• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Summary of the Invention Patent for: “TONER, DEVELOPER, AND IMAGE TRAINING DEVICE”.The present invention relates to a toner, in which the toner has a glass transition temperature [Tg1st (toner)] of 20 ° C to 50 ° C, in which the glass transition temperature [Tg1st (toner)] is measured in a first heating in a differential scanning calorimeter (DSC) of the toner, in which an insoluble matter of tetrahydrofuran (THF) has a glass transition temperature [Tg2nd (insoluble matter of THF)] from -40 ° C to 30 ° C, where a glass transition temperature [Tg2nd (THF insoluble matter)] is measured on a second heating in a differential scanning calorimeter (DSC) of the THF insoluble matter, where the THF insoluble matter comprises a storage module at 100 ° C [G '(100) (THF insoluble matter)] from 1.0 x 105 Pa to 1.0 x 107 Pa, and where a ratio of the modulus of storage of the THF insoluble matter at 40 ° C [G '(40) (THF insoluble matter)] for the 100 ° C storage module [G' (100) (THF insoluble matter)], expressed by [G '(40) (matter insoluble THF) / G '(100) (THF insoluble matter)], is 3.5 x 10 or less.
    公开号:BR112016005072A2
    申请号:R112016005072-0
    申请日:2014-08-29
    公开日:2020-08-11
    发明作者:Shinsuke Nagai；Shinya Nakayama；Tsuyoshi Sugimoto；Susumu Chiba；Kohsuke Nagata；Daisuke Asahina
    申请人:Ricoh Company, Ltd.；
    IPC主号:
    专利说明:

    [0001] [0001] The present invention relates to a toner, a developer and an image forming apparatus. Background art
    [0002] [0002] In recent years, toners have been desired to have small particle size and hot offset resistance to provide high-quality output images, low-temperature fixing capabilities for energy savings, and heat-resistant storage stability to withstand high temperature, high humidity during storage or transport after production. In particular, the ability to fix at low temperatures is very important for the quality of a toner, since the energy consumption for fixing occupies a large part of the energy consumption for an entire image formation process.
    [0003] [0003] Conventionally, toners produced by kneading and spraying were used. The toner produced by the spray kneading method has problems in which it is difficult to reduce its particle size, and particle shapes are irregular and its particle diameter distribution is wide, which results in poor image quality. output, and a large amount of energy is needed to fix such toner. In the case where wax (that is, a release agent) is added to the toner to improve the holding capacity, in addition, the toner produced by the kneading and spraying method contains a large amount of the wax present near the toner surfaces, as that a kneaded product is cracked from a wax interface during spraying. As a result, a release effect is presented, but on the other hand, the toner tends to cause deposition of toner (ie, film formation) on a conveyor, a photoconductor and a shovel. Therefore, such toner is not satisfactory in view of its characteristics as a whole.
    [0004] [0004] To find the aforementioned problems associated with the kneading and spraying method, a method of producing a toner according to a polymerization method has been proposed. A toner produced by the polymerization method is easily produced as small particles, has a marked particle diameter distribution compared to that of the toner produced by the spray method, and can encapsulate a release agent therein. As a method of producing a toner according to the polymerization method, a method is proposed to produce a toner using a urethane modified polyester elongation reaction product as a toner binder, for the purpose of improving fixation capacity in low temperature, and resistance to hot offset (see PTL 1).
    [0005] [0005] In addition, a toner production method is proposed, which is excellent in everything from heat-resistant storage stability, low temperature holding capacity, and resistance to hot offset, as well as excellent in flow capacity. dust and transfer capacity, when a toner is produced as a small diameter toner (see PTLs 2 and 3).
    [0006] [0006] In addition, a method of producing a toner having a maturation stage is revealed to produce a toner binder having a stable molecular weight distribution, and obtain fixation capacity at low temperature (see PTLs 4 and 5).
    [0007] [0007] However, these proposed techniques do not provide a toner having a high level of low temperature fixation capacity, which has been demanded in recent years.
    [0008] [0008] For the purpose of obtaining a high level of fixation capacity at low temperature, therefore, it is proposed a toner containing a resin that includes a crystalline polyester resin, and a release agent, and having a phase separation structure, where resin and release agent (eg, wax) are incompatible with each other in the form of sea islands (see PTL 6).
    [0009] [0009] In addition, a toner containing a crystalline polyester resin, a release agent, and a graft polymer is proposed (see PTL 7).
    [00010] [00010] These proposed techniques can obtain fixation at low temperature, since the crystalline polyester resin is rapidly melted, compared to a non-crystalline polyester resin. However, in the case of a toner containing a crystalline polyester resin, there is a problem that toner aggregates form in a high temperature, high humidity environment.
    [00011] [00011] Furthermore, although recent demands for further quality improvements have required toners to be excellent not only in low temperature fixation capacity and heat-resistant storage stability but also in image brightness, such toners have not been achieved.
    [00012] [00012] In such circumstances, there is currently a demand for excellent toner not only in low temperature fixation capacity as heat resistant storage stability, but also in image brightness. Citation list Patent literature
    [00013] [00013] PTL 1: Japanese open patent application (JP-A) no. 11-133665
    [00014] [00014] PTL 2: JP-A no. 2002-287400
    [00015] [00015] PTL 3: JP-A no. 2002-351143
    [00016] [00016] PTL 4: Japanese patent (JP-B) no. 2579150
    [00017] [00017] PTL 5: JP-A no. 2001-158819
    [00018] [00018] PTL 6: JP-A no. 2004-46095
    [00019] [00019] PTL 7: JP-A no. 2007-271789 SUMMARY OF THE INVENTION TECHNICAL PROBLEM
    [00020] [00020] The present invention aims to solve the problems existing above and achieve the following objective: that is, to provide an excellent toner not only in fixation capacity at low temperature and heat resistant storage stability but also in image brightness. Solution to the problem
    [00021] [00021] Means for solving the above problems are as follows:
    [00022] [00022] That is, a toner of the present invention has a glass transition temperature [Tg1st (toner)] of 20 ° C to 50 ° C, where the glass transition temperature [Tg1st
    [00023] [00023] The present invention can solve the above problems and provide an excellent toner not only in low temperature fixation capacity and heat resistant storage stability but also in image brightness. BRIEF DESCRIPTION OF THE DRAWINGS
    [00024] [00024] Figure 1 is a schematic structural view of an example of an image forming apparatus of the present invention.
    [00025] [00025] Figure 2 is a schematic structural view of another example of an image forming apparatus of the present invention.
    [00026] [00026] Figure 3 is a schematic structural view of yet another example of an image forming apparatus of the present invention.
    [00027] [00027] Figure 4 is a partially enlarged view of Figure 3.
    [00028] [00028] Figure 5 is a schematic structural view of an example of a process cartridge. DESCRIPTION OF MODALITIES TONER
    [00029] [00029] A toner of the present invention has a glass transition temperature [Tg1st (toner)] of 20 ° C to 50 ° C, where the glass transition temperature [Tg1st (toner)] is measured on a first heat in a differential scanning calorimetry (DSC) of the toner.
    [00030] [00030] Tetrahydrofuran insoluble matter (THF) has a glass transition temperature [Tg2nd (THF insoluble matter)] from -40 ° C to 30 ° C, where the glass transition temperature [Tg2nd (THF insoluble matter) ] is measured in a second heating in a differential scanning calorimetry (DSC) of the THF insoluble matter.
    [00031] [00031] THF insoluble matter has a storage module at 100 ° C [G '(100) (THF insoluble matter)] from 1.0 x 105 Pa to 1.0 x 107 Pa.
    [00032] [00032] A ratio of the storage module of THF insoluble matter at 40 ° C [G '(40) (THF insoluble matter)] to the storage module at 100 ° C [G' (100)
    [00033] [00033] The values of [Tg2nd (THF insoluble matter)] and [G '(40) (THF insoluble matter)] can be adjusted by adjusting a resin composition (a dihydric polyol or higher, a divalent acid component or higher), for example.
    [00034] [00034] Specifically, these values can be adjusted in the following way, for example.
    [00035] [00035] To decrease Tg, a polyol containing an alkyl group in a side chain of it is used as a constituent component of a resin.
    [00036] [00036] To increase Tg, the distance between ester bonds in the resin is shortened.
    [00037] [00037] To increase G 'the distance between ester bonds in the resin is shortened and a resin composition containing an aromatic compound is used.
    [00038] [00038] To decrease G ', a straight chain polyester resin is used and a polyol containing an alkyl group on a side chain thereof is used as a constituent component of a resin. THF insoluble matter
    [00039] [00039] The tetrahydrofuran (THF) insoluble matter of the toner is not particularly limited and can be appropriately selected depending on the intended purpose, however it is preferably 15% by mass to 35% by mass, more preferably 20% by mass to 30% by weight. pasta. When the THF insoluble matter is less than 15% by weight, the toner can be degraded to a low temperature fixation capacity. When THF-insoluble matter is greater than 35% by weight, the toner can be degraded in heat-resistant storage stability.
    [00040] [00040] The THF insoluble matter corresponds to a non-crystalline polyester resin of non-linear chain. Although the toner of the present invention has a lower Tg than that of conventional toners, the toner of the present invention can retain sufficient heat resistant storage stability since it contains the THF insoluble matter in a specific amount. Especially in the case where the non-crystalline polyester resin has a urethane bond or a urea bond having high cohesive strength, an effect of maintaining heat resistant storage stability will become more significant. THF insoluble matter and THF soluble matter
    [00041] [00041] The THF soluble matter of the toner and the THF insoluble matter of the toner can be obtained as follows.
    [00042] [00042] A toner (1 part by mass) is added to 40 parts by mass of tetrahydrofuran (THF) and the mixture is refluxed for 6 hours. Subsequently, insoluble components are made sediment with a centrifugal device, to thereby be separated from a supernatant.
    [00043] [00043] Insoluble components are dried at 40ºC for 20 hours to obtain THF insoluble matter.
    [00044] [00044] The solvent is removed from the supernatant separated above, followed by drying at 40ºC for 20 hours, to thereby obtain the THF-soluble matter.
    [00045] [00045] The toner has a glass transition temperature (Tg1st) of 20ºC to 50ºC, preferably 35ºC to 45ºC, where the glass transition temperature (Tg1st) is measured at the first heating in a differential scanning calorimetry (DSC) of the toner.
    [00046] [00046] If the Tg of a conventional toner is reduced to approximately 50ºC or lower, conventional toner tends to cause aggregation of toner particles influenced by temperature variations during transport or storage of toner in the summer or in a tropical region. As a result, toner adhesion occurs in a toner bottle, or in a developer cartridge. In addition, supply failures due to clogged toner in the toner bottle, and defective images due to toner adhesion are likely to occur.
    [00047] [00047] The toner of the present invention has a Tg lower than that of a conventional toner. However, the toner of the present invention can maintain heat-resistant storage stability. Especially in the case where the non-crystalline polyester resin has a urethane bond or a urea bond having high cohesive strength, an effect of maintaining heat resistant storage stability will become more significant.
    [00048] [00048] When [Tg1st (toner)] is lower than 20ºC, degradation in heat-resistant storage stability, blocking in developing devices, and film formation in a photoconductor will result. When the [Tg1st (toner)] is higher than 50ºC, the toner will be degraded in capacity to fix at low temperature. [Tg2nd (toner)]
    [00049] [00049] The glass transition temperature [Tg2nd (toner)] of the toner measured in a second heating in a differential scanning calorimetry (DSC) of the toner is not particularly limited and can be appropriately selected depending on the intended purpose, however it is preferably 0ºC at 30 ° C, more preferably 15 ° C at 30 ° C.
    [00050] [00050] When the [Tg2nd (toner)] is lower than 0ºC, the blocking resistance of a fixed image (printed matter) can be degraded. When [Tg2nd (toner)] is higher than 30ºC, it may be impossible to obtain fixation capacity at sufficient low temperature and brightness.
    [00051] [00051] The value of [Tg2nd (toner)] can be adjusted by adjusting the Tg and the amount of the crystalline polyester resin, for example. [Tg1st (toner)] - [Tg2nd (toner)]
    [00052] [00052] A difference of [Tg1st (toner)] - [Tg2nd (toner)] between the glass transition temperature [Tg1st (toner)] of the toner as measured at the first heating in a differential scanning calorimetry (DSC) and temperature glass transition [Tg2nd (toner)] of the toner as measured in the second heating in DSC is not particularly limited and can be appropriately selected depending on the intended purpose, however it is preferably 10ºC or more. The upper limit of the difference is not particularly limited and can be appropriately selected depending on the intended purpose, but the difference of [Tg1st (toner)] - [Tg2nd (toner)] is preferably 50ºC or less.
    [00053] [00053] When the difference [Tg1st (toner)] - [Tg2nd (toner)] is 10ºC or more, the resulting toner is excellent in fixing capacity at low temperature, which is advantageous. The fact that the difference of [Tg1st (toner)] - [Tg2nd (toner)] is 10ºC or more means that the crystalline polyester resin and the non-crystalline polyester resin, which are present in an incompatible state before heating (before the first heating) become a compatible state after heating (after the first heating). Note that the compatible state after heating does not have to be a fully compatible state. [Tg2nd (THF insoluble matter)]
    [00054] [00054] A glass transition temperature [Tg2nd (THF-insoluble matter)] of the THF-insoluble matter of the toner, which is measured in a second heating in a differential scanning calorimetry (DSC) is -40ºC to 30ºC, preferably 0ºC to 20ºC.
    [00055] [00055] When the glass transition temperature [Tg2nd (THF insoluble matter)] is lower than -40ºC, the heat resistant storage stability will be degraded. When the glass transition temperature [Tg2nd (Matter insoluble in THF)] is higher than 30ºC, the fixing property at low temperature will be degraded.
    [00056] [00056] The glass transition temperature [Tg2nd (THF insoluble matter)] corresponds to Tg2nd of the non-linear non-crystalline polyester resin, and the range above the glass transition temperature [Tg2nd (THF insoluble matter)] is advantageous for low temperature clamping capacity. Also, when the non-linear non-crystalline polyester resin has a urethane bond or a urea bond having high cohesive strength, an effect of maintaining heat resistant storage stability will become more significant. [Tg2nd (THF soluble matter)]
    [00057] [00057] A glass transition temperature [Tg2nd (THF-soluble matter)] of the THF-soluble matter of the toner, which is measured in a second heating in a differential scanning calorimetry (DSC) is preferably 5ºC to 35ºC, more preferably 25ºC at 35ºC.
    [00058] [00058] The THF soluble matter in the toner is usually composed of a crystalline polyester resin and a non-crystalline polyester resin that is a component having a high Tg. The crystalline polyester resin has thermofusion characteristics in which viscosity is drastically reduced in temperature around the starting fixing temperature, since the crystalline polyester resin has crystallinity. Using the crystalline polyester resin having the aforementioned characteristics together with the non-crystalline polyester resin in the toner, the heat resistant storage stability of the toner is excellent up to the start of melting temperature due to crystallinity, and the toner drastically decreases its viscosity at the start of melting temperature due to melting of crystalline polyester resin. Along with the dramatic decrease in viscosity, the non-crystalline polyester resin is melted together with the non-crystalline polyester resin, to dramatically decrease its viscosity to thereby be fixed. Therefore, a toner having excellent heat-resistant storage stability and low temperature holding capacity can be obtained. In addition, the toner has excellent results in terms of a release width (a difference between the minimum holding temperature and hot offset occurrence temperature).
    [00059] [00059] The value of [Tg2nd (THF soluble matter)] can be adjusted by adjusting the Tg of the non-crystalline polyester resin, the Tg of the crystalline polyester resin, and the quantities of the non-crystalline polyester resin and the resin of crystalline polyester. Storage module [G '(100) (THF insoluble matter)] and [[G' (40) (THF insoluble matter)] / [G '(100) (THF insoluble matter)]]
    [00060] [00060] The THF insoluble matter of the toner preferably has a storage module at 100ºC [G '(100) (THF insoluble matter)] from 1.0 x 105 to 1.0 x 107 Pa, preferably 5.0 x 105 Pa to 5.0 x 106 Pa.
    [00061] [00061] The ratio of a storage module for THF-insoluble matter in the toner at 40ºC [G '(40) (THF-insoluble matter)] to the storage module for THF-insoluble matter in the toner at 100ºC [G' ( 100) (THF insoluble matter)], expressed by [[G '(40) THF insoluble matter)] / [G' (100) (THF insoluble matter)]], is 3.5 x 10 or less, preferably 3.3 x 10 or less. The lower limit of the ratio [[G '(40) (THF insoluble matter)] / [G' (100) (THF insoluble matter)]] is not particularly limited and can be appropriately selected depending on the intended purpose, however the [[G '(40) (THF insoluble matter)] / [G' (100) (THF insoluble matter)]] ratio is preferably 2.0 x 10 or more.
    [00062] [00062] When the toner has [G '(100) (THF insoluble matter)] from 1.0 x 105 Pa to 1.0 x 107 Pa and the ratio [[G' (40) (THF insoluble matter) ] / [G '(100) (THF insoluble matter)] of 3.5 x 10 or less, the crystalline polyester resin is melted more together with the non-crystalline polyester resin which is a component having a high Tg. As a result, the ½ average flow start temperature with a thermal flow rating device (flow tester) will decrease and the image brightness will improve. [G ’(100) (toner)]
    [00063] [00063] The toner has a storage module at 100ºC [G '(100) (toner)] from 5.0 x 103 Pa to 5.0 x 104 Pa. When [G' (100) (toner)] is less than 5.0 x 103 Pa, hot offset may occur. When the [G ’(100) (toner)] is greater than 5.0 x 104 Pa, the minimum fixing temperature may increase.
    [00064] [00064] The value of [G '(100) (toner)] can be adjusted by adjusting the composition of non-crystalline polyester resin, of non-linear chain, for example. Measurement method of storage module G ’
    [00065] [00065] The storage module (G ') under various conditions can be measured using, for example, a dynamic viscoelasticity measuring device (ARES, product of TA Instruments, Inc.). A measurement frequency is 1 Hz.
    [00066] [00066] Specifically, a measurement sample is formed into a pellet having a diameter of 8 mm and a thickness of 1 mm to 2 mm, fixed on a parallel plate having a diameter of 8 mm, which is then stabilized at 40ºC, and heated to 200ºC at a heating rate of 2.0ºC / min. with a frequency of 1 Hz (6.28 rad / s) and a voltage quantity of 0.1% (voltage quantity control mode), and a storage module is measured.
    [00067] [00067] In this specification, the storage module at 40ºC can be mentioned as G '(40ºC) and the storage module at 100ºC can be mentioned as G' (100ºC). Fusion point
    [00068] [00068] The melting point of the toner is not particularly limited and can be appropriately selected depending on the intended purpose, however it is preferably 60 ° C to 80 ° C. Volume average particle diameter
    [00069] [00069] The average particle diameter of toner volume is not particularly limited and can be appropriately selected depending on the intended purpose, but is preferably 3 m to 7 m. In addition, a ratio of the average volume particle diameter to the numerical average particle diameter is preferably 1.2 or less. In addition, the toner preferably contains toner particles having a volume average particle diameter of 2 µm or less, in an amount of 1% per number to 10% per number.
    [00070] [00070] The Tg, acid value, hydroxyl value, molecular weight and melting point of the polyester resin and the release agent can be individually measured. Alternatively, each component can be separated from an effective toner by gel permeation chromatography (GPC) or similar, and each separate component can be subjected to the analysis methods described later, to thereby calculate Tg, molecular weight, melting, and mass ratio of a constituent component.
    [00071] [00071] The separation of each component by GPC can be carried out, for example, by the following method.
    [00072] [00072] In GPC using tetrahydrofuran (THF) as a mobile phase, an eluate is subjected to fractionation by means of a fraction collector, a fraction corresponding to a part of a desired molecular weight is collected from a total area of one elution curve.
    [00073] [00073] The collected eluates are concentrated and dried by an evaporator or similar, and a resulting solid content is dissolved in a deuterated solvent, such as deuterated chloroform, and deuterated THF, followed by 1H-NMR measurement. From an integral ratio of each element, a ratio of a monomer to the resin in the elution composition is calculated.
