレイン1gをエチルアルコール(95v/v%)100mlに溶かす。
(c)0.2モル/リットルの水酸化カリウム-エチルアルコール溶液の調製
水酸化カリウム35gをできるだけ少量の水に溶かし、エチルアルコール(95v/v%)を加えて1リットルとし、2~3日放置後ろ過する。標定はJISK 8006によって行う。
(2)操作
試料0.5~20gを丸底フラスコに正しくはかりとり、これにアセチル化試薬5mlを正しく加える。フラスコの口に小さな漏斗をかけ、温度95~100℃のグリセリン浴中に底部約1cmを浸して加熱する。このときフラスコの首が浴の熱を受けて温度が上がるのを防ぐために、中に丸い穴をあけた厚紙の円盤をフラスコの首の付け根にかぶせる。1時間後フラスコを浴から取り出し、放冷後漏斗から水1mlを加えて振り動かして無水酢酸を分解する。さらに分解を完全にするため、再びフラスコをグリセリン浴中で10分間加熱し、放冷後、エチルアルコール5mlで漏斗及びフラスコの壁を洗い、フェノールフタレイン溶液を指示薬として0.2モル/リットルの水酸化カリウムエチルアルコール溶液で滴定する。尚、本試験と並行して空試験を行う。場合によっては、指示薬としてKOH-THF溶液にしても構わない。
(3)計算式
次の式によって水酸基価を算出する。
A={(B-C)×f×28.05/S}+D
A:水酸基価(mgKOH/g)
B:空試験の0.5モル/リットル-水酸化カリウムエチルアルコール溶液の使用量(ml)
C:本試験の0.5モル/リットル-水酸化カリウムエチルアルコール溶液の使用量(ml)
f:0.5モル/リットル-水酸化カリウムエチルアルコール溶液のファクター
S:試料(g)
D:酸価(mgKOH/g)
トナー粒子の平均円形度は、フロー式粒子像分析装置「FPIA-3000」(シスメックス社製)を用い、校正作業時の測定及び解析条件で測定する。
具体的な測定方法は、以下の通りである。まず、ガラス製の容器中に予め不純固形物などを除去したイオン交換水約20mlを入れる。この中に分散剤として「コンタミノンN」(非イオン界面活性剤、陰イオン界面活性剤、有機ビルダーからなるpH7の精密測定器洗浄用中性洗剤の10質量%水溶液、和光純薬工業社製)をイオン交換水で約3質量倍に希釈した希釈液を約0.2ml加える。更に測定試料を約0.02g加え、超音波分散器を用いて2分間分散処理を行い、測定用の分散液とする。その際、分散液の温度が10℃以上40℃以下となる様に適宜冷却する。超音波分散器としては、発振周波数50kHz、電気的出力150Wの卓上型の超音波洗浄器分散器(例えば「VS-150」(ヴェルヴォクリーア社製))を用い、水槽内には所定量のイオン交換水を入れ、この水槽中に前記コンタミノンNを約2ml添加する。
測定には、対物レンズとして「UPlanApro」(倍率10倍、開口数0.40)を搭載した前記フロー式粒子像分析装置を用い、シース液にはパーティクルシース「PSE-900A」(シスメックス社製)を使用する。前記手順に従い調整した分散液を前記フロー式粒子像分析装置に導入し、HPF測定モードで、トータルカウントモードにて3000個のトナー粒子を計測する。そして、粒子解析時の2値化閾値を85%とし、解析粒子径を円相当径1.985μm以上、39.69μm未満に限定し、トナー粒子の平均円形度を求める。
測定にあたっては、測定開始前に標準ラテックス粒子(例えば、Duke Scientific社製の「RESEARCH AND TEST PARTICLES Latex Microsphere Suspensions 5200A」をイオン交換水で希釈)を用いて自動焦点調整を行う。その後、測定開始から2時間毎に焦点調整を実施することが好ましい。
なお、本願実施例では、シスメックス社による校正作業が行われた、シスメックス社が発行する校正証明書の発行を受けたフロー式粒子像分析装置を使用する。解析粒子径を円相当径1.985μm以上、39.69μm未満に限定した以外は、校正証明を受けた時の測定及び解析条件で測定を行う。
トナーの重量平均粒子径D4(μm)、個数平均粒子径D1(μm)は、具体的には以下の方法により測定することができる。
装置としては、100μmのアパーチャーチューブを備えた細孔電気抵抗法による精密粒度分布測定装置「コールター・カウンター Multisizer 3」(登録商標、ベックマン・コールター社製)を用いる。測定条件の設定及び測定データの解析は、付属の専用ソフト「ベックマン・コールター Multisizer 3 Version3.51」(ベックマン・コールター社製)を用いる。尚、測定は実効測定チャンネル数2万5千チャンネルで行なう。
測定に使用する電解水溶液は、特級塩化ナトリウムをイオン交換水に溶解して濃度が約1質量%となるようにしたもの、例えば、「ISOTON II」(ベックマン・コールター社製)が使用できる。
尚、測定、解析を行う前に、以下のように専用ソフトの設定を行う。
専用ソフトの「標準測定方法(SOM)を変更」画面において、コントロールモードの総カウント数を50000粒子に設定し、測定回数を1回、Kd値は「標準粒子10.0μm」(ベックマン・コールター社製)を用いて得られた値を設定する。「閾値/ノイズレベルの測定ボタン」を押すことで、閾値とノイズレベルを自動設定する。また、カレントを1600μAに、ゲインを2に、電解液をISOTON IIに設定し、「測定後のアパーチャーチューブのフラッシュ」にチェックを入れる。
専用ソフトの「パルスから粒径への変換設定」画面において、ビン間隔を対数粒径に、粒径ビンを256粒径ビンに、粒径範囲を2μmから60μmまでに設定する。
具体的な測定法は以下の通りである。