    [00074] [00074] As another method, after concentrating the eluate, hydrolysis is carried out with sodium hydroxide or similar, and a ratio of a constituent monomer is calculated by subjecting the decomposed product to a qualitative or quantitative analysis by high performance liquid chromatography (HPLC) ).
    [00075] [00075] Note that in the case where the method for producing a toner produces toner-based particles by generation of the non-crystalline polyester resin through the chain elongation reaction and / or the crosslinking reaction of the reactive non-linear chain precursor and the curing agent, the polyester resin can be separated from an effective toner by GPC or similar, to thereby determine Tg of the same. Alternatively, a non-crystalline polyester resin is separately generated through a chain elongation reaction and / or crosslinking reaction of the non-linear chain reactive precursor and the curing agent, and Tg can be measured on the synthesized non-crystalline polyester resin. . Separation unit for toner constituent components
    [00076] [00076] An example of a separation unit for each component during a toner analysis will be specifically explained below.
    [00077] [00077] First, 1 g of a toner is added to 100 ml of THF, and the resulting mixture is stirred for 30 minutes at 25ºC, to thereby a solution in which soluble components are dissolved.
    [00078] [00078] The solution is then filtered through a membrane filter having an opening of 0.2 m, to thereby obtain the components soluble in THF in the toner.
    [00079] [00079] Next, the THF-soluble components are dissolved in THF, to thereby prepare a sample for measuring GPC, and the prepared sample is supplied to GPC used for measuring the molecular weight of each resin mentioned above.
    [00080] [00080] Meanwhile, a fraction collector is arranged in a GPC eluate outlet, to fractionate the eluate by a certain count. The eluate is obtained by 5% in terms of the area ratio from the beginning of elution on the elution curve (elevation of the curve).
    [00081] [00081] Next, each fraction eluted, as a sample, in an amount of 30 mg is dissolved in 1 ml of deuterated chloroform, and to that solution, 0.05% by volume of tetramethylsilane (TMS) is added as a material pattern.
    [00082] [00082] A glass tube for NMR having a diameter of 5 mm is charged with the solution, from which a spectrum is obtained by means of a nuclear magnetic resonance device (JNM-AL 400, manufactured by JEOL Ltd.) for performing multiplication 128 times at a temperature of 23ºC to 25ºC.
    [00083] [00083] The monomer compositions and composition ratios of the non-crystalline polyester resin, the crystalline polyester resin, and the like contained in the toner are determined from integral peak ratios of the obtained spectrum.
    [00084] [00084] For example, a peak assignment is performed as follows, and a constituent monomer component ratio is determined from each integral ratio.
    [00085] [00085] The assignment of a peak is as follows:
    [00086] [00086] Around 8.25 ppm: derived from a benzene ring of trimellitic acid (for a hydrogen atom).
    [00087] [00087] Around the region from 8.07 ppm to 8.10 ppm: derived from a benzene ring of terephthalic acid (for four hydrogen atoms).
    [00088] [00088] Around the 7.1 ppm to 7.25 ppm region: derived from a benzene ring of bisphenol A (for four hydrogen atoms).
    [00089] [00089] Around 6.8 ppm: derived from a benzene ring of bisphenol A (for four hydrogen atoms), and derived from a double bond of fumaric acid (for two hydrogen atoms).
    [00090] [00090] Around the region of 5.2 ppm to 5.4 ppm: derived from propylene oxide adduct method of bisphenol A (for a hydrogen atom).
    [00091] [00091] Around the 3.7 ppm to 4.7 ppm region: methylene derivative of a bisphenol A propylene oxide adduct (for two hydrogen atoms), and methylene derivative of a bisphenol ethylene oxide A (for four hydrogen atoms).
    [00092] [00092] Around 1.6 ppm: derived from a methyl group of bisphenol A (for 6 hydrogen atoms).
    [00093] [00093] From these results, for example, the extracted product collected in the fraction in which the non-crystalline polyester resin occupies 90% or more in the full peak ratio in the spectrum can be treated as the non-crystalline polyester resin.
    [00094] [00094] Similarly, the extracted product collected in the fraction in which the crystalline polyester resin occupies 90% or more in the full peak ratio in the spectrum can be treated as the crystalline polyester resin.
    [00095] [00095] In the present invention, a melting point and a glass transition temperature (Tg) can be measured, for example, by means of a differential scanning calorimetry (DSC) system (Q-200, product of TA Instruments Japan Inc.).
    [00096] [00096] Specifically, a melting point and glass transition temperature of a sample are measured in the following ways.
    [00097] [00097] Specifically, first, an aluminum sample container loaded with approximately 5.0 mg of a sample is placed in a support unit, and the support unit is then placed in an electric oven. Then, the sample is heated (first heating) from -80ºC to 150ºC at a heating rate of 10ºC / min. in an atmosphere of nitrogen. Then, the sample is cooled from 150ºC to - 80ºC at a cooling rate of 10ºC, followed by heating again (second heating) at 150ºC at a heating rate of 10ºC / min. DSC curves are measured respectively for the first heating and the second heating by means of differential scanning calorimetry (Q-200, product of TA Instruments Japan Inc.).
    [00098] [00098] The DSC curve for the first heating is selected from the DSC curve obtained by means of an analysis program stored in the Q-200 system, to thereby determine the glass transition temperature of the sample with the first heating. Similarly, the DSC curve for the second heating is selected, and the glass transition temperature of the sample with the second heating can be determined.
    [00099] [00099] In addition, the DSC curve for the first heating is selected from the DSC curve obtained by means of the analysis program stored in the Q-200 system, and a peak peak endothermic temperature of the sample for the first heating is determined as a melting point of the sample. Similarly, the DSC curve for the second heating is selected, and the peak endothermic peak temperature of the sample for the second heating can be determined as a melting point of the sample with the second heating.
    [000100] [000100] In the case where a toner is used as a sample, the glass transition temperature for the first heating is represented as Tg1st, and the glass transition temperature for the second heating is represented as Tg2nd in this specification.
    [000101] [000101] In addition, in this specification, the peak endothermic temperatures and glass transition temperatures of non-crystalline polyester resin, crystalline polyester resin, and other constituent components such as the release agent, for the second heating are considered as a melting point and Tg of each sample, unless otherwise mentioned.
    [000102] [000102] The toner preferably contains a polyester resin. Polyester resin
    [000103] [000103] The polyester resin is not particularly limited and can be appropriately selected depending on the intended purpose, but preferably contains a non-crystalline polyester resin and crystalline polyester resin C.
    [000104] [000104] The non-crystalline polyester resin contains a dicarboxylic acid component as a constituent component, and the dicarboxylic acid component preferably contains terephthalic acid in an amount of 50 mol% or more, which is advantageous in terms of resistant storage stability to heat.
    [000105] [000105] Also, the polyester resin preferably contains non-crystalline polyester resin A, non-crystalline polyester resin B and crystalline polyester resin C.
    [000106] [000106] The non-crystalline polyester resin A is preferably obtained through the reaction between a non-linear reactive precursor and a curing agent.
    [000107] [000107] The non-crystalline polyester resin A preferably has a glass transition temperature of -60 ° C to 0 ° C.
    [000108] [000108] The non-crystalline polyester resin B preferably has a glass transition temperature of 40 ° C to 80 ° C.
    [000109] [000109] A conceivable method for improving toner low-temperature fixability is to decrease the glass transition temperature or the molecular weight of a non-crystalline polyester resin so that the non-crystalline polyester resin fuses with a polyester resin crystalline. However, it can be easily imagined that by simply lowering the glass transition temperature or the molecular weight of the non-crystalline polyester resin to decrease its melting viscosity, the resulting toner will be degraded into heat-resistant storage stability and resistance to hot offset after fixation.
    [000110] [000110] In the toner of the present invention, the non-crystalline polyester resin A has a very low glass transition temperature and has a low temperature deformation property. Consequently, non-crystalline polyester resin A has such a property that it deforms with heating and pressure after fixing and easily adheres to recording media such as low temperature paper. Also, since a reactive precursor of non-crystalline polyester resin A is a non-linear chain, non-crystalline polyester resin A has a branched structure in its molecular skeleton, and the molecular chain of it becomes a three-dimensional network structure. . As a result, non-crystalline polyester resin A has such rubber-like properties as to deform at low temperature, but does not flow, allowing the toner to retain heat-resistant storage stability and resistance to hot offset. Note that when non-crystalline polyester resin A has a urethane bond or a urea bond having high cohesive energy, the toner obtained is more excellent in adhesion on recording media such as paper. Also, the urethane bond or the urea bond behaves as a pseudo-crosslink point to increase the rubber-like properties of the polyester resin. As a result, the toner obtained is more excellent in heat resistant storage stability and resistance to hot offset.
    [000111] [000111] Specifically, in one aspect of the toner of the present invention, by combining non-crystalline polyester resin A, which has a glass transition temperature in an ultra-low temperature region, but does not flow easily due to the high melting viscosity, with non-crystalline polyester resin B and crystalline polyester resin C, it is possible to maintain heat-resistant storage stability and resistance to hot offset even when the glass transition temperature of the toner is set to be lower than that of a conventional toner; and because it makes the toner have a low glass transition temperature, the toner excels at holding at low temperatures. Non-crystalline polyester resin A
    [000112] [000112] The non-crystalline polyester resin A is preferably obtained by the reaction between a reactive non-linear chain precursor and a curing agent.
    [000113] [000113] The non-crystalline polyester resin A preferably has a glass transition temperature of -60 ° C to 0 ° C.
    [000114] [000114] The non-crystalline polyester resin A preferably contains a urethane bond, a urea bond, or both, since it is more excellent in adhesion on recording media such as paper. Also, as a result of containing a urethane bond, a urea bond, or both in the non-crystalline polyester resin, the urethane bond or the urea bond behaves like a pseudo-point.
    [000115] [000115] The non-crystalline polyester resin A contains a dicarboxylic acid component as a constituent component thereof, and the dicarboxylic acid component preferably contains an aliphatic dicarboxylic acid in an amount of 60 mol% or more.
    [000116] [000116] Examples of a dicarboxylic acid component include an aliphatic dicarboxylic acid having 4 to 12 carbon atoms. Examples of aliphatic dicarboxylic acid having 4 to 12 carbon atoms include succinic acid, glutaric acid, adipic acid, pyelic acid, submeric acid, azelaic acid, sebacic acid, and decanedioic acid. Non-linear chain reactive precursor
    [000117] [000117] The non-linear chain reactive precursor is not particularly limited and can be appropriately selected depending on the intended purpose as long as it is a polyester resin containing a reactive group with the curing agent (hereinafter referred to as "prepolymer") .
    [000118] [000118] Examples of the reactive group with the curing agent in the prepolymer include a reactive group with an active hydrogen group. Examples of the group reactive with an active hydrogen group include an isocyanate group, epoxy group, carboxylic acid and an acid chloride group. Among them, an isocyanate group is preferred since it is possible to introduce a urethane bond or a urea bond into the non-crystalline polyester resin.
    [000119] [000119] The prepolymer is a non-linear chain. The non-linear chain means having a branched structure provided by a tri-alcohol or higher, a trivalent or higher carboxylic acid, or both.
    [000120] [000120] The prepolymer is preferably a polyester resin containing an isocyanate group. Polyester resin containing an isocyanate group.
    [000121] [000121] Polyester resin containing an isocyanate group is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of the same include a reaction product between a polyisocyanate and a polyester resin containing an active hydrogen group. The polyester resin containing an active hydrogen group can be obtained, for example, through polycondensation between the following: a diol; a dicarboxylic acid; and a trihydric alcohol or higher, a trivalent carboxylic acid or higher. Trihydric alcohol or higher, trivalent carboxylic acid or higher, or both provide a branched structure for the polyester resin containing an isocyanate group. Diol
    [000122] [000122] The diol is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include aliphatic diols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8 -octanediol, 1,10-decanediol, and 1,12-
    [000123] [000123] These diois can be used individually or in combination of two or more of them. Dicarboxylic acid
    [000124] [000124] The dicarboxylic acid component is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of the same include aliphatic dicarboxylic acids and aromatic dicarboxylic acids. In addition, anhydrides of the same, esterified lower alkyl compounds (C1 to C3) of the same, or halides of the same can also be used.
    [000125] [000125] Aliphatic dicarboxylic acid is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of the same include succinic acid, adipic acid, sebacic acid, decanedioic acid, maleic acid and fumaric acid.
    [000126] [000126] Aromatic dicarboxylic acid is not particularly limited and can be appropriately selected depending on the intended purpose, but is preferably an aromatic dicarboxylic acid having 8 to 20 carbon atoms. Aromatic dicarboxylic acid having 8 to 20 carbon atoms is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of it include phthalic acid, isophthalic acid, terephthalic acid and naphthalenedicarboxylic acids.
    [000127] [000127] Among them, aliphatic dicarboxylic acids having 4 to 12 carbon atoms are preferred.
    [000128] [000128] These dicarboxylic acids can be used individually or in combination of two or more of them. Trihydric alcohol or higher
    [000129] [000129] Tridric alcohol or higher is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of the same include higher trihydric or aliphatic alcohols, trihydric or higher polyphenols, and alkylene oxide adducts of trihydric or higher polyphenols.
    [000130] [000130] Examples of aliphatic trihydric alcohol or higher include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and sorbitol.
    [000131] [000131] Examples of tri-poly or higher polyphenols include trisphenol PA, novolaca phenol and novolaca cresol.
    [000132] [000132] Examples of alkylene oxide adducts of tri-polyphenols or higher include adducts of trivalent or higher polyphenols with, for example, ethylene oxide, propylene oxide, or butylene oxide.
    [000133] [000133] The non-crystalline polyester resin A preferably contains an aliphatic trihydric alcohol or higher as a constituent component thereof.
    [000134] [000134] When the non-crystalline polyester resin (A) contains a tri-aliphatic or higher aliphatic alcohol as a constituent component of it, the non-crystalline polyester resin A has a branched structure in its molecular skeleton, and the molecular chain thereof is makes a network structure three-dimensional. As a result, non-crystalline polyester resin A has such rubber-like properties as to deform at low temperature, but does not flow, allowing the toner to retain heat-resistant storage stability and resistance to hot offset.
    [000135] [000135] The non-crystalline polyester resin A can also use, for example, a trivalent or higher carboxylic acid or an epoxy as the crosslinking component. In that case, however, a still image obtained by fixing the resultant with heat may not show sufficient brightness since many trivalent or higher carboxylic acids are aromatic compounds or an ester bond density of the crosslinking components becomes higher. The use of a crosslinking agent such as an epoxy requires crosslinking reaction after polymerization to the polyester, which makes it difficult to control the distance between crosslinked points, potentially leading to failure to achieve desired viscoelasticity and / or degradation in image density or brightness due to irregularity in the still image. The reason why irregularity in the fixed image originates is that the epoxy tends to react with an oligomer formed during the production of the polyester to form portions having a high cross-linked density. Trivalent or higher carboxylic acid
    [000136] [000136] Trivalent or higher carboxylic acid is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of the same include aromatic trivalent or higher carboxylic acids. In addition, anhydrides thereof, compounds esterified with lower alkyl (C1 to C3), or halides of the same can also be used.
    [000137] [000137] Trivalent or higher aromatic carboxylic acid is preferably a trivalent or higher aromatic carboxylic acid having 9 to 20 carbon atoms Examples of trivalent or higher aromatic carboxylic acid having 9 to 20 carbon atoms include trimellitic acid and pyromelitic acid. Polyisocyanate
    [000138] [000138] Polyisocyanate is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of the same include diisocyanate, and trivalent or higher isocyanate.
    [000139] [000139] Examples of the diisocyanate include: aliphatic diisocyanate; alicyclic diisocyanate; aromatic diisocyanate; aromatic aliphatic diisocyanate; isocyanurate; and a blocking product thereof where the above compounds are blocked with a phenol, oxime or caprolactam derivative.
    [000140] [000140] The aliphatic diisocyanate is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of the same include tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanate methyl caproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethyl hexane diisocyanate and tetramethylene hexane diisocyanate and.
    [000141] [000141] Alicyclic diisocyanate is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of the same include isophorone diisocyanate, and cyclohexyl methane diisocyanate.
    [000142] [000142] The aromatic diisocyanate is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of the same include tolylene diisocyanate, diphenyl methane diisocyanate, 1,5-neftilene diisocyanate, 4,4'-diisocyanate, 4,4'-diisocyanate-3,3'-dimethyl diphenyl, 4,4'-diisocyanate- 3-methyl diphenyl methane and 4,4'-diisocyanate-diphenyl ether.
    [000143] [000143] The aromatic aliphatic diisocyanate is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of the same include , ,  ', ’-tetramethyl xylene diisocyanate.
    [000144] [000144] Isocyanurate is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of the same include tris (isocyanatoalkyl) isocyanurate, and tris (isocyanatocycloalkyl) isocyanurate.
    [000145] [000145] These polyisocyanates can be used individually or in combination of two or more of them. Curing agent
    [000146] [000146] The curing agent is not particularly limited and can be appropriately selected depending on the intended purpose as long as it can react with the prepolymer. Examples of the same include compounds containing an active hydrogen group. Compound containing active hydrogen group
    [000147] [000147] An active hydrogen group in the compound containing an active hydrogen group is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of the same include a hydroxyl group (for example, an alcoholic hydroxyl group and a phenolic hydroxyl group), an amino group, a carboxyl group and a mercapto group. These can be used individually or in combination with two or more of them.
    [000148] [000148] The compound containing the active hydrogen group is not particularly limited and can be appropriately selected depending on the intended purpose, but is preferably selected from amines, since the amines can form a urea bond.
    [000149] [000149] Amines are not particularly limited and can be appropriately selected depending on the intended purpose. Examples of the same include diamine, trivalent amine or higher, amino alcohol, amino mercaptan, amino acid and compounds in which the amino groups of the above compounds are blocked. These can be used individually or in combination with two or more of them.
    [000150] [000150] Among them, diamine, and a mixture of diamine and a small amount of trivalent amine or higher are preferable.
    [000151] [000151] The diamine is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of it include aromatic diamine, alicyclic diamine, and aliphatic diamine. The aromatic diamine is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of it include phenylene diamine, diethyl toluene diamine, and 4,4'-diamino diphenyl methane. The alicyclic diamine is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of the same include 4,4'-diamino-3,3'-dimethyl dicyclohexyl methane, diamino cyclohexane and isophorone diamine. The aliphatic diamine is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of the same include ethylene diamine, tetramethylene diamine and hexamethylene diamine.
    [000152] [000152] The trivalent or higher amine is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of the same include diethylene tyramine and triethylene tetramine.
    [000153] [000153] Amino alcohol is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of the same include ethanol, amine, and hydroxyethyl aniline.
    [000154] [000154] Aminomercaptan is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of the same include aminoethyl mercaptan and aminopropyl mercaptan.
    [000155] [000155] The amino acid is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of the same include aminopropionic acid and aminocaproic acid.
    [000156] [000156] The compound where the amino group is blocked is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of it include a ketimine compound where the amino group is blocked with ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone and an oxazoline compound.
    [000157] [000157] To decrease the Tg of the non-crystalline polyester resin A so that it is more easily endowed with a low-temperature warp property, preferably the non-crystalline polyester resin A contains a diol component as a constituent component of it , and the diol component contains an aliphatic diol having 4 to 12 carbon atoms in an amount of 50% by weight or more.
    [000158] [000158] To decrease the Tg of the non-crystalline polyester resin A so that it is more easily endowed with a low-temperature warp property, preferably the non-crystalline polyester resin A contains the aliphatic diol having 4 to 12 atoms in one 50% by mass or more in all alcohol components.
    [000159] [000159] To decrease the Tg of the non-crystalline polyester resin A so that it is more easily endowed with a low-temperature warp property, preferably the non-crystalline polyester resin A contains a dicarboxylic acid component as a constituent component of it , and the dicarboxylic acid component contains an aliphatic dicarboxylic acid having 4 to 12 carbon atoms in an amount of 50% by weight or more.
    [000160] [000160] A glass transition temperature of the non-crystalline polyester resin A is preferably -60 ° C to 0 ° C, more preferably -40 ° C to -20 ° C. When the glass transition temperature is lower than -60ºC, the toner obtained cannot be prevented from flowing at low temperature, potentially leading to degradation in heat-resistant storage stability and / or resistance to film formation. When the glass transition temperature of the same is higher than 0ºC, the obtained toner cannot deform sufficiently with heating and pressure after fixation, potentially leading to insufficient fixation capacity at low temperature.
    [000161] [000161] A weight average molecular weight of the non-crystalline polyester resin A is not particularly limited and can be appropriately selected depending on the intended purpose. It is preferably 20,000 to 1,000,000, more preferably 50,000 to 300,000, particularly preferably 100,000 to 200,000, as measured in GPC (gel permeation chromatography) measurement.
    [000162] [000162] When the average molecular weight of the same is less than 20,000, the toner obtained flows more easily at low temperature, potentially leading to degradation in heat-resistant storage stability. In addition, the toner can be degraded in resistance to hot offset due to the decreased viscosity of the toner after fusing.
    [000163] [000163] A molecular structure of the non-crystalline polyester resin can be confirmed by solution state or solid state NMR, X-ray diffraction, GC / MS, LC / MS or IR spectroscopy. Simple methods of it include a method for detecting, as a non-crystalline polyester resin, one that has no absorption based on CH (bending vibration out of plane) olefin at 965 cm-1  10 cm-1 and 990 cm-1  10 cm-1 in an infrared absorption spectrum.
    [000164] [000164] A quantity of the non-crystalline polyester resin A is not particularly limited and can be appropriately selected depending on the intended purpose, however it is preferably 5 parts by mass to 25 parts by mass, more preferably 10 parts by mass to 20 parts by mass , with respect to 100 parts per toner mass. When the amount of the same is less than 5 parts per mass, low temperature fixation capacity and resistance to hot offset of a resulting toner can be impaired. When the amount of the same is greater than 25 parts per mass, heat-resistant storage stability of the toner can be impaired, and the brightness of an image obtained after fixation can be reduced. When the amount of the same is within the most preferable range mentioned above, it is advantageous because all the low temperature fastening capacity, resistance to hot offset, and heat resistant storage stability exceed. Non-crystalline polyester resin B
    [000165] [000165] The non-crystalline polyester resin B preferably has a glass transition temperature of 40 ° C to 80 ° C.
    [000166] [000166] The non-crystalline polyester resin B is preferably a linear polyester resin.
    [000167] [000167] The non-crystalline polyester resin B is preferably an unmodified polyester resin. The unmodified polyester resin refers to a polyester resin that is obtained using a polyhydric alcohol and a polyvalent carboxylic acid or a derivative thereof such as a polyvalent carboxylic acid anhydride or a polyvalent carboxylic acid ester, and which is not modified with an isocyanate compound or the like. Preferably, the non-crystalline polyester resin B does not have a urethane bond or a urea bond.
    [000168] [000168] The non-crystalline polyester resin B contains a dicarboxylic acid component as a constituent component, and the dicarboxylic acid component contains terephthalic acid in an amount of 50 mol% or more, which is advantageous in terms of storage stability heat resistant.
    [000169] [000169] Examples of polyhydric alcohol include diols.
    [000170] [000170] Examples of the diol include adducts of bisphenol A with alkylene oxides (C2 to C3) (number of average addition moles: 1 to 10) as polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane; hydrogenated bisphenol A and hydrogenated bisphenol A adducts with alkylene oxides (C2 to C3) (average number of addition moles: 1 to 10).
    [000171] [000171] These can be used individually or in combination of two or more of them.
    [000172] [000172] Examples of polyvalent carboxylic acid include dicarboxylic acids.
    [000173] [000173] Examples of dicarboxylic acid include adipic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, and maleic acid; and succinic acid having, as a substituent, an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 1 to 20 carbon atoms, such as dodecenyl succinic acid and an octyl succinic acid.
    [000174] [000174] These can be used individually or in combination of two or more of them.
    [000175] [000175] Also, to adjust the acid value or hydroxyl value, the non-crystalline polyester resin B may contain a trivalent or higher carboxylic acid, a tri-alcohol or higher or both at the end of its resin chain.
    [000176] [000176] Examples of trivalent or higher carboxylic acid include trimellitic acid, pyromelitic acid and acid anhydrides thereof.
    [000177] [000177] Examples of trihydric alcohol or higher include glycerin, pentaerythritol and trimethyl propane.
    [000178] [000178] A molecular weight of the non-crystalline polyester resin B is not particularly limited and can be appropriately selected depending on the intended purpose. When its molecular weight is too low, the toner obtained may be poor in heat-resistant storage stability and durability under tension such as agitation in a developing device. When its molecular weight is too high, the toner obtained can be increased in viscoelasticity after melting to be poor in fixation capacity at low temperature. Consequently, in GPC (gel permeation chromatography), the non-crystalline polyester resin B preferably has a weight average molecular weight (Mw) of 3,000 to 10,000, and also has a numerical average molecular weight (Mn) of 1,000 to
    [000179] [000179] The average molecular weight (Mw) of the non-crystalline polyester resin B is more preferably 4,000 to
    [000180] [000180] An acid value of the non-crystalline polyester resin B is not particularly limited and can be appropriately selected depending on the intended purpose, however it is preferably 1 mgKOH / g to 50 mgKOH / g, more preferably 5 mgKOH / g to 30 mgKOH / g. When its acid value is 1 mgKOH / g or more, the toner obtained will be negatively chargeable more easily and will be better in affinity with paper after being fixed on it, and as a result can be improved in its ability to fix at low temperature. When its acid value is greater than 50 mgKOH / g, the toner obtained can be degraded under load stability, especially load stability to environmental changes.
    [000181] [000181] The hydroxyl value of the non-crystalline polyester resin B is not particularly limited and can be appropriately selected depending on the intended purpose, however it is preferably 5 mgKOH / g or more.
    [000182] [000182] A glass transition temperature (Tg) of the non-crystalline polyester resin B is preferably 40 ° C to 80 ° C, more preferably 50 ° C to 70 ° C. When the glass transition temperature is lower than 40ºC, the toner obtained can be poor in heat-resistant storage stability and durability in tension such as agitation in a developing device and can also be degraded in film-forming resistance. When the glass transition temperature of the same is higher than 80ºC, the toner obtained cannot deform sufficiently with heating and pressure after fixation, potentially leading to insufficient fixation capacity at low temperature.
    [000183] [000183] A molecular structure of non-crystalline polyester resin B can be confirmed by solution state or solid state NMR, X-ray diffraction, GC / MS, LC / MS or IR spectroscopy. Simple methods of it include a method for detecting, as a non-crystalline polyester resin, one that has no absorption based on CH (bending vibration out of plane) olefin at 965 cm-1  10 cm-1 and 990 cm-1  10 cm-1 in an infrared absorption spectrum.
    [000184] [000184] A quantity of the non-crystalline polyester resin B is not particularly limited and can be appropriately selected depending on the intended purpose, however it is preferably 50 parts by mass for
    [000185] [000185] The crystalline polyester resin C has thermofusion characteristics in which viscosity is drastically reduced in temperature around the starting temperature of fixation, since the crystalline polyester resin C has high crystallinity. Because it uses the crystalline polyester resin C having the above mentioned characteristics together with the non-crystalline polyester resin B in the toner, the heat resistance storage stability of the toner is excellent up to the start temperature of melting due to crystallinity, and the toner drastically decreases its viscosity (sharp melting property) at the start of melting temperature due to the melting of the crystalline polyester resin C. Along with the dramatic decrease in viscosity as a result of melting, the crystalline polyester resin C is melted together with the non-crystalline polyester resin B, to dramatically decrease its viscosity to thereby be fixed. Therefore, a toner having excellent heat-resistant storage stability and low temperature holding capacity can be obtained. In addition, the toner has excellent results in terms of a release width (a difference between the minimum holding temperature and hot offset occurrence temperature).
    [000186] [000186] The crystalline polyester resin C is obtained from polyhydric alcohol and polyvalent carboxylic acid or a derivative thereof as a polyvalent carboxylic acid anhydride or a polyvalent carboxylic acid ester.
    [000187] [000187] Note that in the present invention, the crystalline polyester resin C is one obtained from polyhydric alcohol and polyvalent carboxylic acid or a derivative thereof as a polyvalent carboxylic acid anhydride or a polyvalent carboxylic acid ester, as described above and a resin obtained by modifying a polyester resin, for example, the aforementioned prepolymer and a resin obtained through crosslinking and / or chain elongation reaction of the prepolymer do not belong to the crystalline polyester resin C. Polyhydric alcohol
    [000188] [000188] Polyhydric alcohol is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of the same include diol, and tri-alcohol or higher.
    [000189] [000189] Examples of the diol include saturated aliphatic diol. Examples of saturated aliphatic diol include straight chain saturated aliphatic diol, and branched chain saturated aliphatic diol. Among them, straight chain saturated aliphatic diol is preferable, and straight chain saturated aliphatic diol C2-C12 is more preferable. When the saturated aliphatic diol has a branched chain structure, crystallinity of the crystalline polyester resin C may be low, which can decrease the melting point. When the number of carbon atoms in the saturated aliphatic diol is greater than 12, it can be difficult to provide a material in practice. The number of carbon atoms is therefore preferably 12 or less.
    [000190] [000190] Examples of saturated aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1 , 9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, and 1,14-eicosanedecanediol. Among them, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol and 1,12-dodecanediol are preferable, since they provide high crystallinity to a crystalline polyester resin resulting, and provide excellent sharp fusion properties.
    [000191] [000191] Examples of trihydric alcohol or higher include glycerin, trimethylol ethane, trimethylol propane and pentaerythritol.
    [000192] [000192] These can be used individually or in combination of two or more of them. Polyvalent carboxylic acid
    [000193] [000193] Polyvalent carboxylic acid is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of the same include divalent dicarboxylic acid, and trivalent or higher carboxylic acid.
    [000194] [000194] Examples of divalent carboxylic acid include: saturated aliphatic dicarboxylic acid, such as oxalic acid, succinic acid, glutaric acid, adipic acid, submeric acid, azelaic acid, sebacic acid, 1,9-nonanodicarboxylic acid, 1,10- decanodicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid and 1,18-octanodicarboxylic acid; aromatic dicarboxylic acid of dibasic acid, such as phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, malonic acid, and mesaconic acid; and anhydrides of the above compounds, and lower (C1-C3) alkyl ester of the above compounds.
    [000195] [000195] Examples of trivalent or higher carboxylic acid include 1,2,4-benzene tricarboxylic acid, 1,2,5-benzene tricarboxylic acid, 1,2,4-naphthalene tricarboxylic acid, anhydrides thereof, and (C1) alkyl esters - C3) bottom of it.
    [000196] [000196] In addition, polyvalent carboxylic acid may contain, other than saturated aliphatic dicarboxylic acid or aromatic dicarboxylic acid, dicarboxylic acid containing a sulfonic acid group. In addition, polyvalent carboxylic acid may contain, unlike saturated aliphatic dicarboxylic acid or aromatic dicarboxylic acid, dicarboxylic acid having a double bond.
    [000197] [000197] These can be used individually or in combination of two or more of them.
    [000198] [000198] The crystalline polyester resin C is preferably composed of a straight chain saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms and a straight chain saturated aliphatic diol having 2 to 12 carbon atoms. Specifically, the crystalline polyester resin C preferably contains a constituent unit derived from a saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms, and a constituent unit derived from a saturated aliphatic diol having 2 to 12 carbon atoms. As a result, crystallinity increases, and enhanced melting properties improve, and is therefore preferable, since excellent toner low-temperature fixation is exhibited.
    [000199] [000199] A melting point of crystalline polyester resin C is not particularly limited and can be appropriately selected depending on the intended purpose, but is preferably 60 ° C to 80 ° C. When its melting point is lower than 60 ° C, the crystalline polyester resin tends to be melted at low temperature, which can impair the heat-resistant storage stability of the toner. When the melting point of the same is higher than 80ºC, the melting of the crystalline polyester resin C with heat applied during fixation may be insufficient, which can impair the toner's ability to fix at low temperature.
    [000200] [000200] A molecular weight of crystalline polyester resin C is not particularly limited and can be appropriately selected depending on the intended purpose. Since those having an accentuated molecular weight distribution and low molecular weight have excellent low temperature fixation capacity, and the heat-resistant storage stability of a resulting toner decreases when an amount of a low molecular weight component, a soluble component The o-dichlorobenzene of the crystalline polyester resin C preferably has a weight average molecular weight (Mw) of 3,000 to 30,000, a numerical average molecular weight (Mn) of 1,000 to 10,000, and Mw / Mn of 1.0 to 10, measured by GPC.
    [000201] [000201] In addition, it is more preferred that the average molecular weight (Mw) of the same is 5,000 to 15,000, the numerical average molecular weight (Mn) is 2,000 to 10,000, and the Mw / Mn is 1.0 to 5, 0.
    [000202] [000202] An acid value of crystalline polyester resin C is not particularly limited and can be appropriately selected depending on the intended purpose, however it is preferably 5 mgKOH / g or higher, more preferably 10 mgKOH / g or higher to obtain the ability to fix at low temperature desired in view of the affinity between paper and resin. Meanwhile, its acid value is preferably 45 mgKOH / g or lower in order to improve resistance to hot offset.
    [000203] [000203] A hydroxyl value of crystalline polyester resin C is not particularly limited and can be appropriately selected depending on the intended purpose, however it is preferably 0 mgKOH / g to 50 mgKOH / g, more preferably 5 mgKOH / g to 50 mgKOH / g, to obtain the desired low temperature clamping capacity and excellent loading properties.
    [000204] [000204] A molecular structure of crystalline polyester resin C can be confirmed by solution state or solid state NMR, X-ray diffraction, GC / MS, LC / MS or IR spectroscopy. Simple methods of it include a method for detecting, such as a crystalline polyester C resin, one that has absorption based on CH (bending vibration out of plane) olefin at 965 cm-1  10 cm-1 and 990 cm -1  10 cm-1 in an infrared absorption spectrum.
    [000205] [000205] A quantity of crystalline polyester resin C is not particularly limited and can be appropriately selected depending on the intended purpose, however it is preferably 3 parts by mass to 20 parts by mass, more preferably 5 parts by mass to 15 parts by mass, with respect to 100 parts per toner mass. When the amount of the same is less than 3 parts by mass, the crystalline polyester resin C does not provide sufficient sharp melting properties, which can lead to the insufficient low temperature fixation capacity of a resulting toner. When the amount is greater than 20 parts by mass, a resulting toner may have low, heat-resistant storage stability and tend to cause an image to mist. When the amount of the same is within the most preferable range mentioned above, it is advantageous because a resulting toner is excellent in terms of both high image quality and low temperature holding capacity. Other components
    [000206] [000206] Examples of other components include a release agent, coloring substance, charge control agent, external additive, a flow enhancing agent, a cleaning enhancing agent and a magnetic material. Release agent
    [000207] [000207] The release agent is appropriately selected from those known in the art without any limitation.
    [000208] [000208] Examples of wax that serve as the release agent include: natural wax, such as vegetable wax (for example, carnauba wax, cotton wax, Japan wax and rice wax), animal wax (for example, wax bees and lanolin), mineral wax (for example, ozokelite and ceresin) and petroleum wax (for example, paraffin wax, microcrystalline wax and petrolatum).
    [000209] [000209] Examples of wax other than the natural wax above include synthetic hydrocarbon wax, for example, Fischer-Tropsch wax and polyethylene wax; and synthetic wax (for example, ester wax, ketone wax and ether wax).
    [000210] [000210] In addition, other examples of the release agent include fatty acid amides such as 12-hydroxystearic acid amide, stearic amide, phthalic anhydride imide and chlorinated hydrocarbons; low molecular weight crystalline polymers such as acrylic homopolymers (for example, poly-n-stearyl methacrylate and poly-n-lauryl methacrylate) and acrylic copolymers (for example, n-stearyl ethyl methacrylate copolymers); and crystalline polymers having a long alkyl group as a secondary chain.
    [000211] [000211] Among them, hydrocarbon wax, such as paraffin wax, microcrystalline wax, Fischer-Tropsh wax, polyethylene wax and polypropylene wax are preferable.
    [000212] [000212] A melting point of the release agent is not particularly limited and can be appropriately selected depending on the intended purpose, however it is preferably 60 ° C to 80 ° C. When the melting point is lower than 60ºC, the release agent tends to melt at low temperature, which can impair heat-resistant storage stability. When the melting point is higher than 80ºC, the release agent is not sufficiently melted to thereby cause offset fixation even in the case where the resin is melted and is in the fixation temperature range, which can cause defects in An image.
    [000213] [000213] An amount of the release agent is appropriately selected depending on the intended purpose without any limitation, however it is preferably 2 parts by mass to 10 parts by mass, more preferably 3 parts by mass to 8 parts by mass, in relation to 100 parts by toner mass. When the amount of the same is less than 2 parts per mass, a resulting toner may have insufficient hot offset resistance, and a low temperature holding capacity during setting. When the amount of the same is greater than 10 parts per mass, a resulting toner may have insufficient heat resistant storage stability and tends to cause fogging in an image. When the amount of the same is within the most preferable range mentioned above, it is advantageous because the image quality and the fixation stability can be improved. Colorant
    [000214] [000214] The coloring substance is appropriately selected depending on the intended purpose without any limitation, and examples of it include carbon black, a nigrosine dye, iron black, naphthol yellow S, Hansa yellow, (10G, 5G and G), cadmium yellow, yellow iron oxide, yellow ocher, yellow lead, titanium yellow, polyazole yellow, Oil Yellow, Hansa Yellow (GR, A, RN and R), Pigment Yellow L, Benzidine Yellow (G and GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), tartrazine lake, Lake quinoline yellow, BTH Anthrax Yellow, Isoindolinone yellow, colcothar, lead red, vermilion lead, cadmium red, Cadmium Mercury Red, antimony vermilion, Permanent Red 4R, Para Red, Fiser Red, Red for Aniline Chloroortonitro, Litol Fast Scarlet G, Scarlet Fast Glossy, Carmine Glossy BS, Permanent Red (F2R, F4R, FRL, FRLL and F4RH), Scarlet Fast VD, Rubin Fast Vulcan B, Scarlet Brilliant G, Rubin Litol GX, Red Per keepente F5R, Carmine Brilliant 6B, Pigment Scarlet 3B, Burgundy 5B, Toluidine Brown, Permanent Burgundy F2K, Helium BL Burgundy, Burgundy 10B, BON Light Brown, BON Medium Brown, Lake Eosina, Lake Rhodamine B, Lake
    [000215] [000215] A quantity of the coloring substance is not particularly limited and can be appropriately selected depending on the intended purpose, however it is preferably 1 part by mass to 15 parts by mass, more preferably 3 parts by mass to 10 part by mass, in relation to 100 parts per toner mass.
    [000216] [000216] The coloring substance can be used as a master batch in which the coloring substance forms a composite with a resin. Examples of the binder resin kneaded in the production of, or together with the master batch include: different from the non-crystalline polyester resin B, mentioned above, styrene polymer or substitution thereof (for example, polystyrene, poly-p-chloro-styrene and polyvinyl ); styrene copolymer (for example, styrene-p-chloro-styrene copolymer, styrene-propylene copolymer, styrene-vinyl toluene copolymer, styrene-vinyl naphthalene copolymer, methyl-styrene acrylate copolymer, ethyl acrylate copolymer , butyl styrene acrylate copolymer, octyl styrene acrylate copolymer, methyl styrene methacrylate copolymer, ethyl styrene methacrylate copolymer, butyl styrene methacrylate copolymer, -styrene chloride copolymer , acrylonitrile-styrene copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, isoprene-styrene copolymer, indene-acrylonitrile-styrene copolymer, maleic-styrene acid copolymer, and ester-maleic copolymer styrene); and others including polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, pitch, modified pitch , a terpene resin, an aliphatic or alicyclic hydrocarbon resin, an aromatic petroleum resin, chlorinated paraffin and paraffin wax. These can be used independently or in combination.