(1)Multisizer 3専用のガラス製250ml丸底ビーカーに前記電解水溶液約200mlを入れ、サンプルスタンドにセットし、スターラーロッドの撹拌を反時計回りで24回転/秒にて行う。そして、専用ソフトの「アパーチャーのフラッシュ」機能により、アパーチャーチューブ内の汚れと気泡を除去しておく。
(2)ガラス製の100ml平底ビーカーに前記電解水溶液約30mlを入れる。この中に分散剤として「コンタミノンN」(非イオン界面活性剤、陰イオン界面活性剤、有機ビルダーからなるpH7の精密測定器洗浄用中性洗剤の10質量%水溶液、和光純薬工業社製)をイオン交換水で約3質量倍に希釈した希釈液を約0.3ml加える。
(3)発振周波数50kHzの発振器2個を、位相を180度ずらした状態で内蔵し、電気的出力120Wの超音波分散器「Ultrasonic Dispension System Tetora150」(日科機バイオス社製)を準備する。超音波分散器の水槽内に所定量のイオン交換水を入れ、この水槽中に前記コンタミノンNを約2ml添加する。
(4)前記(2)のビーカーを前記超音波分散器のビーカー固定穴にセットし、超音波分散器を作動させる。そして、ビーカー内の電解水溶液の液面の共振状態が最大となるようにビーカーの高さ位置を調整する。
(5)前記(4)のビーカー内の電解水溶液に超音波を照射した状態で、トナー約10mgを少量ずつ前記電解水溶液に添加し、分散させる。そして、さらに60秒間超音波分散処理を継続する。尚、超音波分散にあたっては、水槽の水温が10℃以上40℃以下となる様に適宜調節する。
(6)サンプルスタンド内に設置した前記(1)の丸底ビーカーに、ピペットを用いてトナーを分散した前記(5)の電解質水溶液を滴下し、測定濃度が約5%となるように調整する。そして、測定粒子数が50000個になるまで測定を行う。
(7)測定データを装置付属の前記専用ソフトにて解析を行い、重量平均粒径(D4)および個数平均粒径(D1)を算出する。尚、専用ソフトでグラフ/体積%と設定した時の、「分析/体積統計値(算術平均)」画面の「平均径」が重量平均粒径(D4)であり、グラフ/個数%と設定したときの、「分析/個数統計値(算術平均)」画面の「平均径」が個数平均粒径(D1)である。
波長分散型蛍光X線「Axios advanced」(PANalytical(パナリティカル)社製)を用いて測定する。サンプル約3gを、27mm測定用の塩化ビニル製リングに入れ、200kNでプレスし、試料を成型する。使用したサンプル量と成形後の試料の厚みを測定し、含有量算出のための入力値として、スルホン酸基に由来する硫黄元素の含有量を求める。分析条件及び解析方法は下記に示す。
(分析条件)
・定量方法:ファンダメンタルパラメータ法
・分析元素:周期表におけるホウ素B~ウランUまでの各元素について測定
・測定雰囲気:真空
・測定サンプル:固体
・コリメーターマスク径:27mm
・測定条件:各元素に最適な励起条件にあらかじめ設定された自動プログラムを用いた
・測定時間:約20分
・その他は装置の推奨する一般値を用いた
(解析方法)
・解析プログラム:UniQuant5
・解析条件:酸化物形態
・バランス成分:CH2
・その他は装置の推奨する一般値を用いた
キャリアの体積分布基準の50%粒径(D50)及び平均円形度は、マルチイメージアナライザー(ベックマン・コールター社製)を用いて、以下のようにして測定される。
約1%NaCl水溶液とグリセリンとを、50体積%:50体積%で混合した溶液を電解液として用いる。ここでNaCl水溶液は、一級塩化ナトリウムを用いて調製されればよく、例えばISOTON(登録商標)-II(コールターサイエンティフィックジャパン社製)であってもよい。グリセリンは、特級あるいは一級の試薬であればよい。
電解液(約30ml)に、分散剤として界面活性剤(好ましくはアルキルベンゼンスルホン塩酸)を、0.1~1.0ml加え、さらに測定試料を2~20mg加える。試料が懸濁された電解液を、超音波分散器で約1分間分散処理して、分散液を得る。
アパーチャーとして200μmアパーチャー、20倍のレンズを用いて、以下の測定条件で円相当径および円形度を算出する。
測定フレーム内平均輝度:220~230
測定フレーム設定:300
SH(スレシュホールド):50
2値化レベル:180
ガラス測定容器に電解液及び前記分散液を入れて、測定容器中のキャリア粒子の濃度を5~10体積%とする。ガラス測定容器内容物を最大撹拌スピードで撹拌する。サンプルの吸引圧を10kPaにする。キャリア比重が大きく沈降しやすい場合は、測定時間を15~30分とする。また、5~10分ごとに測定を中断して、サンプル液の補充および電解溶液-グリセリン混合溶液の補充を行う。
測定個数は2000個とする。測定終了後、本体ソフトにより、粒子画像画面でピンぼけ画像、凝集粒子(複数同時測定)などの除去を行う。
キャリアの円形度および円相当径は、下記式で算出される。
円形度=(4×Area)/(MaxLength2×π)
円相当径=(4・Area/π)1/2
ここで、「Area」とは二値化されたキャリア粒子像の投影面積であり、「MaxLength」とは該キャリア粒子像の最大径と定義される。円相当径は、「Area」を真円の面積としたときの真円の直径で表される。円相当径は、4~100μmを256分割され、体積基準で対数表示して用いる。これを用い、体積分布基準の50%粒径(D50)を求める。平均円形度は、各粒子の円形度を足し合わせ、全粒子数で割った値を平均円形度とする。