    [000217] [000217] The master batch can be prepared by mixing and kneading the coloring substance with the resin for the master batch. In mixing and kneading, an organic solvent can be used to improve the interactions between the coloring substance and the resin. In addition, the master batch can be prepared by a flashing method in which an aqueous paste containing a coloring substance is mixed and kneaded with a resin and an organic solvent, and then the coloring substance is transferred to the resin to remove water and the organic solvent. This method is preferably used because a wet mass of the coloring substance is used as is, and it is not necessary to dry the wet mass of the coloring substance to prepare a coloring substance. In mixing and kneading the coloring substance and resin, a high shear dispersion medium (for example, a three-roller mill) is preferably used. Load control agent
    [000218] [000218] The charge control agent is not particularly limited and can be appropriately selected depending on the intended purpose without any limitation, and examples thereof include nigrosine dyes, triphenyl methane dyes, chrome complex metal dyes, pigments of molybdic acid chelate, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus, phosphorus compounds, tungsten, tungsten compounds, fluorine active agents, metal salts salicylic acid, and metal salts of salicylic acid derivatives.
    [000219] [000219] Specific examples of the same include nigrosine dye BONTRON 03, a quaternary ammonium salt BONTRON P-51, azo dye containing metal BONTRON S-34, a metal complex based on oxynaphonic acid E-82, a metal complex based on salicylic acid E-84, and a condensate of phenol E-89 (all of which are manufactured by
    [000220] [000220] A quantity of the charge control agent is not particularly limited and can be appropriately selected depending on the intended purpose, however it is preferably 0.1 part by mass to 10 parts by mass, more preferably 0.2 parts by mass at 5 parts per mass, based on 100 parts per mass of toner. When the amount of the same is greater than 10 parts per mass, the charge capacity of the toner becomes excessive, which can reduce the effect of the charge control agent, increase the electrostatic force for a developing roller, leading to the ability to low developer flow, or low image density of the resulting image. These charge control agents can be dissolved and dispersed after being melted and kneaded together with the master batch, and / or resin. Charge control agents can, of course, be directly added to an organic solvent when dissolution and dispersion are carried out. Alternatively, charge control agents can be attached to surfaces of toner particles after the production of the toner particles. External additive
    [000221] [000221] With respect to the external additive, other than oxide particles, a combination of inorganic particles and hydrophobic treated inorganic particles can be used. The average primary particle diameter of the hydrophobic treated particles is preferably 1 nm to 100 nm. More preferred are 5 nm to 70 nm of inorganic particles.
    [000222] [000222] Furthermore, it is preferred that the external additive contains at least one type of hydrophobic treated inorganic particles having the average primary particle diameter of 20 nm or less, and at least type of inorganic particles having the average primary particle diameter 30 nm or greater. In addition, the external additive preferably has a specific BET surface area of 20 m2 / g to 500 m2 / g.
    [000223] [000223] The external additive is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of the same include silica particles, hydrophobic silica, fatty acid metal salts (eg, zinc stearate, and aluminum stearate), metal oxide (eg, titania, alumina, tin oxide and antimony oxide ), and a fluoropolymer.
    [000224] [000224] Examples of the suitable additive include hydrophobic silica, titania, titanium oxide, and alumina particles. Examples of the silica particles include R972, R974, RX200, RY200, R202, R805, R812 (all manufactured by Nippon Aerosil Co., Ltd.). Examples of titania particles include P-25 (manufactured by Nippon Aerosil Co., Ltd.), STT-30 and STT-65C-S (both manufactured by Titan Kogyo, Ltd.), TAF-140 (manufactured by Fuji Titanium Industry Co.,
    [000225] [000225] Examples of hydrophobic treated titanium oxide particles include: T-805 (manufactured by Nippon Aerosil Co., Ltd.); STT-30A, STT-65S-S (both manufactured by Titan Kogyo, Ltd.); TAF- 500T, TAF- 1500T (both manufactured by Fuji Titanium Industry Co., Ltd.); MT-100S, MT-100T (both manufactured by Tayca Corporation), and IT-S (manufactured by Ishihara Sangyo Kaisha, Ltd.).
    [000226] [000226] Hydrophobic treated oxide particles, hydrophobic treated silica particles, hydrophobic treated titania particles and hydrophobic treated aluminum particles are obtained, for example, by treating hydrophilic particles with a silane coupling agent, such as methyl trimethoxysilane, methyl triethoxysilane, and octyl trimethoxysilane. In addition, oxide particles treated with silicone oil, or inorganic particles treated with silicone oil, which have been treated by adding silicone oil optionally with heat, are also suitably used as the external additive.
    [000227] [000227] Examples of silicone oil include dimethyl silicone oil, methyl phenyl silicone oil, chlorophenyl silicone oil, methyl hydrogen silicone oil, alkyl modified silicone oil, fluorine modified silicone oil, modified silicone oil polyether, alcohol modified silicone oil, amino modified silicone oil, epoxy modified silicone oil, epoxy polyether modified silicone oil, phenol modified silicone oil, carboxyl modified silicone oil, silicone oil modified by mercapto, silicone oil modified by methacryl, and silicone oil modified by -methyl styrene.
    [000228] [000228] Examples of inorganic particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, tin oxide, sand quartz, clay, mica, wollastonite, diatomaceous earth, chromic oxide, cerium oxide, red iron oxide, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, carbide silicon and silicon nitride. Among these, silica and titanium dioxide are preferable.
    [000229] [000229] An amount of the external additive is not particularly limited and can be appropriately selected depending on the intended purpose, however it is preferably 0.1 part by mass to 5 parts by mass, more preferably 0.3 parts by mass to 3 parts by mass , with respect to 100 parts per toner mass.
    [000230] [000230] The average particle diameter of primary particles of inorganic particles is not particularly limited and can be appropriately selected depending on the intended purpose, however it is preferably 100 nm or less, more preferably 3 nm to 70 nm. When it is less than the range mentioned above, the inorganic particles are incorporated into the toner particles, and therefore the function of the inorganic particles may not be effectively displayed. When the average particle diameter of the same is greater than the range mentioned above, the inorganic particles can irregularly damage a photoconductor surface, and therefore not preferable. Improve flow capacity agent
    [000231] [000231] The flowability enhancing agent is not particularly limited and can be appropriately selected depending on the intended purpose as long as it is capable of surface treatment of the toner to increase hydrophobicity, and avoid degradation of flow properties and charge properties toner even in a high humidity environment. Examples of the same include a silane coupling agent, a silylation agent, a silane coupling agent containing a fluoroalkyl group, an organic titanate based coupling agent, an aluminum based coupling agent, silicone and modified silicone oil. It is particularly preferable that the titanium oxide or silica is used as hydrophobic silica or hydrophobic titanium oxide treated with the aforementioned flow improving agent. Agent to improve cleaning ability
    [000232] [000232] The cleaning ability enhancing agent is not particularly limited and can be appropriately selected depending on the intended purpose as long as it can be added to the toner for the purpose of removing the developer remaining on a photoconductor or primary transfer element after transfer. Examples of the same include: fatty acid metal salt such as zinc stearate, calcium stearate, and stearic acid; and polymer particles produced by soap-free emulsion polymerization, such as polymethyl methacrylate particles, and polystyrene particles. The polymer particles are preferably those having a relatively narrow particle size distribution, and polymer particles having a volume average particle diameter of 0.01 µm to 1 µm are preferably used. Magnetic material
    [000233] [000233] The magnetic material is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of it include iron powder, magnetite and ferrite. Among them, a white magnetic material is preferable in terms of a color tone. Method for measuring particle size distribution
    [000234] [000234] The average volume particle diameter (D4) and numerical average particle diameter (Dn) of the toner and their ratio (D4 / Dn) can be measured, for example, by using Coulter Counter TA-II or Coulter Multisizer II (both products are from Beckman Coulter, inc.) In the present invention, Coulter Multisizer II was used. The measurement method will be explained below.
    [000235] [000235] First, 0.1 ml to 5 ml of a surfactant (preferably alkyl benzene sulfonate (non-ionic surfactant)) was added as a dispersant to 100 ml up to 150 ml of an electrolyte. Note that the electrolyte is approximately 1 mass% of aqueous solution prepared by using a primary sodium chloride, and, for example, ISOTON-II (from Beckman Coulter, Inc.) is used as the electrolyte. Then, to the resulting mixture, 2 mg to 20 mg of a sample are added and suspended, and the mixture is dispersed by means of an ultrasonic wave dispersion medium for approximately 1 minute to approximately 3 minutes. The volume and number of the toner or toner particles are measured from the dispersion liquid obtained using the aforementioned measuring device with an aperture of 100 m, and then the volume distribution and toner number distribution are calculated. From the distributions obtained, the average volume particle diameter (D4) and the numerical average particle diameter (Dn) of the toner can be determined.
    [000236] [000236] Note that, as a channel, the following 13 channels are used: 2.00 m or greater, but less than 2.52m; 2.52 m or greater, but less than 3.17 m; 3.17 m or greater, but less than 4.00 m; 4.00 m or greater, but less than 5.04 m; 5.04 m or greater, but less than 6.35 m; 6.35 m or greater, but less than 8.00 m; 8.00 m or greater, but less than 10.08 m; 10.08 m or greater, but less than 12.70 m; 12.70 m or greater, but less than 16.00 m; 16.00 or greater, but less than 20.20 m; 20.20 m or greater, but less than 25.40 m; 25.40 m or greater, but less than 32.00 m; and 32.00 m or greater, but less than 40.30 m. The target particles for measurement are particles having diameters of 2.0 m or greater, but less than 40.30 m. Molecular weight measurement
    [000237] [000237] A molecular weight of each constituent component of a toner can be measured, for example, by the following method.
    [000238] [000238] GPC-8220GPC gel permeation chromatography measuring device (GPC) (manufactured by TOSOH CORPORATION)
    [000239] [000239] Column: TSKgel SuperHZM-H 15 cm, three connected columns (manufactured by TOSOH CORPORATION) Temperature: 40ºC Solvent: THF Flow rate: 0.35 mL / min. Sample: 100 L of a 0.15 mass% sample to be supplied
    [000240] [000240] Regarding the sample pre-treatment, the sample is dissolved in tetrahydrofuran (THF) (containing a stabilizer, manufactured by Wako Chemical Industries, ltd.), To provide a concentration of 0.15% by mass, the solution The resulting filter is then filtered through a filter having a pore size of 0.2 µm, and the filtrate from the filtration is used as a sample. The measurement is performed by providing 100 L of the tetrahydrofuran (THF) sample solution.
    [000241] [000241] For the measurement of the sample's molecular weight, a sample's molecular weight distribution is calculated from the relationship between the logarithmic value of the calibration curve prepared from several standard monodispersible polystyrene samples and the number of counts. Like standard polystyrene samples to prepare the calibration curve, Showdex Standard Std. Nos. S-7300, S-210, S-390, S-875, S-1980, S-10.9, S-629, S-3.0, and S-0.580 from SHOWA DENKO K.K., and toluene are used. As a detector, a refractive index (IR) detector is used. Toner production method
    [000242] [000242] A toner production method is not particularly limited and can be appropriately selected depending on the intended purpose, however the toner is preferably granulated by dispersing, in an aqueous medium, an oil phase containing the polyester resin and if necessary, also containing the release agent and the coloring substance.
    [000243] [000243] Also, the toner is more preferably granulated by dispersing, in an aqueous medium, an oil phase containing as the non-crystalline polyester resin, a polyester resin which is a prepolymer containing a urethane bond, a bond urea or both; and a polyester resin containing no urethane bond, urea bond, or both; preferably still containing the crystalline polyester resin; and if necessary, also containing the release agent, the coloring substance, etc.
    [000244] [000244] As an example of such a toner production method, a conventionally dissolving suspension method is listed. As an example of the toner production method, a method for forming toner-based particles while forming the non-crystalline polyester resin through a chain elongation reaction and / or a crosslinking reaction between the reactive non-linear chain precursor and the curing agent will be described below. In such a method, preparation of an aqueous medium, preparation of an oil phase containing a toner material, emulsification and / or dispersion of the toner material, and removal of an organic solvent are carried out. Preparation of aqueous medium (aqueous phase)
    [000245] [000245] The preparation of the aqueous phase can be carried out, for example, by dispersing resin particles in an aqueous medium. An amount of the resin particles in the aqueous medium is not particularly limited and can be appropriately selected depending on the intended purpose, however it is preferably 0.5 parts by weight to 10 parts by weight in relation to 100 parts by weight of the aqueous medium.
    [000246] [000246] The aqueous medium is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of the same include water, a water miscible solvent and a mixture thereof. These can be used independently or in combination. Among them, water is preferable.
    [000247] [000247] The water-miscible solvent is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of the same include alcohol, dimethyl formamide, tetrahydrofuran, celosolve and lower ketone. Alcohol is not particularly limited and can be selected appropriately depending on the intended purpose. Examples of the same include methanol, isopropanol and ethylene glycol. The lower ketone is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of it include acetone and methyl ethyl ketone. Oil phase preparation
    [000248] [000248] The oil phase containing the toner materials can be prepared by dissolving or dispersing, in an organic solvent, toner materials containing at least the non-crystalline polyester resin which is a prepolymer containing a urethane bond, a urea binding, or both; a polyester resin containing no urethane bond, urea bond, or both; and the crystalline polyester resin, and if necessary, also containing the curing agent, the releasing agent, the coloring substance, etc.
    [000249] [000249] The organic solvent is not particularly limited and can be appropriately selected depending on the intended purpose, however it is preferably an organic solvent having a boiling point of less than 150 ° C, since removal is easy.
    [000250] [000250] The organic solvent having a boiling point below 150ºC is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of it include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichlorethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, and methyl isobutyl ketone. These can be used individually or in combination with two or more of them.
    [000251] [000251] Among them, ethyl acetate, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride are particularly preferable, and ethyl acetate is more preferable. Emulsification or dispersion
    [000252] [000252] Emulsification or dispersion of the toner materials can be carried out by dispersing the oil phase containing the toner materials in the aqueous medium. In the course of emulsifying or dispersing the toner material, the curing agent and prepolymer are allowed to perform a chain elongation reaction or crosslinking reaction.
    [000253] [000253] The reaction conditions (for example, reaction time and reaction temperature) for generating the prepolymer are not particularly limited and can be appropriately selected depending on a combination of the curing agent and prepolymer.
    [000254] [000254] The reaction time is not particularly limited and can be appropriately selected depending on the intended purpose, however it is preferably 10 minutes to 40 hours, more preferably 2 hours to 24 hours.
    [000255] [000255] The reaction temperature is not particularly limited and can be appropriately selected depending on the intended purpose, however it is preferably 0ºC to 150ºC, more preferably 40ºC to 98ºC.
    [000256] [000256] A method for stably forming a dispersion liquid in the aqueous medium is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of the same include a method in which an oil phase, which was prepared by dissolving and / or dispersing a toner material in a solvent, is added to an aqueous medium phase, followed by shear force dispersion.
    [000257] [000257] A dispersion medium used for dispersion is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of the same include a low speed shear dispersion medium, a high speed shear dispersion medium, a friction dispersion medium, a high pressure jet forming dispersion medium and an ultrasonic wave dispersion medium. .
    [000258] [000258] Among them, the high speed shear dispersion medium is preferable, because it can control the particle diameters of the dispersed elements (oil droplets) in the range of 2 m to 20 m.
    [000259] [000259] In the case where high speed shear dispersion medium is used, conditions for dispersion, such as rotation speed, dispersion time, and dispersion temperature, can be appropriately selected depending on the intended purpose.
    [000260] [000260] The rotational speed is not particularly limited and can be appropriately selected depending on the intended purpose, however it is preferably 1,000 rpm at
    [000261] [000261] The dispersion time is not particularly limited and can be appropriately selected depending on the intended purpose, however it is preferably 0.1 minute to 5 minutes in the case of a batch system.
    [000262] [000262] The dispersion temperature is not particularly limited and can be appropriately selected depending on the intended purpose, however it is preferably 0 ° C to 150 ° C, more preferably 40 ° C to 98 ° C under pressure. Note that, in general terms, dispersion can be carried out easily, since the dispersion temperature is higher.
    [000263] [000263] An amount of the aqueous medium used for emulsifying or dispersing the toner material is not particularly limited and can be appropriately selected depending on the intended purpose, however it is preferably 50 parts per mass to 2,000 parts per mass, more preferably 100 parts per mass mass to 1,000 parts by mass, relative to 100 parts by mass of toner material.
    [000264] [000264] When the amount of the aqueous medium is less than 50 parts per mass, the dispersion state of the toner material is impaired, which can result in a failure to obtain toner-based particles having desired particle diameters. When the amount of it is greater than
    [000265] [000265] When the oil phase containing the toner material is emulsified or dispersed, a dispersant is preferably used for the purpose of stabilizing dispersed elements, such as oil droplets, and provides a format particle size distribution as well as providing desirable formats of toner particles.
    [000266] [000266] The dispersant is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of the same include a surfactant, a water-insoluble inorganic compound dispersant, and a polymer protective colloid. These can be used individually or in combination with two or more of them. Among them, the surfactant is preferable.
    [000267] [000267] The surfactant is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of the same include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.
    [000268] [000268] The anionic surfactant is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include alkyl benzene sulfonic acid salts, -olefin sulfonic acid salts and phosphoric acid esters. Among those, those having a fluoroalkyl group are preferable. Organic solvent removal
    [000269] [000269] A method for removing the organic solvent from the dispersion liquid such as the emulsified paste is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of it include: a method in which an entire reaction system is gradually heated to evaporate the organic solvent in the oil droplets; and a method in which the dispersion liquid is sprayed in a dry atmosphere to remove the organic solvent in the oil droplets.
    [000270] [000270] When the organic solvent is removed, toner-based particles are formed. The toner-based particles can be subjected to washing and drying, and can additionally be subjected to classification. The classification can be carried out in a liquid by removing small particles by cyclone, a decanter, or centrifugal separator, or it can be carried out in particles after drying.
    [000271] [000271] The toner-based particles obtained can be mixed with particles such as the external additive, and the charge control agent. By applying a mechanical impact during mixing, particles such as the external additive can be prevented from falling off the surfaces of the toner-based particles.
    [000272] [000272] A method for applying mechanical impact is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of it include: a method for applying thrust force to a mixture by a paddle rotating at high speed; a method for adding a mixture to a high-speed air flow and accelerating the flow speed to thereby cause the particles to collide with other particles, or to cause the composite particles to collide on an appropriate impact plate.
    [000273] [000273] A device used for this method is appropriately selected depending on the intended purpose without any limitation, and examples of it include ANGMILL (product of Hosokawa Micron Corporation), a device produced by modifying type I mill (product of Nippon Pneumatic Mfg. Co., Ltd.) to reduce spray air pressure, a hybridization system (product of Nara Machinery Co., Ltd.), a krypton system (product of Kawasaki Heavy Industries, Ltd.) and an automatic mortar. Developer
    [000274] [000274] A developer of the present invention contains at least the toner, and may also contain other appropriately selected components, such as carrier, if necessary.
    [000275] [000275] Therefore, the developer has excellent transfer properties, and load capacity and can stably form high quality images. Note that the developer may be a one-component developer, or a two-component developer, but is preferably a two-component developer when used on a high-speed printer corresponding to the recent high information processing speed, because life in service can be improved.
    [000276] [000276] In the case where the developer is used as a component developer, the diameters of the toner particles do not vary widely even when toner is supplied and consumed repeatedly, the toner does not cause film to form on a development roller, nor it melts into a layer thickness adjustment element like a paddle to fine tune the thickness of a toner layer, and provides excellent and stable development capability and image even when it is shaken in the development device for a long period of time.
    [000277] [000277] In the case where the developer is used as a two-component developer, the diameters of the toner particles in the developer do not vary widely even when the toner is supplied and consumed repeatedly, and the toner can provide excellent and stable development capacity even when the toner is agitated in the developer device for a long period of time.
    [000278] [000278] Carrier The carrier is appropriately selected depending on the intended purpose without any limitation, however it is preferably a carrier containing a core, and a resin layer covering the core. Core
    [000279] [000279] A core material is appropriately selected depending on the intended purpose without any limitation, and examples of it include a material of 50 emu / g 90 emu / g of manganese-strontium (Mn-Sr) and a material of 50 emu / ga 90 emu / g (Mn-Mg) of magnesium-manganese. To ensure sufficient image density, the use of a hard magnetic material such as iron powder (100 emu / g or higher) and magnetite (75 emu / g to 120 emu / g) is preferable. In addition, the use of a soft magnetic material such as a 30 emu / g and 80 emu / g copper-zinc material is preferable because an impact applied to a photoconductor by the developer loaded on a brush-like support element can be reduced, which is an advantage to improve image quality.