キャリアの磁化の強さは、振動磁場型磁気特性装置VSM(Vibrating sample magnetometer)や直流磁化特性記録装置(B-Hトレーサー)などで求めることが可能である。好ましくは、振動磁場型磁気特性装置で測定できる。振動磁場型磁気特性装置の例には、理研電子(株)製の振動磁場型磁気特性自動記録装置BHV-30が含まれる。これを用いて、以下の手順で測定することができる。円筒状のプラスチック容器にキャリアを十分に密に充填し、一方で1000/4π(kA/m)(1000エルステッド)の外部磁場を作り、この状態で容器に充填されたキャリアの磁化モーメントを測定する。さらに、該容器に充填したキャリアの実際の質量を測定して、キャリアの磁化の強さ(Am2/kg)を求める。
撹拌機、窒素導入管を備えた耐圧容器Aに、窒素雰囲気下、下記材料を入れた。
トルエン:20質量部
上記容器Aに接続され、流量調節機能を備えた容器Bを0℃に保持し、これに下記材料を入れた。
スチレン(St) :81.5質量部
トルエン(Tol1) :18.5質量部
上記容器Aに接続され、流量調節機能を備えた容器Cを0℃に保持し、これに下記材料を入れた。
n-ブチルアクリレート(Ba) :14.3質量部
メチルメタクリレート(MMA) : 2.4質量部
メタクリル酸(MAA) : 1.8質量部
トルエン(Tol2) :21.5質量部
上記容器Aに接続され、流量調節機能を備えた容器Dを-10℃に保持し、これに下記材料を入れた。
ジt-ブチルパーオキサイド(PBD) : 7.6質量部
トルエン(Tol3) :32.4質量部
前記容器Bから前記容器Aに投入する際の流量を25質量部/時に設定した。前記容器Cから前記容器Aに投入する際の流量は、8質量部/時から開始し、一定の加速度で流量を増大させて4時間後に12質量部/時となるように設定した。前記容器Dから前記容器Aに投入する際の流量は、10質量部/時に設定した。前記容器A内を毎分200回転で撹拌し、140℃に加熱した。前記容器B、前記容器C、及び前記容器Dから同時に各材料の投入を開始した。全ての投入が終わった時点からさらに3時間撹拌した。溶媒を留去させてスチレンアクリル樹脂1を得た。スチレンアクリル樹脂1の物性を表2に示す。
表1に示す条件に変更した以外は、スチレンアクリル樹脂の製造例1と同様にして、スチレンアクリル樹脂2、3、及び6を得た。スチレンアクリル樹脂2、3、及び6の物性を表2に示す。
撹拌機、窒素導入管を備えた耐圧容器Aに、窒素雰囲気下、下記材料を入れた。
トルエン:20質量部
上記容器Aに接続され、流量調節機能を備えた容器Bを0℃に保持し、これに下記材料を入れた。
スチレン(St) :70.6質量部
トルエン(Tol1) :29.4質量部
上記容器Aに接続され、流量調節機能を備えた容器Cを0℃に保持し、これに下記材料を入れた。
n-ブチルアクリレート(Ba) :20.0質量部
メチルメタクリレート(MMA) : 4.8質量部
メタクリル酸(MAA) : 1.8質量部
2-ヒドロキシエチルメタクリレート(HEMA): 2.8質量部
トルエン(Tol2) :10.6質量部
上記容器Aに接続され、流量調節機能を備えた容器Dを-10℃に保持し、これに下記材料を入れた。
ジt-ブチルパーオキサイド(PBD) : 5.4質量部
トルエン(Tol3) :34.6質量部
前記容器Bから前記容器Aに投入する際の流量を25質量部/時に設定した。前記容器Cから前記容器Aに投入する際の流量は10質量部/時とし、前記容器Dから前記容器Aに投入する際の流量は、10質量部/時に設定した。前記容器A内を毎分200回転で撹拌し、140℃に加熱した。前記容器B、前記容器C、前記容器Dから同時に各材料の投入を開始した。全ての投入が終わった時点からさらに3時間撹拌した。溶媒を留去させてスチレンアクリル樹脂4を得た。スチレンアクリル樹脂4の物性を表2に示す。
表1に示す条件に変更した以外は、スチレンアクリル樹脂の製造例4と同様にして、スチレンアクリル樹脂5及び9を得た。スチレンアクリル樹脂5及び9の物性を表2に示す。
還流冷却管、撹拌機、窒素導入管を備えた反応容器に、窒素雰囲気下、下記材料を入れた。
スチレン(St) :81.5質量部
トルエン(Tol1) :100 質量部
n-ブチルアクリレート(Ba) :14.3質量部
メチルメタクリレート(MMA) : 2.4質量部
メタクリル酸(MAA) : 1.8質量部
ジt-ブチルパーオキサイド(PBD) : 7.2質量部
前記容器内を毎分200回転で撹拌し、110℃に加熱して10時間撹拌した。さらに、140℃に加熱して6時間重合した。溶媒を留去させてスチレンアクリル樹脂7を得た。スチレンアクリル樹脂7の物性を表2に示す。
表1に示す条件に変更した以外は、スチレンアクリル樹脂の製造例7と同様にして、スチレンアクリル樹脂8を得た。スチレンアクリル樹脂8の物性を表2に示す。
還流冷却管、撹拌機、窒素導入管を備えた反応容器に、窒素雰囲気下、下記材料を入れて70℃のオイルバスで加熱した。
メタノール : 60質量部
テトラヒドロフラン :200質量部
上記容器内を毎分200回転で撹拌しながら、下記材料の混合物を2時間かけて滴下した。
スチレン :65 質量部
n-ブチルアクリレート :25 質量部
アクリル酸 :10 質量部
ジt-ブチルパーオキサイド(PBD):3.5質量部
さらに10時間重合した。溶剤を留去、固形物を粉砕した後、40℃の減圧乾燥器で乾燥して主鎖樹脂を得た。
還流冷却管、撹拌機、窒素導入管を備えた反応容器に、窒素雰囲気下、下記材料を入れた。
上記で得られた主鎖樹脂 :100質量部
2-アミノベンゼンスルホン酸 :110質量部
ピリジン :400質量部
上記容器を毎分200回転で撹拌し、これに亜リン酸トリフェニル:420質量部を加え、120℃で6時間加熱した。反応終了後、毎分200回転で撹拌したメタノール:700質量部に上記反応液を投入して沈殿物を回収した。得られた沈殿物を1モル/リットル-塩酸による洗浄と脱イオン水による洗浄を3回繰り返した。40℃の減圧乾燥器で乾燥して、スルホン酸基含有スチレンアクリル樹脂を得た。
次いで、還流冷却管、撹拌機、窒素導入管を備えた反応容器に、窒素雰囲気下、下記材料を入れて80℃のオイルバスで加熱した。
トリメチルオルトホルメート:400質量部
上記容器内を毎分200回転で撹拌し、これに、上記で得られたスルホン酸基含有スチレンアクリル樹脂:100質量部を30分間かけて添加し、さらに12時間撹拌した。毎分200回転で撹拌したメタノール:5000質量部に上記反応液を投入して沈殿物を回収した。メタノール洗浄と脱イオン水による洗浄を3回繰り返した後、減圧乾燥した。これにより、スルホン酸メチルエステル基を有するスルホン酸系樹脂1を得た。スルホン酸系樹脂1の物性を表3-1に、スルホン酸系樹脂1の構造を表3-2に示す。
還流冷却管、撹拌機、窒素導入管を備えた反応容器に、窒素雰囲気下、下記材料を入れた。
メタノール :240質量部
2-ブタノン :140質量部
2-プロパノール :100質量部
スチレン : 77質量部
2-エチルヘキシルアクリレート : 15質量部
2-アクリルアミド-2-メチルプロパンスルホン酸: 8質量部
前記容器内を毎分200回転で撹拌し、80℃に加熱した。重合開始剤であるt-ブチルペルオキシ-2-エチルヘキサノエート1質量部を2-ブタノン30質量部で希釈した溶液を30分かけて滴下して5時間撹拌を継続し、更にt-ブチルペルオキシ-2-エチルヘキサノエート1質量部を2-ブタノン30質量部で希釈した溶液を30分かけて滴下して、更に5時間撹拌して重合した。温度を維持したまま脱イオン水500質量部を静かに添加し、有機層と水層の界面が乱れないように毎分80回転で2時間撹拌した。1時間静置した後に水層を除去した。脱イオン水による洗浄を3回繰り返した後、残った有機層に無水硫酸ナトリウム20質量部を添加した。定性濾紙No.2(アドバンテック東洋株式会社製)を用いて濾過した後、溶媒を留去した。これを40℃の減圧乾燥器で乾燥し、スルホン酸基を有するスルホン酸系樹脂2を得た。得られたスルホン酸系樹脂2の物性を表3-1に、スルホン酸系樹脂2の構造を表3-2に示す。
(単量体組成物の形成工程)
・スチレン(St) :70 質量部
・n-ブチルアクリレート(Ba) :30 質量部
・ピグメントブルー15:3 : 8 質量部
・サリチル酸アルミニウム化合物(ボントロンE-88:オリエント化学社製)
:0.5質量部
・上記スチレンアクリル樹脂1 :18 質量部
・上記スルホン酸系樹脂1 :3.5質量部
・ジビニルベンゼン(DVB) :0.9質量部
・ワックス(HNP-10:日本精蝋社製):10 質量部
上記材料の混合物を調整した。これに15mmのセラミックビーズを入れ、アトライターを用いて3時間分散した。ビーズを除去して単量体組成物を得た。
(分散剤の水分散液の形成工程)
冷却管、撹拌機、窒素導入管を備えた反応容器に、イオン交換水700質量部に、0.1モル/リットルのNa3PO4水溶液450質量部を投入し、70℃に加温した。窒素雰囲気下、TK式ホモミキサー(特殊機化工業製)を用いて、10,000rpmにて撹拌した。これに1.0モル/リットルのCaCl2水溶液70質量部を添加し、リン酸カルシウムを含む水分散液を得た。
(単量体組成物の造粒工程)
窒素雰囲気下、前記単量体組成物を上記水分散液に投入した。前記TK式ホモミキサーにて12000回転/分で6分間の造粒を行った。単量体組成物を投入してから3分後に、表4に示す開始剤1のトルエン溶液15質量部を添加した。
(重合工程)
高速撹拌装置からプロペラ撹拌羽根に撹拌機を代え、90℃の油浴中、窒素雰囲気下、150回転/分で12時間重合した。その後、温度30℃まで冷却速度0.1℃/分で冷却した。
(洗浄・乾燥工程)
上記水分散液を150回転/分で撹拌しながら塩酸を投入して水分散液のpHを1.5にした。そのまま2時間撹拌した後、ろ過と水による洗浄を3回繰り返した。ろ過により固形分を回収し、これを温度40℃の減圧乾燥器で1日間乾燥して、トナー粒子1を得た。
(外添工程)
次に、下記からなる混合物をヘンシェルミキサーで混合し、トナー1を得た。
・上記トナー粒子1 :100質量部
・n-C4H9Si(OCH3)3で処理した疎水性酸化チタン(BET比表面積:120m2/g) :0.8質量部
・ヘキサメチルジシラザン処理した後シリコーンオイルで処理した疎水性シリカ(BET比表面積が180m2/g) :0.8質量部
トナー1の物性を表6-1及び6-2に示す。トナー1について後述する性能評価を行った。トナー1の性能評価の結果を表7に示す。
実施例1において、原材料の種類及び使用量、反応温度を表5に示す条件に変更した以外は実施例1と同様にして、トナー2乃至6、10、12、14乃至16、18及び19を得た。トナー2乃至6、10、12、14乃至16、18及び19の物性を表6-1及び6-2に示す。実施例1と同様にして、トナー2乃至6、10、12、14乃至16、18及び19の性能評価を行った。トナー2乃至6、10、12、14乃至16、18及び19の性能評価の結果を表7に示す。
実施例1において、原材料の種類及び使用量、開始剤の投入時期、反応温度を表5に示す条件に変更し、単量体組成物の造粒工程において、単量体組成物を投入するのと同時に重合開始剤を投入した以外は実施例1と同様にして、トナー7を得た。トナー7の物性を表6-1及び6-2に示す。実施例1と同様にして、トナー7の性能評価を行った。トナー7の性能評価の結果を表7に示す。