    [000280] [000280] These can be used individually or in combination of two or more of them.
    [000281] [000281] The average volume particle diameter of the core is not particularly limited and can be appropriately selected depending on the specific purpose, however it is preferably 10 µm to 150 µm, more preferably 40 µm to 100 µm. When the average particle diameter of its volume is less than 10 m, the proportion of fine particles in the distribution of carrier particle diameters increases, causing dispersion of the carrier due to low magnetization per carrier particle. When the average particle diameter of the volume is greater than 150 µm, the specific surface area reduces, which can cause toner dispersion, causing reproducibility especially in a solid image portion in a full color print containing many portions of solid image.
    [000282] [000282] In the case where toner is used for a two-component developer, toner is used for mixing with the carrier. A quantity of the carrier in the two-component developer is not particularly limited and can be appropriately selected depending on the intended purpose, however it is preferably 90 parts by mass to 98 parts by mass, more preferably 93 parts by mass to 97 parts by mass, in relation to to 100 parts by mass of the two-component developer.
    [000283] [000283] The developer of the present invention can be suitably used in image formation by various electrophotographs known as a method of developing a magnetic component, a method of developing a non-magnetic component, and a method of developing two components. Toner accommodating container
    [000284] [000284] A toner accommodating container of the present invention accommodates the toner of the present invention. The container therefor is not particularly limited and can be appropriately selected from known containers. Examples of the same include those having a lid and a main container body.
    [000285] [000285] The size, shape, structure and material of the main container body are not particularly limited. The main container body is preferably, for example, hollow cylindrical in shape. Particularly preferably, it is a hollow cylindrical body whose inner surface has concave-convex portions spirally arranged some or all of which can operate as an accordion and in which the accommodated developer can be transferred to an exit orifice by rotation. The material for the container that accommodates developer is not particularly limited and is preferably those from which the main container body can be formed with high dimensional accuracy. Examples of the same include polyester resins, polyethylene resins, polypropylene resins, polystyrene resins, polyvinyl chloride resins, polyacrylic acids, polycarbonate resins, ABS resins and polyacetal resins.
    [000286] [000286] The container that accommodates toner above has excellent handling capacity; that is, it is suitable for storage, transportation and is suitably used for supplying the toner being loosely mounted on, for example, the process cartridge described below and image forming apparatus. Image forming apparatus and image forming method
    [000287] [000287] An imaging apparatus of the present invention includes at least one element that contains electrostatic imaging, an electrostatic imaging unit, and a developing unit, and if necessary, includes further units.
    [000288] [000288] An imaging method of the present invention includes at least one electrostatic imaging step and a developing step, and if necessary, includes still other steps.
    [000289] [000289] The imaging method of the present invention can be suitably performed by the imaging apparatus of the present invention, the electrostatic imaging step can be suitably performed by the electrostatic imaging unit, the imaging step development can be properly carried out by the developing unit and the other steps can be properly carried out by the other units. Element that contains electrostatic imaging
    [000290] [000290] The material, structure and size of the element containing electrostatic imaging are not particularly limited and those known in the art can be appropriately selected. Regarding the material, the element that contains electrostatic imaging is, for example, an inorganic photoconductor made of amorphous silicon or selenium, or an organic photoconductor made of polysilane or phthalopolymetin. Among them, an amorphous silicon photoconductor is preferred since it has a long service life.
    [000291] [000291] The amorphous silicon photoconductor can be, for example, a photoconductor having a support and an electrically photoconductive layer of a Si, which is formed on the support heated to 50ºC to 400ºC with a film formation method such as vapor deposition at vacuum, cathodic sublimation, ion coating, thermal CVD (chemical vapor deposition), photo-CVD or plasma CVD. Among them, plasma CVD is suitably employed, in which gaseous raw materials are decomposed through the application of direct current or discharge of microwave shine or high frequency to form a Si deposition film on the support.
    [000292] [000292] The shape of the element containing electrostatic imaging is not particularly limited and can be appropriately selected depending on the intended purpose, but is preferably a hollow cylindrical shape. The outside diameter of the element containing electrostatic imaging having a hollow cylindrical shape is not particularly limited and can be appropriately selected depending on the intended purpose, however it is preferably 3 mm to 100 mm, more preferably 5 mm to 50 mm, particularly preferably 10 mm to 30 mm. Electrostatic imaging training unit and electrostatic imaging training stage
    [000293] [000293] The electrostatic imaging unit is not particularly limited and can be appropriately selected depending on the intended purpose as long as it is a unit configured to form an electrostatic imaging on the element containing electrostatic imaging. Examples of the same include a unit including at least one charge element configured to charge a surface of the element containing electrostatic imaging and an exposure element configured to expose the surface of the element containing electrostatic imaging to light in the image direction.
    [000294] [000294] The electrostatic imaging step is not particularly limited and can be appropriately selected depending on the intended purpose as long as it is a step of forming an electrostatic imaging on the element containing electrostatic imaging. The electrostatic imaging step can be performed using the electrostatic imaging unit, for example, by loading a surface of the element that contains electrostatic imaging and then exposing its surface to light in the image direction. Load and load element
    [000295] [000295] The load element is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include known contact type charging devices having, for example, an electrically conductive or semiconductive roller, brush, film and rubber paddle; and non-contact charging devices using corona discharge such as corotron and scorotron.
    [000296] [000296] The charge can be carried out, for example, by applying voltage to the surface of the element that contains electrostatic imaging using the charge element.
    [000297] [000297] The load element can have any shape like a load roller as well as a magnetic brush or a hair brush. The format of the same can be properly selected according to the specification or configuration of the image formation device.
    [000298] [000298] The load element is not limited to the load elements of the aforementioned contact type. However, contact type charge elements are preferably used from the point of view of producing an image forming apparatus in which the amount of ozone generated from the charge elements is reduced. Display and display element
    [000299] [000299] The exposure element is not particularly limited and can be appropriately selected depending on the purpose of obtaining exposure in the desired image direction on the surface of the element containing electrophotographic latent image loaded with the charge element. Examples of the same include various display devices such as an optical copy display device, a stem lens assembly display device, a laser optical display device, and a liquid crystal shutter display device.
    [000300] [000300] A light source used for the display element is not particularly limited and can be appropriately selected according to the intended purpose. Examples of it include conventional light-emitting devices such as a fluorescent lamp, a tungsten lamp, a halogen lamp, a mercury lamp, a sodium lamp, a light emitting diode (LED), a laser diode (LD) and an electroluminescence device (EL).
    [000301] [000301] Also, several types of filters can be used to emit only light having a desired wavelength range. Examples of filters include a sharp cut filter, a band pass filter, an infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter.
    [000302] [000302] The exposure can be carried out, for example, by exposing in the image direction the surface of the electrostatic imaging support element to light using the exposure element.
    [000303] [000303] In the present invention, light can be applied in the direction of image from the side facing the support of the element that contains electrostatic latent image. Developing unit and development stage
    [000304] [000304] The development unit is not particularly limited and can be appropriately selected depending on the intended purpose as long as it is a development unit containing a toner to reveal the electrostatic imaging formed on the electrostatic imaging support element to thereby form a visible image.
    [000305] [000305] The development step is not particularly limited and can be appropriately selected depending on the intended purpose as long as it is a step of developing the electrostatic imaging formed on the electrostatic imaging support element with a toner to thereby form a visible image . The development step can be performed by the development unit.
    [000306] [000306] The development unit can employ a dry or wet development process, and can be a single color or multi-color development unit.
    [000307] [000307] The developer unit is preferably a developer device containing: a stirring device for loading the friction toner generated during stirring; a magnetic field generation unit fixed inside; and a developer-containing element configured to support a developer containing the toner on a surface thereof and be rotatable.
    [000308] [000308] In the development unit, the toner particles and carrier particles are agitated and mixed so that the toner particles are charged by the friction generated between them. The charged toner particles are retained in a chain-like manner on the surface of the rotating magnetic roller to form magnetic brushes. The magnetic roller is arranged close to the electrostatic imaging developing element and in this way, some of the toner particles forming the magnetic brushes on the magnetic roller are transferred to the surface of the electrostatic imaging development element by the action of electrically attractive force. . As a result, the electrostatic imaging is developed with the toner particles to form a visual toner image on the surface of the electrostatic imaging development element. Other units and other steps
    [000309] [000309] Examples of the other units include a transfer unit, a fixation unit, a cleaning unit, a load disposal unit, a recycling unit and a control unit.
    [000310] [000310] Examples of the other steps include a transfer step, a fixation step, a cleaning step, a load elimination step, a recycling step, and a control step. Transfer unit and transfer step
    [000311] [000311] The transfer unit is not particularly limited and can be appropriately selected depending on the intended purpose as long as it is a unit configured to transfer the visible image to over a recording medium. Preferably, the transfer unit includes: a primary transfer unit configured to transfer the visible images to an intermediate transfer element to form a composite transfer image; and a secondary transfer unit configured to transfer the composite transfer image onto a recording medium.
    [000312] [000312] The transfer step is not particularly limited and can be appropriately selected depending on the intended purpose as long as it is a step of transferring the visible image onto a recording medium. In this step, preferably the visible images are primarily transferred to an intermediate transfer element, and the images thus visible transferred are secondarily transferred to the recording medium.
    [000313] [000313] For example, the transfer step can be performed using the transfer unit by loading the photoconductor with a transfer charger to transfer the visible image.
    [000314] [000314] Here, when the image to be secondarily transferred to the recording medium is a color image of toners of various colors, a configuration can be employed in which the transfer unit sequentially overlays the color toners on top of each other on the intermediate transfer element to form an image on the intermediate transfer element, and the image on the intermediate transfer element is secondarily transferred in a moment to over the recording medium by the intermediate transfer unit.
    [000315] [000315] The intermediate transfer element is not particularly limited and can be appropriately selected from known transfer elements depending on the intended purpose. For example, the intermediate transfer element is preferably a transfer belt.
    [000316] [000316] The transfer unit (including the primary and secondary transfer units) preferably includes at least one transfer device that transfers the visible images from the photoconductor onto the recording medium. Examples of the transfer device include a corona transfer device employing corona discharge, a transfer belt, a transfer roller, a pressure transfer roller and an adhesive transfer device.
    [000317] [000317] The recording medium is not particularly limited and can be appropriately selected depending on the purpose, as long as it can receive an unfixed, developed image. Examples of the recording medium include plain paper and a PET base for OHP, with plain paper being used typically. Fixing unit and fixing step
    [000318] [000318] The fixation unit is not particularly limited and can be appropriately selected depending on the intended purpose as long as it is a unit configured to fix a transferred image that has been transferred to the recording medium, but is preferably known heating pressure elements. Examples of these include a combination of a heat roller and a pressure roller, and a combination of a heat roller, a pressure roller and an endless belt.
    [000319] [000319] The fixation step is not particularly limited and can be appropriately selected according to the purpose, as long as it is a step of fixing a visible image that has been transferred to the recording medium. The fixing step can be performed every time an image of each color toner is transferred onto the recording medium, or at a time (at the same time) in a laminated image of color toners.
    [000320] [000320] The fixing step can be performed by the fixing unit.
    [000321] [000321] The heating pressurizing element normally performs heating preferably at 80ºC to 200ºC.
    [000322] [000322] Notably, in the present invention, known photofixing devices can be used instead of or in addition to the fixing unit depending on the intended purpose.
    [000323] [000323] A surface pressure in the fixation step is not particularly limited and can be appropriately selected depending on the intended purpose, however it is preferably 10 N / cm2 to 80 N / cm2. Cleaning unit and cleaning step
    [000324] [000324] The cleaning unit is not particularly limited and can be appropriately selected depending on the intended purpose, as long as it can remove the remaining toner in the photoconductor. Examples of the same include a magnetic brush cleaning means, an electrostatic brush cleaning means, a magnetic roller cleaning means, a paddle cleaning means, a brush cleaning means and a mesh cleaning means.
    [000325] [000325] The cleaning step is not particularly limited and can be appropriately selected depending on the intended purpose, as long as it is a step of removing the remaining toner in the photoconductor. It can be performed by the cleaning unit. Unloading unit and unloading step
    [000326] [000326] The unloading unit is not particularly limited and can be appropriately selected depending on the intended purpose, as long as it is a unit configured to apply a unloading polarization to the photoconductor to thereby eliminate the load. The example of the same includes a charge-elimination lamp.
    [000327] [000327] The charge elimination step is not particularly limited and can be appropriately selected depending on the intended purpose, as long as it is a step of applying a charge elimination bias to the photoconductor to thereby eliminate the charge. It can be performed by the load shedding unit. Recycling unit and recycling step
    [000328] [000328] The recycling unit is not particularly limited and can be appropriately selected depending on the intended purpose, as long as it is a unit configured to recycle the toner that was removed in the cleaning step for the development device. Examples of it include a known transport unit.
    [000329] [000329] The recycling step is not particularly limited and can be appropriately selected depending on the intended purpose, as long as it is a recycling step for the toner that was removed in the cleaning step for the developing device. The recycling step can be carried out by the recycling unit. Control unit and inspection step
    [000330] [000330] The control unit is not particularly limited and can be appropriately selected depending on the intended purpose, as long as it can control the operation of each of the units above. Examples of it include devices such as sequencer and computer.
    [000331] [000331] The control step is not particularly limited and can be appropriately selected depending on the intended purpose, as long as it is a step of controlling the operation of each of the units above. The control step can be performed by the control unit.
    [000332] [000332] An embodiment for carrying out an imaging method by an imaging apparatus of the present invention will now be explained with reference to figure 1. An imaging apparatus 100A illustrated in figure 1 includes a photoconductor drum 10 serving such as the element containing electrostatic imaging (hereinafter referred to as a “photoconductor 10”), a charge roller 20 serving as the charging unit, an exposure device 30 serving as the exposure unit, a developing device 40 serving as the developing unit, an intermediate transfer element 50, a cleaning device 60 serving as the cleaning unit which includes a cleaning paddle and a charge removal lamp 70 serving as the charge removal unit.
    [000333] [000333] The intermediate transfer element 50 is an endless belt and designed to be movable in an direction indicated by an arrow by three rollers 51 which are arranged inside the belt and around which the belt is stretched. A portion of the three rollers 51 also functions as a transfer bias roll which can apply a predetermined transfer polarity (primary transfer bias) to the intermediate transfer element 50. Also, a cleaning device 90 including a cleaning pad is arranged near the intermediate transfer element 50. In addition, a transfer roller 80 serving as the transfer unit that can apply a transfer bias to transfer (a secondary transfer) a developed image (toner image) onto the transfer paper 95 serving as a recording medium it is disposed close to the intermediate transfer element 50 facing the intermediate transfer element 50. In addition, around the intermediate transfer element 50, a corona loading device 58 for applying a charge to the toner image transferred in the intermediate transfer element 50 is arranged between a po contact fraction of the electrostatic imaging element 10 with the intermediate transfer element 50 and a contact portion of the intermediate transfer element 50 with the transfer paper 95 in a rotational direction of the intermediate transfer element 50.
    [000334] [000334] Developing device 40 includes developing belt 41 which serves as the developer-containing element; and a 45K black developer unit, a 45Y yellow developer unit, a 45M magenta developer unit and a 45C cyan developer unit that are arranged around the 41 development belt. Here, the 45K black developer unit includes a container 42K developer roll, 43K developer supply roll and 44K developer roll. The 45Y yellow developer unit includes a 42Y developer container, a 43Y developer supply roller and a 44Y developer roller. The 45M magenta developer unit includes a 42M developer container, a 43M developer supply roller and a 44M developer roller. The cyan 45C developer unit includes a 42C developer container, a 43C developer supply roller and a 44C developer roller. Also, the developing belt 41 is an endless belt that is rotatively stretched around a plurality of belt rollers and is partially in contact with the electrostatic imaging element 10.
    [000335] [000335] In the image forming apparatus 100 shown in figure 1, the loading roller 20 uniformly loads a surface of the photoconductive drum 10, and then the display device exposes the photoconductive drum 10 in the image direction to form an electrostatic latent image. . Next, the electrostatic latent image formed in the photoconductive drum 10 is developed with a toner supplied from the developing device 45 to form a toner image. In addition, the toner image is transferred (transferred primarily) onto the intermediate transfer element 50 by voltage applied from the roll 51 and then transferred (transferred secondary) to onto transfer paper 95. As a result, a transferred image is formed on transfer paper 95. Notably, a residual toner that remains in the photoconductive drum 10 is removed by the cleaning device 60, and the photoconductive drum 10 is once discharged by the charge eliminator lamp
    [000336] [000336] Figure 2 is a schematic structural view of another example of an image forming apparatus of the present invention. An imaging apparatus 100B has the same configuration as the imaging apparatus 100A illustrated in Figure 1, except that the developing belt 41 is not included and that, around the photoconductive drum 10, the black developing unit 45K, the 45Y yellow developer unit, the 45M magenta developer unit and the 45C cyan developer unit are arranged facing the element that contains electrostatic imaging.
    [000337] [000337] Figure 3 is a schematic structural view of yet another example of an image forming apparatus of the present invention. The color imaging apparatus shown in Figure 2 includes a main copying device body 150, a paper feed table 200, a scanner 300 and an automatic document feeder (ADF) 400.
    [000338] [000338] An intermediate transfer element 50 which is an endless belt is disposed in a central part of the copying device main body 150. The intermediate transfer element 50 is stretched around the support rollers 14, 15 and 16 and can rotate in a clockwise direction in figure 3. Near the support roller 15, a cleaning device for the intermediate transfer element 17 is arranged to remove a residual toner that remains in the intermediate transfer element 50. In the intermediate transfer element 50 stretched around the support rollers 14 and 15, a tandem type developing device 120 is arranged in which four image forming units 18 of yellow, cyan, magenta and black are arranged in parallel so that they are facing each other along a transport direction. The display device 21 serving as the display element is arranged in proximity to the tandem type developing device 120. In addition, a secondary transfer device 22 is arranged on one side of the intermediate transfer element 50 opposite the side on which the tandem type developing device 120 is arranged. In the secondary transfer device 22, the secondary transfer belt 24 which is an endless belt is stretched around a pair of rollers 23, and the transfer paper carried on the secondary transfer belt 24 and the intermediate transfer element 50 can get in touch with each other. Here, a clamping device 25 serving as the clamping unit is arranged in proximity to the secondary transfer device 22. Clamping device 25 includes a clamping strap 26 which is an endless belt and a pressure roller 27 which is arranged to be pressed against the fastening strap.
    [000339] [000339] Here, in the tandem-type image forming apparatus, a sheet reversing device 28 is arranged close to the secondary transfer device 22 and the fixing device 25 to invert the recording paper in case of forming images on both sides transfer paper.
    [000340] [000340] In the following, a method for forming a full color image (color copy) using the tandem type developing device 120 will be explained. First, a color document is placed on a document table 130 of the automatic document feeder (ADF) 400. Alternatively, the automatic document feeder 400 is opened, the color document is placed on a contact glass 32 of the scanner 300 , and the automatic document feeder 400 is closed.
    [000341] [000341] When a start button (not shown) is pressed, scanner 300 activates after the color document is transferred and moved to contact glass 32 in case the color document has been placed in the automatic document feeder 400, or directly if the color document was placed on contact glass 32,
    [000342] [000342] The black, yellow, magenta and cyan image information is transmitted to the imaging units 18 (black imaging unit, yellow imaging unit, magenta imaging unit and training unit cyan image processing) on the 120 tandem developer and black, yellow, magenta and cyan toner images are formed on the imaging units. As shown in Figure 4, the imaging units 18 (black imaging unit, yellow imaging unit, magenta imaging unit, and cyan imaging unit) in the tangem developing device 120 include: elements containing 10 electrostatic imaging (element containing 10K black electrostatic imaging, element containing 10Y yellow electrostatic imaging, element containing 10M magenta electrostatic imaging and element containing cyan 10C electrostatic imaging); a charging device 160 configured to uniformly charge elements containing electrostatic imaging 10; an exposure device configured to expose in the direction of image to a light (L illustrated in figure 4) the elements that contain electrostatic imaging based on color image information to form an electrostatic imaging corresponding to color images in the elements that contain electrostatic imaging; a developing device 61 configured to develop electrostatic latent images with color toners (black toner, yellow toner, magenta toner and cyan toner) to form a toner image of the color toners; a transfer charger 62 configured to transfer the toner image onto the intermediate transfer element 50; a cleaning device 63; and a load shedding unit 64. Each imaging unit 18 can form monochrome images (black image, yellow image, magenta image and cyan image) based on the color image formations.