実施例7において、原材料の種類及び使用量、反応温度を表5に示す条件に変更した以外は実施例7と同様にして、トナー8、9、11及び17を得た。トナー8、9、11及び17の物性を表6-1及び6-2に示す。実施例1と同様にして、トナー8、9、11及び17の性能評価を行った。トナー8、9、11及び17の性能評価の結果を表7に示す。
実施例1において、単量体組成物の形成工程においてスチレンアクリル樹脂1を添加せず、重合工程において、重合終了後に冷却せずに90℃で保持した以外は実施例1と同様にして、コア粒子の分散液を得た。
・ スチレン :16.3質量部(81.5質量%)
・ n-ブチルアクリレート :2.86質量部(14.3質量%)
・ メチルメタクリレート :0.48質量部(2.4質量%)
・ メタクリル酸 :0.36質量部(1.8質量%)
前記コア粒子の分散液に、上記化合物の混合物と、イオン交換水35質量部に溶解させた2,2’-アゾビス(2-メチル-N-(2-ヒドロキシエチル)プロピオンアミド(VA-086 和光純薬工業社製):0.35質量部とを、同時にそれぞれ30分かけて滴下した。そのまま5時間重合を継続した後、室温まで冷却した。
実施例1における洗浄・乾燥工程、及び外添工程と同様にしてトナー13を得た。トナー13の物性を表6-1及び6-2に示す。実施例1と同様にして、トナー13の性能評価を行った。トナー13の性能評価の結果を表7に示す。
市販のカラーレーザープリンター(LBP-5400、キヤノン製)を使用し、シアンカートリッジのトナーを取り出して、これにトナーを充填し、該カートリッジをシアンステーションに装着した。次いで、受像紙(キヤノン製オフィスプランナー 64g/m2)上に、縦2.0cm横15.0cmの未定着のトナー画像(0.5mg/cm2)を、通紙方向に対し上端部から2.0cmの部分と下端部から2.0cmの部分に形成した。次いで、市販のカラープリンター(LBP-5400,キヤノン製)から取り外した定着ユニットを定着温度とプロセススピードが調節できるように改造し、これを用いて未定着画像の定着試験を行った。常温常湿下、プロセススピードを240mm/秒に設定し、110℃~240℃の範囲で設定温度を5℃おきに変化させながら、各温度で上記トナー画像の定着を行った。低温定着性能は、低温側から高温へ変化させ、低温オフセットが発生しなくなった温度により評価した。また、下記評価基準に従って、耐オフセット性能、グロス性能、耐しみ込み性能を評価した。
A:低温オフセットが発生しない最低温度より50℃以上高い温度領域で高温オフセットが発生しない
B:低温オフセットが発生しない最低温度より40℃以上高い温度領域で高温オフセットが発生しない
C:低温オフセットが発生しない最低温度より30℃以上高い温度領域で高温オフセットが発生しない
D:低温オフセットが発生しない最低温度より20℃以上高い温度領域で高温オフセットが発生しない
E:低温オフセットが発生しない最低温度より20℃未満高い温度領域で高温オフセットが発生
低温オフセット及び高温オフセットが発生しなかった定着画像について、ハンディ光沢度計グロスメーターPG-3D(日本電色工業製)を用いて、光の入射角75°の条件で測定し、以下の基準で評価した。
A:ベタ画像部の光沢度の最高値が35以上である
B:ベタ画像部の光沢度の最高値が30以上35未満である
C:ベタ画像部の光沢度の最高値が25以上30未満である
D:ベタ画像部の光沢度の最高値が20以上25未満である
E:ベタ画像部の光沢度の最高値が20未満である
光沢度が最高値となった画像の光沢値(t1)と、該画像を作成したときの定着器の温度より10℃高い温度で作成した画像の光沢値(t2)との変化率[変化率(%)=(t1-t2)×100/t1]について、以下の基準で評価した。
A:光沢度の変化率が5%未満である(耐しみ込み性能が特に優れている)
B:光沢度の変化率が5%以上10%未満である(耐しみ込み性能が優れている)
C:光沢度の変化率が10%以上15%未満である(耐しみ込み性能が問題ないレベルである)
D:光沢度の変化率が15%以上20%未満である(耐しみ込み性能がやや劣る)
E:光沢度の変化率が20%以上である(耐しみ込み性能が劣る)
市販のカラーレーザープリンター(LBP-5400、キヤノン製)を使用し、定着ユニットの温度を変更できるように改造した。上記グロス性能の評価と同様の方法により、予め、定着ユニットの温度と各トナーの光沢度の相関を求め、各トナーの光沢度が最高値となるときの温度に定着ユニットの温度を設定して、以下の評価を行った。シアンカートリッジのトナーを取り出して、これにトナーを50g充填した。該カートリッジを温度35℃、湿度90%RHの環境下で14日間静置した。これとは別に、トナーを温度35℃、湿度90%RHの環境下で14日間静置した。上記カートリッジをシアンステーションに装着し、受像紙(キヤノン製オフィスプランナー 64g/m2)上に、印字率1%の連続印字を行い、500枚に1回の割合でベタ画像を形成した。カートリッジ内のトナーが25g以下となった時点で、上記の静置したトナーを20g追加し、同様に連続印字を行う、という作業を繰り返した。下記評価基準に従って、耐久安定性能を評価した。
(耐久安定性能の評価基準)
A:トナーを追加した量が4回追加した後に、ベタ画像濃度が1.5未満となる。(耐久安定性能が特に優れている)
B:トナーを3回追加した後に、ベタ画像濃度が1.5未満となる。(耐久安定性能が良好である)
C:トナーを2回追加した後に、ベタ画像濃度が1.5未満となる。(耐久安定性能が通常のレベルである)
D:トナーを1回追加した後に、ベタ画像濃度が1.5未満となる。(耐久安定性能がやや劣る)
E:トナーを追加することなく、ベタ画像濃度が1.5未満となる。(耐久安定性能が劣る)
Claims (10)
- 結着樹脂、着色剤、及びワックスを少なくとも有するトナー粒子と、無機微粒子とを含有するトナーであって、
前記トナーは、y軸に周波数1Hzにおける貯蔵弾性率(G’1)と周波数10Hzにおける貯蔵弾性率(G’10)との比(G’10/G’1)を、x軸に前記貯蔵弾性率の測定温度(℃)をプロットして作成された(温度-G’10/G’1)曲線において、
温度60.0乃至135.0℃に極大値Aを有し、
温度35.0乃至85.0℃に極大値Bを有し、
該極大値Aを示す温度をTa(℃)、該極大値Bを示す温度をTb(℃)としたとき、
前記Ta(℃)は前記Tb(℃)より大きく、前記Ta(℃)と前記Tb(℃)との差(Ta-Tb)(℃)が15.0乃至90.0℃であり、
前記Ta(℃)におけるG’10/G’1の値(G’a)が5.0以上であることを特徴とするトナー。 - 前記トナーは、前記Tb(℃)におけるG’10/G’1の値(G’b)と前記G’aとの差(G’a-G’b)が1.0乃至15.0であることを特徴とする請求項1に記載のトナー。
- 前記トナーは、前記Ta(℃)における前記G’1の値(G’1Ta)が1000乃至300000Paであることを特徴とする請求項1又は2に記載のトナー。
- 前記トナーは、前記トナーのテトラヒドロフラン可溶成分のゲルパーミエーションクロマトグラフィーによるポリスチレン換算の分子量分布において、分子量5000乃至30000にピーク分子量(Mp)を有し、重量平均分子量(Mw)が6000乃至200000であり、前記重量平均分子量(Mw)と個数平均分子量(Mn)との比(Mw/Mn)が3.0乃至20.0であることを特徴とする請求項1乃至3のいずれか一項に記載のトナー。
- 前記トナーは、ソックスレー抽出法によるテトラヒドロフラン不溶成分を含有し、前記テトラヒドロフラン不溶成分の含有量が、トナーに対し5.0乃至35.0質量%であることを特徴とする請求項1乃至4のいずれか一項に記載のトナー。
- 前記トナーは、ソックスレー抽出法による2-プロパノール可溶成分を含有し、前記2-プロパノール可溶成分の含有量が、トナーに対し10.0乃至50.0質量%であることを特徴とする請求項1乃至5のいずれか一項に記載のトナー。
- 前記トナーは、コアシェル構造を有するトナー粒子を含有するトナーであって、シェル相を構成する樹脂として、共重合成分としてアクリル酸或いはメタクリル酸を有するスチレンアクリル樹脂を、結着樹脂100質量部に対し、3.0乃至40.0質量部含有し、前記スチレンアクリル樹脂は、酸価が3.0乃至30.0mgKOH/gであり、前記スチレンアクリル樹脂は、テトラヒドロフラン可溶成分を85.0質量%以上含有し、前記スチレンアクリル樹脂は、メタノール不溶成分を90.0質量%以上含有することを特徴とする請求項1乃至6のいずれか一項に記載のトナー。
- 前記スチレンアクリル樹脂は、ゲルパーミエーションクロマトグラフィーによるポリスチレン換算の重量平均分子量(Mw)が2500乃至150000であり、前記重量平均分子量(Mw)と個数平均分子量(Mn)との比(Mw/Mn)が1.10乃至10.00であり、示差走査熱量計によるガラス転移点(Tg)が55.0乃至95.0℃であることを特徴とする請求項7に記載のトナー。
- 前記スチレンアクリル樹脂は、滴下重合法あるいは多段滴下重合法により製造された樹脂であることを特徴とする請求項7又は8に記載のトナー。
- 前記トナーは、ソックスレー抽出法によるテトラヒドロフラン可溶成分を含有し、前記テトラヒドロフラン可溶成分の蛍光X線測定によるスルホン酸基に由来する硫黄元素の含有量が、前記テトラヒドロフラン可溶成分の含有量に対し0.005乃至0.300質量%であることを特徴とする請求項1乃至9のいずれか一項に記載のトナー。
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CN200980139894XA CN102177472B (zh) | 2008-10-07 | 2009-10-07 | 调色剂 |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012078649A (ja) * | 2010-10-04 | 2012-04-19 | Canon Inc | トナー |
JP2015000917A (ja) * | 2013-06-14 | 2015-01-05 | 三菱レイヨン株式会社 | 重合体粒子、重合体分散液、水性被覆材および塗装物 |
US9969874B2 (en) | 2013-02-14 | 2018-05-15 | Mitsubishi Chemical Corporation | Polymer particle, polymer dispersion, method for producing said polymer dispersion, coating material produced from said polymer dispersion, and coated article |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010041677A1 (ja) * | 2008-10-07 | 2010-04-15 | キヤノン株式会社 | トナー |
CN103026301B (zh) * | 2010-07-22 | 2014-12-31 | 佳能株式会社 | 调色剂 |
JP5500127B2 (ja) | 2011-06-28 | 2014-05-21 | コニカミノルタ株式会社 | トナーの製造方法 |