    [000343] [000343] Meanwhile, on the paper feed table 200, one of the paper feed rolls 142 is selectively rotated to feed a sheet (recording paper) from one of the paper feed cassettes 144 equipped in multiple stages in a group of paper 143. The sheet is separated one by one by a separation roller 145 and sent to a paper feed path 146. The sheet (embossing paper) is transferred by a conveyor roll 147 and is guided to a paper path paper feed 148 on the copier main body 150, and to collide with a registration roller 49. Alternatively, a paper feed roller 142 is rotated to feed a sheet of recording paper into a bypass tray 54 The sheet (embossing paper) is separated one by one by a separation roller 52 and is guided to a manual paper feed path 53, and to collide with the registration roller
    [000344] [000344] The sheet (recording paper) on which the composite toner image has been transferred is carried by the secondary transfer device 22, and then transported to the fixture 25. On the fixture 25, the composite color image (color transferred image) is fixed on the sheet (recording paper) by the action of heat and pressure. Next, the sheet (embossing paper) is switched by a switch claw 55, and unloaded by an unloading roller 56 and stacked in a paper unloading tray 57. Alternatively, the sheet is switched by the switch claw 55, and is reversed by the reversing device 28 to thereby be guided to a transfer position again. After an image is similarly formed on the rear surface, the embossing paper is discharged by the discharge roller 56 stacked in the paper discharge tray
    [000345] [000345] A process cartridge of the present invention is shaped so that it can be mounted on various imaging devices in a fixable and detachable mode, including at least one element that contains electrostatic imaging configured to contain an electrostatic imaging on the same; and a developing unit configured to reveal the electrostatic imaging loaded on the element containing the electrostatic imaging with the developer of the present invention to form a toner image. Note that the process cartridge of the present invention may include other units, if necessary.
    [000346] [000346] The developer unit includes at least one developer-accommodating container that accommodates the developer of the present invention, and a developer-containing element configured to contain and transfer the developer accommodated in the developer-accommodating container. Note that the developer unit may also include, for example, an adjustment element configured to regulate the thickness of the loaded developer.
    [000347] [000347] Figure 5 illustrates an example of the process cartridge of the present invention. A process cartridge 110 includes a photoconductive drum 10, a corona loading device 52, a developing device 40, a transfer roller 80 and a cleaning device 90. Examples
    [000348] [000348] The present invention will be described by way of Examples below. The present invention is not to be construed as being limited to the examples. Unless otherwise specified, “part (s)” means “part (s) by mass”. Unless otherwise specified, "%" means "% by mass".
    [000349] [000349] Measurements in the Examples below were obtained by the methods described in this specification.
    [000350] [000350] A reaction vessel in which a stir bar and a thermometer had been placed was loaded with 170 parts of isophorone diamine and 75 parts of methyl ethyl ketone, and the resulting mixture was left to react for 5 hours at 50ºC, to how to obtain satinin compound 1. The satinin compound 1 was found to have an amine value of 418. Production Example A-1 Synthesis of prepolymer A-1
    [000351] [000351] A reaction vessel equipped with a condenser, stirrer and nitrogen introducing tube was charged with 3-methyl-1,5-pentanediol, isophthalic acid and adipic acid so that the molar ratio of hydroxyl groups to carboxyl groups, represented by OH / COOH was 1.1, the diol component was composed of 100 mol% of 3-methyl-1,5-pentanediol, the dicarboxylic acid component was composed of 45 mol% of isophthalic acid, and 55 mol% in relation to the total amount of trimethylol propane was 1.5 mol% in relation to the total amount of monomers, together with titanium tetraisopropoxide (1,000 ppm in relation to the resin component). Subsequently, the mixture was heated to 200ºC for approximately 4 hours, and heated to 230ºC for 2 hours, followed by carrying out a reaction until the effluent water stopped. Subsequently, the result was allowed to react additionally for 5 hours under reduced pressure from 10 mmHg to 15 mmHg, to thereby supply intermediate polyester A-1.
    [000352] [000352] Next, a reaction vessel equipped with a condenser, a stirrer and a nitrogen introducing tube was loaded with the obtained intermediate polyester A-1, and isophorone diisocyanate (IPDI) in a molar ratio (isocyanate groups) of IPDI / intermediate polyester hydroxyl groups) of 2.0, and after diluted with ethyl acetate to provide a 50% ethyl acetate solution, the mixture was allowed to react for 5 hours at 100ºC, to thereby obtain pre -polymer A-1. Synthesis of non-crystalline polyester resin A-1
    [000353] [000353] The prepolymer obtained A-1 was stirred in a reaction vessel equipped with a heating device, a stirrer, and a nitrogen introducing tube, and into the reaction vessel, the satin compound 1 was added so that the amine amount of the satinin 1 compound was equimolar to the amount of the prepolymer A1 isocyanate. After stirring for 10 hours at 45ºC, an elongated prepolymer product was removed. The elongated prepolymer product obtained was dried at 50 ° C under reduced pressure until the amount of ethyl acetate residues in the elongated prepolymer product became 100 ppm or less, to thereby obtain non-crystalline polyester resin A- 1. It was found that this resin has a weight average molecular weight (Mw) of 164,000 and a Tg of -40ºC.
    [000354] [000354] A reaction vessel equipped with a condenser, stirrer and nitrogen introducing tube was loaded with 3-methyl-1,5-pentanediol and adipic acid so that the molar ratio of hydroxyl groups to carboxyl groups , represented by OH / COOH was 1.1, the diol component was composed of 100 mol% of 3-methyl-1,5-pentanediol, the dicarboxylic acid component was composed of 80 mol% of adipic acid and 20 mol% of adipic acid, and an amount of trimethylol propane was 1.5 mol% relative to the total amount of monomers, along with titanium tetraisopropoxide (1,000 ppm relative to the resin component). Subsequently, the mixture was heated to 200ºC for approximately 4 hours, and heated to 230ºC for 2 hours, followed by carrying out a reaction until the effluent water stopped. Subsequently, the result was allowed to react additionally for 5 hours under reduced pressure from 10 mmHg to 15 mmHg, to thereby supply intermediate polyester A-2.
    [000355] [000355] Next, a reaction vessel equipped with a condenser, a stirrer and a nitrogen introducing tube was loaded with the obtained intermediate polyester A-2, and isophorone diisocyanate (IPDI) in a molar ratio (isocyanate groups) of IPDI / intermediate polyester hydroxyl groups) of 2.0, and after diluted with ethyl acetate to provide a 50% ethyl acetate solution,
    [000356] [000356] The prepolymer obtained A-2 was stirred in a reaction vessel equipped with a heating device, a stirrer, and a nitrogen introducing tube, and into the reaction vessel, the satin compound 1 was added in drops so that the amine amount of the satinin 1 compound was equimolar to the amount of the prepolymer A-2 isocyanate. After stirring for 10 hours at 45ºC, an elongated prepolymer product was removed. The elongated prepolymer product obtained was dried at 50 ° C under reduced pressure until the amount of ethyl acetate residues in the elongated prepolymer product became 100 ppm or less, to thereby obtain non-crystalline polyester resin A- 2. It was found that this resin has a weight average molecular weight (Mw) of 175,000 and a Tg of -55ºC. Production example A-3 Synthesis of non-crystalline polyester resin A-3
    [000357] [000357] A reaction vessel equipped with a condenser, a stirrer and a nitrogen introducing tube was charged with 2 mol of bisphenol A ethylene oxide adduct, 2 mol of bisphenol A propylene epoxide adduct, terephthalic acid and anhydride trimellitic so that the molar ratio of hydroxyl groups to carboxyl groups, represented by OH / COOH was 1.3, the diol component was composed of 90 mol% of ethylene oxide adduct 2 mol of bisphenol A and 10% propylene oxide adduct 2 mol of bisphenol A and dicarboxylic acid was composed of 90 mol% of terephthalic acid, and 10 mol% of trimellitic anhydride, together with titanium tetraisopropoxide (1,000 ppm in relation to the resin component). Subsequently, the mixture was heated to 200ºC for approximately 4 hours, and heated to 230ºC for 2 hours, followed by carrying out a reaction until the effluent water stopped. Subsequently, the result was allowed to react additionally for 5 hours under reduced pressure from 10 mmHg to 15 mmHg, to thereby supply intermediate polyester A-3.
    [000358] [000358] Next, a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube was loaded with the obtained intermediate polyester A-3, and isophorone diisocyanate (IPDI) in a molar ratio (isocyanate groups) of IPDI / intermediate polyester hydroxyl groups) of 2.0, and after diluted with ethyl acetate to provide a 50% ethyl acetate solution, the mixture was allowed to react for 5 hours at 100ºC, to thereby obtain prepolymer A-3. Synthesis of non-crystalline polyester resin A-3
    [000359] [000359] The prepolymer obtained A-3 was stirred in a reaction vessel equipped with a heating device, a stirrer, and a nitrogen introducing tube, and into the reaction vessel, the satinin compound 1 was added so that the amine amount of the satinin compound 1 was equimolar to the amount of the prepolymer A3 isocyanate. After stirring for 10 hours at 45ºC, an elongated prepolymer product was removed. The elongated prepolymer product obtained was dried at 50 ° C under reduced pressure until the amount of ethyl acetate residues in the elongated prepolymer product became 100 ppm or less, to thereby obtain non-crystalline polyester resin A- 3. It was found that this resin has an average molecular weight (Mw) of 130,000 and a Tg of 54ºC. Production example A-4 Synthesis of non-crystalline polyester resin A-4 Synthesis of prepolymer A-4
    [000360] [000360] A reaction vessel equipped with a condenser, stirrer and nitrogen introducing tube was charged with 1,2-propylene glycol, terephthalic acid, adipic acid and trimellitic anhydride so that the molar ratio of hydroxyl groups to carboxyl groups, represented by OH / COOH was 1.3, the diol component was composed of 100 mol% of 1,2-propylene glycol, the dicarboxylic acid component was composed of 80 mol% of terephthalic acid, and 20% mol of adipic acid, and an amount of trimellitic anhydride was 2.5 mol% of the total amount of monomers, along with titanium tetraisopropoxide (1,000 ppm in relation to the resin component). Subsequently, the mixture was heated to 200ºC for approximately 4 hours, and heated to 230ºC for 2 hours, followed by carrying out a reaction until the effluent water stopped. Subsequently, the result was allowed to react additionally for 5 hours under reduced pressure from 10 mmHg to 15 mmHg, to thereby supply intermediate polyester A-4.
    [000361] [000361] Next, a reaction vessel equipped with a condenser, a stirrer and a nitrogen introducing tube was loaded with the obtained intermediate polyester A-4, and isophorone diisocyanate (IPDI) in a molar ratio (isocyanate groups) of IPDI / intermediate polyester hydroxyl groups) of 2.0, and after diluted with ethyl acetate to provide a 50% ethyl acetate solution, the mixture was allowed to react for 5 hours at 100ºC, to thereby obtain pre -polymer A-4. Synthesis of non-crystalline polyester resin A-4
    [000362] [000362] The prepolymer obtained A-4 was stirred in a reaction vessel equipped with a heating device, a stirrer, and a nitrogen introducing tube, and into the reaction vessel, the satinin compound 1 was added so that the amine amount of the satinin compound 1 was equimolar to the amount of the pre-polymer A-4 isocyanate. After stirring for 10 hours at 45ºC, an elongated prepolymer product was removed. The elongated prepolymer product obtained was dried at 50 ° C under reduced pressure until the amount of ethyl acetate residues in the elongated prepolymer product became 100 ppm or less, to thereby obtain non-crystalline polyester resin A- 4. It was found that this resin has an average molecular weight (Mw) of 140,000 and a Tg of 56ºC. Production example A-5 Synthesis of non-crystalline polyester resin A-5 Synthesis of prepolymer A-5
    [000363] [000363] A reaction vessel equipped with a condenser, stirrer and nitrogen introducing tube was charged with 3-methyl-1,5-pentanediol, isophthalic acid, adipic acid and trimellitic anhydride so that the molar ratio of groups of hydroxyl for carboxyl groups, represented by OH / COOH was 1.5, the diol component was composed of 100 mol% of 3-methyl-1,5-pentanediol, the dicarboxylic acid component was composed of 40 mol% of isophthalic acid, and 60 mol% of adipic acid, and an amount of trimellitic anhydride was 1 mol% in relation to the total amount of monomers, together with titanium tetraisopropoxide (1,000 ppm in relation to the resin component). Subsequently, the mixture was heated to 200ºC for approximately 4 hours, and heated to 230ºC for 2 hours, followed by carrying out a reaction until the effluent water stopped. Subsequently, the result was allowed to react additionally for 5 hours under reduced pressure from 10 mmHg to 15 mmHg, to thereby supply intermediate polyester A-5.
    [000364] [000364] Next, a reaction vessel equipped with a condenser, a stirrer and a nitrogen introducing tube was loaded with the obtained intermediate polyester A-5, and isophorone diisocyanate (IPDI) in a molar ratio (isocyanate groups) of IPDI / intermediate polyester hydroxyl groups) of 2.0, and after diluted with ethyl acetate to provide a 50% ethyl acetate solution, the mixture was allowed to react for 5 hours at 100ºC, to thereby obtain pre -polymer A-5. Synthesis of non-crystalline polyester resin A-5
    [000365] [000365] The prepolymer obtained A-5 was stirred in a reaction vessel equipped with a heating device, a stirrer, and a nitrogen introducing tube, and into the reaction vessel, the satinin compound 1 was added so that the amount of the amine of the satinin compound 1 was equimolar to the amount of the isocyanate of the prepolymer A-5. After stirring for 10 hours at 45ºC, an elongated prepolymer product was removed. The elongated prepolymer product obtained was dried at 50 ° C under reduced pressure until the amount of ethyl acetate residues in the elongated prepolymer product became 100 ppm or less, to thereby obtain non-crystalline polyester resin A- 5. It was found that this resin has a weight average molecular weight (Mw) of 150,000 and a Tg of -35ºC. Production example A-6 Synthesis of non-crystalline polyester resin A-6 Synthesis of prepolymer A-6
    [000366] [000366] A reaction vessel equipped with a condenser, a stirrer and a nitrogen introducing tube was charged with 1,6-hexanediol, isophthalic acid, adipic acid and trimellitic anhydride so that the molar ratio of hydroxyl groups to groups of carboxyl, represented by OH / COOH was 1.5, the diol component was composed of 100 mol% of 1,6-hexanediol, the dicarboxylic acid component was composed of 80 mol% of isophthalic acid, and 20 mol% of adipic acid, and an amount of trimellitic anhydride was 1 mol% of the total amount of monomers, along with titanium tetraisopropoxide
    [000367] [000367] Next, a reaction vessel equipped with a condenser, a stirrer and a nitrogen introducing tube was loaded with the obtained intermediate polyester A-6, and isophorone diisocyanate (IPDI) in a molar ratio (isocyanate groups) of IPDI / intermediate polyester hydroxyl groups) of 2.0, and after diluted with ethyl acetate to provide a 50% ethyl acetate solution, the mixture was allowed to react for 5 hours at 100ºC, to thereby obtain pre -polymer A-6. Synthesis of non-crystalline polyester resin A-6
    [000368] [000368] The prepolymer obtained A-6 was stirred in a reaction vessel equipped with a heating device, a stirrer, and a nitrogen introducing tube, and into the reaction vessel, the satinin compound 1 was added so that the amine amount of the satinin 1 compound was equimolar to the amount of the pre-polymer A-6 isocyanate. After stirring for 10 hours at 45ºC, an elongated prepolymer product was removed. The elongated prepolymer product obtained was dried at 50 ° C under reduced pressure until the amount of ethyl acetate residues in the elongated prepolymer product became 100 ppm or less, to thereby obtain non-crystalline polyester resin A- 6. It was found that this resin has a weight average molecular weight (Mw) of 120,000 and a Tg of -5ºC. Production example B-1 Synthesis of non-crystalline polyester resin B-1
    [000369] [000369] A four-necked flask equipped with a nitrogen introducing tube, a drain tube, a stirrer and a thermocouple was loaded with ethylene oxide adduct 2 mol of bisphenol A, propylene oxide adduct 2 mol of bisphenol A, terephthalic acid, and adipic acid, so that the molar ratio of the propylene oxide adduct 2 mol of bisphenol A to the ethylene oxide adduct 2 mol of bisphenol A (propylene oxide adduct 2 mol of bisphenol A / adduct of ethylene oxide bisphenol A 2 mol) was 60/40, the molar ratio of terephthalic acid to adipic acid (terephthalic acid / adipic acid) was 97/3, and the molar ratio of hydroxyl groups to carboxyl groups, represented by OH / COOH, it was 1.3. The resulting mixture was allowed to react with titanium tetraisopropoxide (500 ppm in relation to the resin component) for 8 hours at 230ºC under atmospheric pressure, and reacted for 4 hours under reduced pressure from 10 mmHg to 15 mmHg. Subsequently, trimellitic anhydride was added to the reaction vessel in an amount of 1 mol% in relation to the total resin component, and the result was allowed to react for 3 hours at 180ºC, under atmospheric pressure, to thereby obtain non-crystalline polyester resin. B-1. It was found that this resin has a weight average molecular weight (Mw) of 5,300 and a Tg of -67ºC.