US9733583B2 (en) | 2015-04-08 | 2017-08-15 | Canon Kabushiki Kaisha | Toner |
US9733584B2 (en) | 2015-04-08 | 2017-08-15 | Canon Kabushiki Kaisha | Toner |
US9897932B2 (en) | 2016-02-04 | 2018-02-20 | Canon Kabushiki Kaisha | Toner |
JP6887833B2 (ja) | 2016-03-18 | 2021-06-16 | キヤノン株式会社 | トナー及びトナーの製造方法 |
US10503090B2 (en) | 2017-05-15 | 2019-12-10 | Canon Kabushiki Kaisha | Toner |
US10635011B2 (en) | 2018-04-27 | 2020-04-28 | Canon Kabushiki Kaisha | Toner |
JP7210222B2 (ja) | 2018-10-19 | 2023-01-23 | キヤノン株式会社 | トナー |
JP7270895B2 (ja) * | 2018-11-29 | 2023-05-11 | 株式会社リコー | トナー、画像形成装置、画像形成方法、及びトナー収容ユニット |
JP7391658B2 (ja) | 2018-12-28 | 2023-12-05 | キヤノン株式会社 | トナー |
JP7267740B2 (ja) | 2018-12-28 | 2023-05-02 | キヤノン株式会社 | トナー |
EP3674802B1 (en) | 2018-12-28 | 2022-05-18 | Canon Kabushiki Kaisha | Toner and toner manufacturing method |
JP7443047B2 (ja) | 2018-12-28 | 2024-03-05 | キヤノン株式会社 | トナー |
JP7286314B2 (ja) | 2018-12-28 | 2023-06-05 | キヤノン株式会社 | トナー |
JP7309481B2 (ja) | 2019-07-02 | 2023-07-18 | キヤノン株式会社 | トナー |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11288129A (ja) * | 1998-03-31 | 1999-10-19 | Nippon Zeon Co Ltd | コア・シェル構造トナー及びその製造方法 |
JP2007156297A (ja) * | 2005-12-08 | 2007-06-21 | Canon Inc | トナー |
JP2007256720A (ja) * | 2006-03-24 | 2007-10-04 | Canon Inc | トナー |
JP2007279666A (ja) * | 2006-03-13 | 2007-10-25 | Canon Inc | トナー及びトナーの製造方法 |
JP2008224939A (ja) * | 2007-03-12 | 2008-09-25 | Canon Inc | トナー |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5744278A (en) | 1996-04-09 | 1998-04-28 | Canon Kabushiki Kaisha | Toner for developing an electrostatic image and process for producing a toner |
WO1999052019A1 (fr) * | 1998-03-31 | 1999-10-14 | Nippon Zeon Co., Ltd. | Toner destine au developpement d'une image electrostatique, et procede de production associe |
JP2005266383A (ja) * | 2004-03-19 | 2005-09-29 | Ricoh Co Ltd | 静電荷像現像用トナー、フルカラートナーキット、画像形成方法及び画像形成装置 |
JP4510733B2 (ja) * | 2005-04-07 | 2010-07-28 | キヤノン株式会社 | イエロートナー |
JP4544053B2 (ja) * | 2005-06-23 | 2010-09-15 | コニカミノルタビジネステクノロジーズ株式会社 | トナー、トナーの製造方法 |
JP4728836B2 (ja) | 2006-02-23 | 2011-07-20 | 株式会社リコー | 画像形成装置、プロセスカートリッジおよびトナー |
WO2007138912A1 (ja) * | 2006-05-25 | 2007-12-06 | Canon Kabushiki Kaisha | トナー |
JP4732240B2 (ja) | 2006-05-30 | 2011-07-27 | キヤノン株式会社 | トナー |
JP2008015244A (ja) * | 2006-07-06 | 2008-01-24 | Fuji Xerox Co Ltd | 静電荷像現像用トナー、並びに、これを用いた静電荷像現像用現像剤および画像形成方法 |
JP2008058620A (ja) | 2006-08-31 | 2008-03-13 | Nippon Zeon Co Ltd | 非磁性一成分静電荷像現像用トナーの製造方法 |
US7927776B2 (en) * | 2006-12-08 | 2011-04-19 | Samsung Electronics Co., Ltd. | Toner for electrophotography |
US8062819B2 (en) * | 2007-04-17 | 2011-11-22 | Konica Minolta Business Technologies, Inc. | Magenta toner for developing electrostatic image |
EP2249207B1 (en) | 2008-02-25 | 2014-09-03 | Canon Kabushiki Kaisha | Toner |
JP4560587B2 (ja) * | 2008-02-25 | 2010-10-13 | キヤノン株式会社 | トナー |
WO2010041677A1 (ja) * | 2008-10-07 | 2010-04-15 | キヤノン株式会社 | トナー |
-
2009
- 2009-10-07 WO PCT/JP2009/067473 patent/WO2010041677A1/ja active Application Filing
- 2009-10-07 JP JP2010503300A patent/JP4618820B2/ja active Active
- 2009-10-07 KR KR1020117005226A patent/KR101317127B1/ko not_active IP Right Cessation
- 2009-10-07 EP EP09819211A patent/EP2345935A4/en not_active Withdrawn
- 2009-10-07 CN CN200980139894XA patent/CN102177472B/zh active Active
-
2010
- 2010-02-17 US US12/706,910 patent/US7858282B2/en not_active Expired - Fee Related
- 2010-12-03 US US12/960,406 patent/US8383313B2/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11288129A (ja) * | 1998-03-31 | 1999-10-19 | Nippon Zeon Co Ltd | コア・シェル構造トナー及びその製造方法 |
JP2007156297A (ja) * | 2005-12-08 | 2007-06-21 | Canon Inc | トナー |
JP2007279666A (ja) * | 2006-03-13 | 2007-10-25 | Canon Inc | トナー及びトナーの製造方法 |
JP2007256720A (ja) * | 2006-03-24 | 2007-10-04 | Canon Inc | トナー |
JP2008224939A (ja) * | 2007-03-12 | 2008-09-25 | Canon Inc | トナー |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012078649A (ja) * | 2010-10-04 | 2012-04-19 | Canon Inc | トナー |
US9969874B2 (en) | 2013-02-14 | 2018-05-15 | Mitsubishi Chemical Corporation | Polymer particle, polymer dispersion, method for producing said polymer dispersion, coating material produced from said polymer dispersion, and coated article |
JP2015000917A (ja) * | 2013-06-14 | 2015-01-05 | 三菱レイヨン株式会社 | 重合体粒子、重合体分散液、水性被覆材および塗装物 |
Also Published As
Publication number | Publication date |
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EP2345935A1 (en) | 2011-07-20 |
US20100143834A1 (en) | 2010-06-10 |
JPWO2010041677A1 (ja) | 2012-03-08 |
KR20110038733A (ko) | 2011-04-14 |
US20110081609A1 (en) | 2011-04-07 |
US7858282B2 (en) | 2010-12-28 |
US8383313B2 (en) | 2013-02-26 |
CN102177472A (zh) | 2011-09-07 |
EP2345935A4 (en) | 2012-11-21 |
KR101317127B1 (ko) | 2013-10-08 |
CN102177472B (zh) | 2013-07-31 |
JP4618820B2 (ja) | 2011-01-26 |
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