    [000370] [000370] A four-necked flask equipped with a nitrogen introducing tube, a drain tube, a stirrer and a thermocouple was loaded with ethylene oxide adduct 2 mol of bisphenol A, 1,3-propylene glycol, terephthalic acid , and adipic acid, so that the molar ratio of the propylene oxide adduct 2 mol of bisphenol A to 1,3 propylene glycol (propylene oxide adduct 2 mol of bisphenol A / 1,3 propylene glycol) was 90/10, the molar ratio of terephthalic acid to adipic acid (terephthalic acid / adipic acid) was 80/20, and the molar ratio of hydroxyl groups to carboxyl groups, represented by OH / COOH, was 1.4. The resulting mixture was allowed to react with titanium tetraisopropoxide (500 ppm in relation to the resin component) for 8 hours at 230ºC under atmospheric pressure, and was additionally reacted for 4 hours under reduced pressure from 10 mmHg to 15 mmHg. Subsequently, trimellitic anhydride was added to the reaction vessel in an amount of 1 mol% in relation to the total resin component, and the result was allowed to react for 3 hours at 180ºC, under atmospheric pressure, to thereby obtain non-crystalline polyester resin. B-2. It was found that this resin has an average molecular weight (Mw) of 5,600 and a Tg of -61ºC. Production example B-3 Synthesis of non-crystalline polyester resin B-3
    [000371] [000371] A four-necked flask equipped with a nitrogen introducing tube, a drain tube, a stirrer and a thermocouple was loaded with ethylene oxide adduct 2 mol of bisphenol A, propylene oxide adduct 2 mol of bisphenol A, isophthalic acid, and adipic acid, so that the molar ratio of the propylene oxide adduct 2 mol of bisphenol A to the ethylene oxide adduct 2 mol of bisphenol A (propylene oxide adduct 2 mol of bisphenol A / adduct of ethylene oxide bisphenol A 2 mol) was 30/70, the molar ratio of isophthalic acid to adipic acid (isophthalic acid / adipic acid) was 80/20, and the molar ratio of hydroxyl groups to carboxyl groups, represented by OH / COOH, it was 1.2. The resulting mixture was allowed to react with titanium tetraisopropoxide (500 ppm in relation to the resin component) for 8 hours at 230ºC under atmospheric pressure, and reacted for 4 hours under reduced pressure from 10 mmHg to 15 mmHg. Subsequently, trimellitic anhydride was added to the reaction vessel in an amount of 1 mol% in relation to the total resin component, and the result was allowed to react for 3 hours at 180ºC, under atmospheric pressure, to thereby obtain non-crystalline polyester resin. B-3. It was found that this resin has an average molecular weight (Mw) of 5,500 and a Tg of 50ºC. Production example B-4 Synthesis of non-crystalline polyester resin B-4
    [000372] [000372] A four-necked flask equipped with a nitrogen introduction tube, a drain tube, a stirrer and a thermocouple was loaded with ethylene oxide adduct 2 mol of bisphenol A, propylene oxide adduct 3 mol of bisphenol A, isophthalic acid, and adipic acid, so that the molar ratio of the ethylene oxide adduct 2 mol of bisphenol A to the propylene oxide adduct 3 mol of bisphenol A (ethylene oxide adduct 2 mol of bisphenol A / propylene oxide adduct bisphenol A 3 mol) was 85/15, the molar ratio of isophthalic acid to adipic acid (isophthalic acid / adipic acid) was 80/20, and the molar ratio of hydroxyl groups to carboxyl groups, represented by OH / COOH, it was 1.3. The resulting mixture was allowed to react with titanium tetraisopropoxide (500 ppm in relation to the resin component) for 8 hours at 230ºC under atmospheric pressure, and was additionally reacted for 4 hours under reduced pressure from 10 mmHg to 15 mmHg. Subsequently, trimellitic anhydride was added to the reaction vessel in an amount of 1 mol% in relation to the total resin component, and the result was allowed to react for 3 hours at 180ºC, under atmospheric pressure, to thereby obtain non-crystalline polyester resin. B-4. It was found that this resin has an average molecular weight (Mw) of 5,000 and a Tg of 48ºC. Production example B-5 Synthesis of non-crystalline polyester resin B-6
    [000373] [000373] A four-necked flask equipped with a nitrogen introducing tube, a drain tube, a stirrer and a thermocouple was loaded with ethylene oxide adduct 2 mol of bisphenol A, propylene oxide adduct 3 mol of bisphenol A, terephthalic acid, and adipic acid, so that the molar ratio of the ethylene oxide adduct 2 mol of bisphenol A to the propylene oxide adduct 3 mol of bisphenol A (ethylene oxide adduct 2 mol of bisphenol A / propylene oxide adduct bisphenol A 3 mol) was 85/15, the molar ratio of terephthalic acid to adipic acid (terephthalic acid / adipic acid) was 80/20, and the molar ratio of hydroxyl groups to carboxyl groups, represented by OH / COOH, it was 1.3. The resulting mixture was allowed to react with titanium tetraisopropoxide (500 ppm in relation to the resin component) for 8 hours at 230ºC under atmospheric pressure, and was additionally reacted for 4 hours under reduced pressure from 10 mmHg to 15 mmHg. Subsequently, trimellitic anhydride was added to the reaction vessel in an amount of 1 mol% in relation to the total resin component, and the result was allowed to react for 3 hours at 180ºC, under atmospheric pressure, to thereby obtain non-crystalline polyester resin. B-5. It was found that this resin has an average molecular weight (Mw) of 5,000 and a Tg of 51ºC. Production example C-1 Synthesis of crystalline polyester resin C-1
    [000374] [000374] A 5 L four-necked flask equipped with a nitrogen introducing tube, a drain tube, an agitator and a thermocouple was loaded with sebacic acid and 1,6-hexanediol, so that the molar ratio of groups of hydroxyl for carboxyl groups represented by OH / COOH, was 0.9. The resulting mixture was allowed to react with titanium tetraisopropoxide (500 ppm in relation to the resin component) for 10 hours at 180ºC, heated to 200ºC and reacted for 3 hours, followed by an additional reaction for 2 hours under pressure of 8.3 kPa, to thereby obtain crystalline C-1 polyester resin. It was found that this resin has an average molecular weight (Mw) of 25,000 and a Tg of 67ºC. Example 1 Preparation of master batch (MB)
    [000375] [000375] Water (1,200 parts), 500 parts carbon black (Printex 35, product of Evonik Degussa Japan Co., Ltd.) [quantity of oil absorption DBP = 42 mL / 100 mg, pH = 9.5] , and 500 parts of the non-crystalline polyester resin B-1 were added and mixed together using NESCHEL MIXER (manufactured by NIPPON COLE & ENGINEERING CO., LTD.) and the resulting mixture was kneaded using a two-roller mill for 30 minutes at 150ºC. The resulting kneaded product was rolled and cooled, followed by spraying with a sprayer, to thereby obtain master batch 1. Preparation of wax dispersion liquid
    [000376] [000376] A container to which a stir bar and a thermometer had been placed was loaded with 50 parts of paraffin wax (HNP-9, manufactured by Nippon Seiro Co., Ltd., hydrocarbon wax, melting point: 75ºC, value: 8.8) as the release agent 1, and 450 parts of ethyl acetate, followed by heating to 80ºC with mixture. The temperature was maintained at 80ºC for 5 hours, followed by cooling to 30ºC for 1 hour. The resulting mixture was dispersed using a bead mill (ULTRA VISCOMILL, product of AIMEX Co., Ltd.) under the conditions: a liquid feed rate of 1 kg / h, a circumferential disk speed of 6 m / s , 0.5 mm zirconia beads packed at 80% by volume, and 3 passes, to thereby obtain wax dispersion liquid 1.
    [000377] [000377] A container equipped with a stir bar and a thermometer was loaded with 50 parts of C-1 crystalline polyester resin and 450 parts of ethyl acetate, and the resulting mixture was heated to 80ºC with stirring. The temperature was maintained at 80ºC for 5 hours, followed by cooling to 30ºC for 1 hour. The resulting mixture was dispersed by means of a bead mill (ULTRA VISCOMILL, manufactured by AIMEX Co., Ltd.) under the following conditions: a liquid feed rate of 1 kg / h, a circumferential disk speed of 6 m / s, 0.5 mm zirconia beads packed in diameter packed at 80% by volume, and 3 passes, to thereby obtain crystalline polyester resin dispersion liquid 1. Preparation of oil phase
    [000378] [000378] One container was loaded with 50 parts of the wax dispersion liquid 1, 150 parts of the non-crystalline polyester resin A-1, 50 parts of the crystalline polyester resin dispersion liquid 1, 750 parts of the non-crystalline polyester resin crystalline B-1, 50 parts of the master batch 1 (pigment), and 2 parts of the satinin 1 compound. The resulting mixture was mixed using a TK Homomixer (manufactured by PRIMIX Corporation) at 5,000 rpm for 60 minutes, for that how to get oil phase 1.
    [000379] [000379] Note that the quantities above are quantities of the solid contents of the materials. Synthesis of organic particle emulsion (particle dispersion liquid)
    [000380] [000380] A reaction vessel equipped with a stir bar and a thermometer was loaded with 683 parts of water, 11 parts of a sulfuric acid ester salt of ethylene oxide adduct of methacrylic acid (ELEMINOL RS-30 , manufactured by Sanyo Chemical Industries, Ltd.), 138 parts of styrene, 138 parts of methacrylic acid and 1 part of ammonium persulfate, and the resulting mixture was stirred for 15 minutes at 400 rpm, to thereby obtain a white emulsion. The emulsion obtained was heated to a system temperature of 75ºC, and was then allowed to react for 5 hours. To the result, 30 parts of a 1% aqueous solution of ammonium persulfate were added, followed by aging for 5 hours at 75ºC, to thereby obtain an aqueous dispersion liquid of a vinyl resin (a copolymer of styrene / methacrylic acid / sodium salt of sulfuric acid ester, ethylene oxide adduct, methacrylic acid), i.e., particle dispersion liquid 1.
    [000381] [000381] The dispersion liquid of particle 1 was measured by means of LA-920 (product by HORIBA, Ltd.), and as a result, the average particle diameter of its volume was found to be 0.14 µm. Part of the particle dispersion liquid 1 was dried, and a resin component was isolated. Preparation of aqueous phase
    [000382] [000382] Water (990 parts), 83 parts of particle dispersion liquid 1, 37 parts of a 48.5% aqueous solution of dodecyl diphenyl ether disulfonate (ELEMINOL MON-7, manufactured by Sanyo Chemical Industries
    [000383] [000383] To a container loaded with oil phase 1, 1,200 parts of aqueous phase 1 were added, and the resulting mixture was mixed using a TK Homomixer at 13,000 rpm for 20 minutes, to thereby obtain emulsified paste 1.
    [000384] [000384] A container equipped with an agitator and a thermometer was loaded with the emulsified paste 1, followed by removal of the solvent in it at 30ºC for 8 hours. Subsequently, the result was matured at 45ºC for 4 hours, in order to obtain dispersion paste 1. Washing and drying
    [000385] [000385] After submitting 100 parts of the dispersion paste to filtration under reduced pressure, the result was subjected twice to a series of treatments (1) to (4) described below, to thereby produce the filtration mass 1: ( 1) Ion-exchange water (100 parts) was added to the filtration mass, followed by mixing with TK Homomixer (at 12,000 rpm for 10 minutes) and then filtration; (2) 10% aqueous sodium hydroxide solution (100 parts) was added to the filtration mass obtained in (1), followed by mixing with TK Homomixer (at 12,000 rpm for 30 minutes) and then filtration under reduced pressure; (3) 10% hydrochloric acid by mass (100 parts) was added to the filtration mass obtained in (2), followed by mixing with TK Homomixer (at 12,000 rpm for 10 minutes) and then filtration; and (4) Ion-exchanged water (300 parts) was added to the filtration mass obtained in (3), followed by mixing with TK Homomixer (at 12,000 rpm for 10 minutes) and then filtration.
    [000386] [000386] The filtration mass 1 was dried with an air circulation dryer at 45ºC for 48 hours, and then it was induced to pass through a sieve with a mesh size of 75 m, to thereby prepare the toner 1 Example 2
    [000387] [000387] Toner 2 was obtained in the same way as in example 1 except that the amount of non-crystalline polyester resin A-1 was changed to 120 parts and the amount of non-crystalline polyester resin B-1 was changed to 78 parts in Preparation of oil phase. Example 3
    [000388] [000388] Toner 3 was obtained in the same way as in example 1 except that the amount of non-crystalline polyester resin A-1 was changed to 180 parts and the amount of non-crystalline polyester resin B-1 was changed to 720 parts in Preparation of oil phase. Example 4
    [000389] [000389] Toner 4 was obtained in the same way as in example 1 except that the non-crystalline polyester resin A-1 was changed to the non-crystalline polyester resin A-2 and the non-crystalline polyester resin B-1 was changed for non-crystalline polyester resin B-3. Example 5
    [000390] [000390] Toner 5 was obtained in the same way as in example 1 except that the amount of non-crystalline polyester resin A-1 was changed to 120 parts, the amount of non-crystalline polyester resin B-1 was changed to 820 parts and the amount of the C-1 crystalline polyester resin was changed to 10 parts in the Oil Phase Preparation. Example 6
    [000391] [000391] Toner 6 was obtained in the same way as in example 1 except that the amount of non-crystalline polyester resin A-1 was changed to 180 parts and the amount of crystalline polyester resin C-1 was changed to 20 parts in Preparation of oil phase. Example 7
    [000392] [000392] Toner 7 was obtained in the same way as in example 1 except that the non-crystalline polyester resin A-1 and the quantity thereof were changed respectively for the non-crystalline polyester resin A-2 and 180 parts, and non-crystalline polyester resin B-1 and the amount thereof were changed to non-crystalline polyester resin B-3 and 720 parts respectively. Example 8
    [000393] [000393] Toner 8 was obtained in the same way as in example 1 except that the non-crystalline polyester resin A-1 was changed to 120 parts, and the non-crystalline polyester resin B-1 and the quantity thereof were changed respectively for B-2 non-crystalline polyester resin and 780 parts in oil phase preparation. Example 9
    [000394] [000394] Toner 9 was obtained in the same way as in example 1 except that the non-crystalline polyester resin A-1 was changed to the non-crystalline polyester resin A-2. Example 10
    [000395] [000395] Toner 10 was obtained in the same way as in example 1 except that the non-crystalline polyester resin B-1 was changed to the non-crystalline polyester resin B-2. Comparative example 1
    [000396] [000396] Toner 11 was obtained in the same way as in example 1 except that the non-crystalline polyester resin A-1 was changed to the non-crystalline polyester resin A-5 and the non-crystalline polyester resin B-1 was changed for non-crystalline polyester resin B-4 in the oil phase preparation. Comparative example 2
    [000397] [000397] Toner 12 was obtained in the same way as in example 1 except that the non-crystalline polyester resin A-1 was changed to the non-crystalline polyester resin A-5 and the non-crystalline polyester resin B-1 was changed for non-crystalline polyester resin B-5 in the oil phase preparation. Comparative example 3
    [000398] [000398] Toner 13 was obtained in the same way as in example 1 except that the non-crystalline polyester resin A-1 was changed to the non-crystalline polyester resin A-3 and the non-crystalline polyester resin B-1 was changed for non-crystalline polyester resin B-2 in the oil phase preparation. Comparative example 4
    [000399] [000399] Toner 14 was obtained in the same way as in example 1 except that the non-crystalline polyester resin A-1 was changed to the non-crystalline polyester resin A-4 and the non-crystalline polyester resin B-1 was changed for non-crystalline polyester resin B-3 and crystalline polyester resin C-1 was not used in the oil phase preparation. Comparative example 5
    [000400] [000400] Toner 15 was obtained in the same way as in example 1 except that the non-crystalline polyester resin A-1 was changed to the non-crystalline polyester resin A-6 and the non-crystalline polyester resin B-1 was changed for non-crystalline polyester resin B-4 in the oil phase preparation. Comparative example 6
    [000401] [000401] Toner 16 was obtained in the same way as in example 1 except that the non-crystalline polyester resin A-1 was changed to the non-crystalline polyester resin A-6 and the non-crystalline polyester resin B-1 was changed for non-crystalline polyester resin B-5 in the oil phase preparation. Comparative example 7
    [000402] [000402] Toner 17 was obtained in the same way as in example 1 except that the amount of non-crystalline polyester resin A-1 was changed to 50 parts and the amount of non-crystalline polyester resin B-1 was changed to 850 parts in the preparation of oil phase. Comparative example 8
    [000403] [000403] Toner 18 was obtained in the same way as in example 1 except that the amount of non-crystalline polyester resin A-1 was changed to 750 parts and the amount of non-crystalline polyester resin B-1 was changed to 150 parts in the preparation of oil phase.
    [000404] [000404] Ratios of composition of the obtained toners are shown in Table 1.
    [000405] [000405] Each 1 part of the toners was added to 40 parts of tetrahydrofuran (THF) and the mixture was refluxed for 6 hours. Subsequently, insoluble components were made sediment with a centrifugal device, to thereby be separated from a supernatant.
    [000406] [000406] The insoluble components were dried at 40ºC for 20 hours to obtain THF insoluble matter.
    [000407] [000407] The solvent was removed from the supernatant separated above, followed by drying at 40ºC for 20 hours, in order to obtain THF soluble matter.
    [000408] [000408] Table 2 shows [Tg1st (toner)], [Tg2nd (THF insoluble matter), [Tg2nd (toner)], [G '(100) toner)], [Tg2nd (THF soluble matter), [ G '(100) (THF insoluble matter), [Tg2nd (THF soluble matter)], [G' (100) (THF insoluble matter)], [[G '(40) (THF insoluble matter)] / [G '(100) (THF insoluble matter)]] and quantities of THF-insoluble matter in the toners obtained. Evaluation
    [000409] [000409] Each of the toners obtained was used to prepare developers by the following method, and the following evaluation was carried out on the prepared developers. The results are shown in table 3. Developer production Carrier production
    [000410] [000410] To 100 parts of toluene, 100 parts of a silicone resin (straight organo silicone), 5 parts of - (2-aminoethyl) aminopropyl trimethoxy silane, and 10 parts of carbon black were added, and the resulting mixture was dispersed by means of a homomixer for 20 minutes, in order to prepare a resin layer coating liquid. To spherical magnetite particle surfaces having an average particle diameter of 50 µm (1,000 parts), the resin layer coating liquid was applied by means of a fluidized bed coating device, to thereby prepare a conveyor. Developer production
    [000411] [000411] By means of a ball mill, 5 parts by mass of each toner and 95 parts by mass of the conveyor were mixed, to thereby produce a developer. Offset resistance
    [000412] [000412] Each developer was loaded into an IMAGIO MP C4300 unit (product of Ricoh Company, Ltd.) and a solid rectangular image of 2 cm x 15 cm was formed on sheets of PPC paper (type 6000 <70W> A4 of long grain (product of Ricoh Company, Ltd.) so that the toner was deposited in an amount of 0.40 mg / cm2. In the formation of the images, the surface temperature of the fixation roller was changed, and if offset, in the which an image that remains after developing the solid image is fixed in places other than the intended places, occurred has been observed to assess resistance to offset.Note that the lowest temperature at which no offset has occurred is defined as a minimum fixing temperature.
    [000413] [000413] Evaluation criteria for cold offset A: less than 110ºC B: 110ºC or higher but lower than 120ºC
    [000414] [000414] Evaluation criteria for hot offset A: 170ºC or higher B: 160ºC or higher, but lower than 170ºC C: 150ºC or higher, but lower than 160ºC D: lower than 150ºC Storage stability resistant to heat
    [000415] [000415] Each of the toners was loaded into a 50 mL glass container, which was then left to rest in a 50 ° C thermostat bath for 24 hours, followed by cooling to 24 ° C. The toner thus treated was measured for degree of penetration according to the penetration test (JIS K2235-1991) and evaluated for heat-resistant storage stability according to the following criteria. Evaluation criteria A. The degree of penetration was 20 mm or greater B. The degree of penetration was 15 mm or greater, but less than 25 mm. C. The degree of penetration was 10 mm or greater, but less than 15 mm. The degree of penetration was less than 10 mm. Brightness
    [000416] [000416] A device provided for modifying a fixing portion of the MF2200 copier (product of Ricoh Company, Ltd.) using a TEFLON roll (trademark) as a fixing roll was used to perform a copy test on sheets of paper type 6200 (product of Ricoh Company, Ltd.)
    [000417] [000417] Each 5 g of the toners was stored under an environment of 40ºC and 70% RH for 2 weeks. After that, the toner was sieved through a metal mesh having an opening of 106 µm for 5 seconds, and a quantity of the toner in the metal mesh was measured and evaluated according to the following evaluation criteria. Evaluation criteria A: the amount of toner in the metal mesh was 0 mg B: the amount of toner in the metal mesh was greater than 0 mg, but less than 2 mg. C: the amount of toner in the metal mesh was 2 mg or more but less than 50 mg.
    [000418] [000418] The modalities of the present invention are as follows, for example.
    [000419] [000419] 1. Toner, where the toner has a glass transition temperature [Tg1st (toner)] of 20 ° C to 50 ° C, where the glass transition temperature [Tg1st (toner)] is measured in a first heating in a differential scanning calorimetry (DSC) of the toner, in which a matter insoluble in tetrahydrofuran (THF) has a glass transition temperature [Tg2nd (matter insoluble in THF)] from -40 ° C to 30 ° C, where at a glass transition temperature [Tg2nd (THF-insoluble matter)] is measured in a second heating in a differential scanning calorimetry (DSC) of the THF-insoluble matter, where the THF-insoluble matter comprises a storage module at 100 ° C [G '(100) (THF insoluble matter)] from 1.0 x 105 Pa to 1.0 x 107 Pa, and where a ratio of the storage module of THF insoluble matter at 40 ° C [G '(40) (THF-insoluble matter)] for the 100 ° C storage module [G' (100) (THF-insoluble matter)], expressed as [[G '(40) (THF-insoluble matter)] / [G '(1 00) (THF insoluble matter), is 3.5 x 10 or less.
    [000420] [000420] 2. Toner according to 1, where the toner has a glass transition temperature [Tg2nd (toner)] from 0 ° C to 30 ° C, where the glass transition temperature [Tg1st (toner)] is measured in a second heat in a differential scanning calorimetry (DSC) of the toner.
    [000421] [000421] 3. Toner, according to 1 or 2, in which a THF-insoluble matter in the toner has a glass transition temperature [Tg2nd (THF-insoluble matter)] from 5 ° C to 35 ° C, where the glass transition temperature [Tg2nd (THF insoluble matter)] is measured in a second heating in a differential scanning calorimetry (DSC) of THF insoluble matter.
    [000422] [000422] 4. Toner, according to any one from 1 to 3, where the toner comprises a storage module at 100 ° C [G '(100) (THF insoluble matter)] of 5.0 x 103 Pa at 5.0 x 104 Pa.
    [000423] [000423] 5. Toner, according to any one from 1 to 4, in which the toner comprises a non-crystalline polyester resin and a crystalline polyester resin as binder resins, in which the non-crystalline polyester resin comprises a component of dicarboxylic acid as a constituent component, and wherein the dicarboxylic acid component comprises terephthalic acid in an amount of 50 mol% or more.
    [000424] [000424] 6. Toner, according to any one from 1 to 4, in which the toner includes:
    [000425] [000425] 7. Toner, according to any one from 1 to 6, in which the amount of THF insoluble matter in the toner is 15% by mass to 35% by mass.
    [000426] [000426] 8. Toner, according to any of 1 to 7, in which the THF insoluble matter has a storage module at 100 ° C [G '(100) (THF-insoluble matter)] of 5.0 x 105 Pa to 5.0 x 106 Pa.
    [000427] [000427] 9. Developer including: toner according to any one from 1 to 8; and a carrier.
    [000428] [000428] 10. Imaging apparatus including: a member containing electrostatic imaging; an electrostatic imaging unit configured to form an electrostatic imaging on the element containing electrostatic imaging; and a developing unit containing a toner and configured to reveal the electrostatic imaging formed on the element containing an electrostatic imaging to form a visible image, wherein the toner is the toner according to any one from 1 to 8.
    权利要求:
    Claims (10)
    [1]
    1. Toner characterized by the fact that it comprises a glass transition temperature [Tg1st (toner)] of 20 ° C to 50 ° C, in which the glass transition temperature [Tg1st (toner)] is measured in a first heating in calorimetry differential scanning (DSC) of the toner, where the tetrahydrofuran (THF) insoluble matter of the toner has a glass transition temperature [Tg2nd (THF insoluble matter)] of -40 ° C to 30 ° C, where the temperature glass transition [Tg2nd (THF insoluble matter)] is measured in a second heating in differential scanning calorimetry (DSC) of the THF insoluble matter, where the THF insoluble matter comprises a storage module at 100 ° C [G '(100) (THF insoluble matter)] from 1.0 x 105 Pa to 1.0 x 107 Pa, and where a ratio of the storage module of THF insoluble matter at 40 ° C [G' (40) (THF-insoluble matter)] for the storage module of THF-insoluble matter at 100 ° C [G '(100) (THF-insoluble matter)], expressed by [[G' (40 ) (THF insoluble matter)] / [G '(100) (THF insoluble matter)]], is 3.5 x 10 or less.
    [2]
    2. Toner, according to claim 1, characterized by the fact that the toner has a glass transition temperature [Tg2nd (toner)] from 0 ° C to 30 ° C, in which the glass transition temperature [Tg2nd (toner) )] is measured in a second heating in differential scanning calorimetry (DSC) of the toner.
    [3]
    3. Toner according to claim 1 or 2, characterized by the fact that a THF soluble matter in the toner has a glass transition temperature [Tg2nd (THF soluble matter)] from 5 ° C to 35 ° C, in that the glass transition temperature [Tg2nd (soluble matter of THF)] is measured in a second heating in differential scanning calorimetry (DSC) of the soluble matter in THF.
    [4]
    4. Toner according to any one of claims 1 to 3, characterized in that the toner comprises a storage module at 100 ° C [G '(100) (toner)] from 5.0 x 103 Pa at 5 , 0 x 104 Pa.
    [5]
    5. Toner according to any one of claims 1 to 4, characterized in that the toner comprises a non-crystalline polyester resin and a crystalline polyester resin as binder resins, wherein the non-crystalline polyester resin comprises a component dicarboxylic acid as a constituent component, and wherein the dicarboxylic acid component comprises terephthalic acid in an amount of 50 mol% or more.
    [6]
    6. Toner according to any one of claims 1 to 4, characterized in that it comprises: a crystalline polyester resin; a non-crystalline polyester resin that contains a urethane bond, a urea bond, or both; and a non-crystalline polyester resin that is free of a urethane bond or a urea bond.
    [7]
    7. Toner according to any one of claims 1 to 6, characterized by the fact that the amount of THF-insoluble matter in the toner is 15% by mass to 35% by mass.
    [8]
    8. Toner according to any one of claims 1 to 7, characterized in that the THF-insoluble matter has a storage module at 100 ° C [G '(100) (THF-insoluble matter)] of 5, 0 x 105 Pa to 5.0 x 106 Pa.
    [9]
    9. Developer characterized by the fact that it comprises: a toner as defined in any one of claims 1 to 8; and a carrier.
    [10]
    10. Imaging apparatus characterized by the fact that it comprises: an electrostatic imaging bearing member; an electrostatic imaging unit configured to form an electrostatic imaging on the electrostatic imaging bearing member; and a developing unit containing a toner and configured to reveal the electrostatic imaging formed on the electrostatic imaging bearing member to form a visible image, wherein the toner is as defined in any of claims 1 to 8.
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112016005072A2|2020-08-11|toner, developer and image forming machine
    AU2017272147B2|2019-03-07|Toner, Developer And Image Forming Apparatus
    US10156801B2|2018-12-18|Toner
    US10859932B2|2020-12-08|Toner, toner accommodating unit, and image forming apparatus
    US9639016B2|2017-05-02|Toner, developer, image forming apparatus, and process cartridge
    RU2640092C1|2017-12-26|Toner, developer and image forming apparatus
    BR102016005258A2|2017-02-14|toner, developer, and imaging device
    US11036154B2|2021-06-15|Toner, toner storage unit, image forming apparatus, and image forming method
    US9588451B2|2017-03-07|Toner, developer, and image forming apparatus
    KR101910723B1|2018-10-22|Polyester resin for toner, toner, developer, and image formation device
    BR112016018061B1|2021-10-05|TONER, DEVELOPER AND IMAGE FORMATION APPARATUS
    同族专利:
    公开号 | 公开日
    AU2014316026B2|2016-12-22|
    AU2014316026A1|2016-02-25|
    EP3042242B1|2017-11-08|
    JP5884797B2|2016-03-15|
    JP2015052697A|2015-03-19|
    KR20160045138A|2016-04-26|
    EP3042242A1|2016-07-13|
    KR101724248B1|2017-04-06|
    RU2625260C1|2017-07-12|
    CN105683841B|2019-11-01|
    EP3042242A4|2016-07-27|
    US20160231661A1|2016-08-11|
    CN105683841A|2016-06-15|
    WO2015034028A1|2015-03-12|
    US9557669B2|2017-01-31|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    JP2579150B2|1986-10-27|1997-02-05|日本合成化学工業株式会社|Toner binder|
    DE69705102T2|1996-10-09|2001-10-31|Canon Kk|Toners for electrostatic image development and imaging processes|
    JP3817348B2|1996-10-09|2006-09-06|キヤノン株式会社|Toner for developing electrostatic image and image forming method|
    JP3762075B2|1997-10-31|2006-03-29|三洋化成工業株式会社|Dry toner|
    JP4011246B2|1999-12-02|2007-11-21|花王株式会社|Method for producing polyester polymer|
    JP4101542B2|2001-03-23|2008-06-18|株式会社リコー|Image forming method|
    JP2002287400A|2001-03-27|2002-10-03|Ricoh Co Ltd|Dry toner, manufacturing method for the toner and image forming apparatus using the toner|
    JP4175505B2|2002-05-24|2008-11-05|株式会社リコー|Color toner for electrostatic image development|
    JP2004045668A|2002-07-10|2004-02-12|Ricoh Co Ltd|Developer for electrostatic charge pattern development, image forming apparatus, and image forming method|
    JP4003877B2|2002-08-22|2007-11-07|株式会社リコー|Toner for developing electrostatic image, developer, image forming method and image forming apparatus|
    US20040229148A1|2003-02-28|2004-11-18|Seiko Epson Corporation|Toner and image-forming apparatus using the same|
    JP2004264495A|2003-02-28|2004-09-24|Seiko Epson Corp|Toner and image forming device using same|
    JP4037329B2|2003-06-25|2008-01-23|株式会社リコー|Toner for developing electrostatic image, developer, image forming method, image forming apparatus, and process cartridge|
    JP4070702B2|2003-10-10|2008-04-02|株式会社リコー|Toner for developing electrostatic image, developer, image forming method and image forming apparatus|
    US7642032B2|2003-10-22|2010-01-05|Ricoh Company, Limited|Toner, developer, image forming apparatus and image forming method|
    EP1530100B1|2003-10-22|2009-02-11|Ricoh Company, Ltd.|Image forming method using toner|
    EP2328034B1|2003-12-10|2014-03-19|Sanyo Chemical Industries, Ltd.|Composite resin particles|
    CN1938649B|2004-02-03|2012-10-24|株式会社理光|Toner, and developer, container packed with toner, process cartridge, image forming apparatus and method for forming image|
    JP4105650B2|2004-03-16|2008-06-25|株式会社リコー|Toner, developer, developing device, image forming apparatus|
    JP2006039424A|2004-07-29|2006-02-09|Ricoh Co Ltd|Image forming apparatus, toner used for the same and toner container housing the toner|
    JP2006058652A|2004-08-20|2006-03-02|Toshiba Corp|Toner|
    US7455942B2|2004-09-17|2008-11-25|Ricoh Company, Ltd.|Toner, developer, toner container, process cartridge, image forming apparatus, and image forming method using the same|
    JP2006349894A|2005-06-15|2006-12-28|Canon Inc|Toner, method for manufacturing toner, image forming method and image forming apparatus|
    JP4928851B2|2006-03-14|2012-05-09|株式会社リコー|Toner for developing electrostatic image and image forming apparatus using the toner for developing electrostatic image|
    JP2007271789A|2006-03-30|2007-10-18|Sanyo Chem Ind Ltd|Toner binder and toner|
    CN101449213B|2006-06-08|2012-01-18|佳能株式会社|Toner|
    JP4658010B2|2006-09-15|2011-03-23|株式会社リコー|Toner and manufacturing method thereof, developer, toner-containing container, process cartridge, image forming method, and image forming apparatus|
    JP4668887B2|2006-11-22|2011-04-13|株式会社リコー|Toner, image forming apparatus using the same, image forming method, and process cartridge|
    EP1925983B1|2006-11-22|2014-11-12|Ricoh Company, Ltd.|Toner and developer|
    JP5042889B2|2007-03-16|2012-10-03|株式会社リコー|Toner and developer, and image forming method using the same|
    EP1990683B1|2007-05-11|2012-09-05|Ricoh Company, Ltd.|Toner, image forming apparatus, image forming method and process cartridge using the toner|
    JP5090057B2|2007-05-11|2012-12-05|株式会社リコー|Toner, and image forming apparatus and image forming method using the same|
    JP5128858B2|2007-06-19|2013-01-23|株式会社リコー|Toner and method for producing the same|
    JP5054443B2|2007-06-20|2012-10-24|株式会社リコー|Image forming apparatus, image forming method, and process cartridge|
    JP5315808B2|2007-06-22|2013-10-16|株式会社リコー|Toner, developer, toner containing container, image forming method, image forming apparatus, and process cartridge|
    JP5224114B2|2007-09-13|2013-07-03|株式会社リコー|Image forming apparatus and image forming method|
    JP5036478B2|2007-10-09|2012-09-26|株式会社リコー|toner|
    JP2009116313A|2007-10-18|2009-05-28|Ricoh Co Ltd|Toner, developer, image forming method, image forming apparatus and process cartridge|
    JP5124308B2|2008-02-26|2013-01-23|株式会社リコー|Toner, developer using the toner, container with toner, process cartridge, and image forming method|
    JP5568888B2|2008-05-23|2014-08-13|株式会社リコー|Toner, developer, toner container, process cartridge, and image forming method|
    JP2010008734A|2008-06-27|2010-01-14|Ricoh Co Ltd|Toner, image forming method using the same, and process cartridge|
    JP5157733B2|2008-08-05|2013-03-06|株式会社リコー|Toner, developer, toner container, process cartridge, and image forming method|
    EP2562202B1|2010-04-23|2016-03-16|Nicca Chemical Co., Ltd.|Amorphous polyester resin, binder resin for toner for electrostatic image development and amorphous polyester resin production method|
    JP2011237663A|2010-05-12|2011-11-24|Ricoh Co Ltd|Toner, developer and image forming method|
    JP5522540B2|2010-09-15|2014-06-18|株式会社リコー|Toner, developer, developer container, process cartridge, image forming apparatus, and image forming method|
    JP5573528B2|2010-09-15|2014-08-20|株式会社リコー|Resin for toner, toner using the resin for toner, and two-component developer|
    JP5594591B2|2010-09-30|2014-09-24|株式会社リコー|Toner for electrophotography, developer using the toner, image forming apparatus, image forming method, process cartridge|
    JP2012093562A|2010-10-27|2012-05-17|Ricoh Co Ltd|Toner, image forming method, and developer|
    JP2012108462A|2010-10-28|2012-06-07|Ricoh Co Ltd|Toner and developer|
    JP5765132B2|2010-12-06|2015-08-19|株式会社リコー|Toner for developing electrostatic image, developer using the toner, image forming apparatus, and process cartridge|
    JP2013080200A|2011-05-02|2013-05-02|Ricoh Co Ltd|Electrophotographic toner, developer, and image forming apparatus|
    JP2013050629A|2011-08-31|2013-03-14|Mitsubishi Corp|Binder composition for electrophotographic toner|
    JP5408210B2|2011-09-02|2014-02-05|株式会社リコー|Toner and developer|
    JP5769016B2|2011-09-22|2015-08-26|株式会社リコー|Toner for electrophotography, developer using the toner, image forming apparatus, and process cartridge|
    US20130095422A1|2011-10-17|2013-04-18|Atsushi Yamamoto|Toner|
    JP5709065B2|2011-10-17|2015-04-30|株式会社リコー|Toner, developer using the toner, and image forming apparatus|
    JP5850314B2|2011-10-26|2016-02-03|株式会社リコー|Toner, developer using the toner, and image forming apparatus|
    JP5850316B2|2011-11-09|2016-02-03|株式会社リコー|Dry electrostatic image developing toner and image forming apparatus|
    JP5240394B1|2011-12-01|2013-07-17|株式会社リコー|Toner for electrophotography, developer, image forming method, process cartridge, image forming apparatus, toner container|
    JP6066447B2|2011-12-14|2017-01-25|株式会社リコー|Toner and image forming method using the same|
    JP6086291B2|2011-12-15|2017-03-01|株式会社リコー|Toner, developer, and toner production method|
    JP5948854B2|2011-12-20|2016-07-06|株式会社リコー|Electrophotographic developer, image forming apparatus, and process cartridge|
    JP2013148862A|2011-12-20|2013-08-01|Ricoh Co Ltd|Toner, developer and image forming apparatus|
    JP5896137B2|2012-03-07|2016-03-30|株式会社リコー|Toner production method|
    JP6056483B2|2012-03-13|2017-01-11|株式会社リコー|Developer and image forming apparatus|
    JP5957988B2|2012-03-14|2016-07-27|株式会社リコー|Toner for developing electrostatic image, developer, developer container, image forming method, process cartridge|
    JP2013218288A|2012-03-15|2013-10-24|Ricoh Co Ltd|Toner for electrostatic charge image development, developer using the same, and image forming apparatus|
    JP6020099B2|2012-03-15|2016-11-02|株式会社リコー|Colorless transparent toner, toner set, developer, image forming apparatus and image formed product|
    JP5900072B2|2012-03-21|2016-04-06|株式会社リコー|Electrophotographic toner, developer, image forming apparatus, and electrophotographic toner manufacturing method|
    JP6236797B2|2012-03-28|2017-11-29|株式会社リコー|Toner manufacturing method, developer manufacturing method, and image forming method|
    JP6011051B2|2012-06-18|2016-10-19|株式会社リコー|Toner, developer, and image forming apparatus|
    JP6098243B2|2012-07-23|2017-03-22|株式会社リコー|Toner and method for producing the toner|
    US9176406B2|2012-08-17|2015-11-03|Ricoh Company, Ltd.|Toner, development agent, image forming apparatus, and process cartridge|
    JP6060692B2|2012-08-31|2017-01-18|株式会社リコー|Toner, developer, and image forming apparatus|
    JP5482951B2|2012-09-18|2014-05-07|株式会社リコー|Toner for electrostatic image formation, developer, process cartridge, image forming apparatus|
    JP6123451B2|2012-09-18|2017-05-10|株式会社リコー|Electrostatic image forming toner, developer, and image forming apparatus|
    JP2014174527A|2013-03-13|2014-09-22|Ricoh Co Ltd|Magenta toner, developer, toner cartridge, image forming apparatus, and printing|
    JP6375625B2|2013-03-15|2018-08-22|株式会社リコー|Image forming apparatus|
    JP6458515B2|2014-03-03|2019-01-30|株式会社リコー|Toner for electrostatic image development, developer, and image forming apparatus|
    JP2016011977A|2014-06-27|2016-01-21|株式会社リコー|Image forming apparatus and image forming method|JP6217368B2|2013-12-10|2017-10-25|株式会社リコー|Toner, developer, and image forming apparatus|
    JP6260315B2|2014-02-05|2018-01-17|株式会社リコー|Toner, developer, process cartridge, and image forming apparatus|
    EP3112937B1|2014-02-26|2018-10-10|Ricoh Company, Ltd.|Toner, developer, and image formation device|
    JP6458515B2|2014-03-03|2019-01-30|株式会社リコー|Toner for electrostatic image development, developer, and image forming apparatus|
    JP2016011977A|2014-06-27|2016-01-21|株式会社リコー|Image forming apparatus and image forming method|
    JP6459052B2|2015-03-06|2019-01-30|株式会社リコー|Toner, developer, image forming apparatus, and process cartridge|
    JP6776564B2|2015-05-12|2020-10-28|株式会社リコー|Toner, developer, image forming equipment and process cartridge|
    JP6544052B2|2015-06-01|2019-07-17|株式会社リコー|Toner, developer, and image forming apparatus|
    JP6485228B2|2015-06-02|2019-03-20|株式会社リコー|Toner, developer, and image forming apparatus|
    JP2017010002A|2015-06-23|2017-01-12|株式会社リコー|Toner, developer, image forming apparatus, and developer storage unit|
    JP6428541B2|2015-09-16|2018-11-28|京セラドキュメントソリューションズ株式会社|Liquid developer|
    JP6551544B2|2016-01-18|2019-07-31|株式会社リコー|Toner, developer, and image forming apparatus|
    JP2017227710A|2016-06-21|2017-12-28|株式会社東芝|Image formation device|
    US10289016B2|2016-12-21|2019-05-14|Canon Kabushiki Kaisha|Toner|
    US10303072B2|2017-02-08|2019-05-28|Ricoh Company, Ltd.|Toner, developer, and image forming device|
    JP2019152856A|2018-03-02|2019-09-12|株式会社リコー|Image forming apparatus and image forming method|
    US11054757B2|2018-09-27|2021-07-06|Ricoh Company, Ltd.|Toner, image forming apparatus, image forming method, and process cartridge|
    JP2020148893A|2019-03-13|2020-09-17|株式会社リコー|Image forming apparatus and image forming method|
    法律状态:
    2018-11-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2020-08-25| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-11-03| B350| Update of information on the portal [chapter 15.35 patent gazette]|
    2022-02-15| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    优先权:
    申请号 | 申请日 | 专利标题
    JP2013-185194|2013-09-06|
    JP2013185194A|JP5884797B2|2013-09-06|2013-09-06|Toner, developer, and image forming apparatus|
    PCT/JP2014/073417|WO2015034028A1|2013-09-06|2014-08-29|Toner, developer, and image forming apparatus|
    [返回顶部]