toner

Abstract

This toner offers excellent low-temperature fixation and heat-resistant storage properties, is less prone to drum fusion, and can suppress image defects in double-sided printing. [Solution] A toner having toner particles containing a binder resin and wax, wherein the binder resin contains a crystalline resin, and in the viscoelasticity measurement of the toner, when the temperature is raised from 30°C to 100°C at a rate of 2°C / min to obtain a curve G'1(T) of the storage modulus G' against temperature T, and then the temperature is lowered from 100°C to 30°C at a rate of 2°C / min to obtain a curve G'2(T) of the storage modulus G' against temperature T, and then the temperature is raised from 30°C to 100°C at a rate of 2°C / min to obtain a curve G'3(T) of the storage modulus G' against temperature T, the storage modulus at a specific temperature in each curve satisfies the following formula. G'1(100)≦5.0×10 4 Pa G'3(50)≧7.0×10 7 Pa G'3(70)≧2.0×10 6 Pa G'3(70) / G'2(70)≧10

Description

Technical Field

[0001] The present disclosure relates to toner used in electrophotographic systems, electrostatic recording systems, electrostatographic printing systems, and toner jet systems.

Background Art

[0002] In recent years, in order to achieve a low-carbon society, low power consumption has been strongly desired even in electrophotographic devices such as full-color printers and full-color copiers.

[0003] In order to achieve low power consumption, it is important to melt the toner at a lower temperature in the fixing process. Therefore, in order to improve the sharp melting property, a crystalline resin is contained in the binder resin of the toner. On the other hand, toner containing a crystalline resin may have a reduced storage stability at high temperatures, or a phenomenon (drum fusion) may occur in which the toner strongly adheres to the photoreceptor and leads to image defects. In addition, the solidification of the melted toner in the fixing process may be slow, and when the output recording media are stacked, defects (paper discharge adhesion phenomenon) may occur due to the transfer of a part of the fixed image to other recording media or the adhesion of the fixed images to each other.

[0004] In order to suppress the paper discharge adhesion phenomenon, for example, Patent Document 1 discloses a toner containing an amorphous polyester having an alkyl group with a specific number of carbon atoms at the terminal and a crystalline polyester composed of a specific number of carbon atoms. Further, Patent Document 2 discloses a toner in which the complex viscosity when performing dynamic viscoelasticity measurement by different heat processes falls within a specific range.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] The toner in the above document has a certain effect in suppressing the paper discharge adhesion phenomenon. However, according to the study by the inventors, during double-sided printing, a part of the fixed image may come into contact with and transfer to the member in contact with the recording medium in the electrophotographic apparatus, resulting in image defects (hereinafter referred to as double-sided printing image defects). The present disclosure relates to a toner having good low-temperature fixing property and heat-resistant storage property, being less likely to cause drum fusion, and further capable of suppressing double-sided printing image defects.

Means for Solving the Problems

[0007] The present disclosure is a toner having toner particles containing a binder resin and a wax, the binder resin contains a crystalline resin, in the viscoelastic measurement of the toner, Step (i): The temperature is raised from 30°C to 100°C at a rate of 2°C / min to obtain a curve G´1(T) of the storage modulus G´ [Pa] with respect to the temperature T [°C], Step (ii): After step (i), the temperature is lowered from 100°C to 30°C at a rate of 2°C / min to obtain a curve G´2(T) of the storage modulus G´ [Pa] with respect to the temperature T [°C], Step (iii): After step (ii), the temperature is raised from 30°C to 100°C at a rate of 2°C / min to obtain a curve G´3(T) of the storage modulus G´ [Pa] with respect to the temperature T [°C], Let the storage modulus G´ at 100°C in the curve G´1(T) be G´1(100) [Pa], the storage modulus G´ at 70°C in the curve G´2(T) be G´2(70) [Pa], the storage modulus G´ at 50°C in the curve G´3(T) be G´3(50) [Pa], and the storage modulus G´ at 70°C in the curve G´3(T) be G´3(70) [Pa], The toner relates to the case where the G´1(100), the G´2(70), the G´3(50), and the G´3(70) satisfy the following formulas (1) to (4). G´1(100)≦5.0×10 4Pa ···(1) G'3(50)≧7.0×10 7 Pa ···(2) G'3(70)≧2.0×10 6 Pa ···(3) G'3(70) / G'2(70)≧10 ···(4) [Effects of the Invention]

[0008] According to this disclosure, it is possible to provide a toner that has good low-temperature fixability and heat resistance for storage, is less prone to drum fusion, and can suppress image defects in double-sided printing. [Modes for carrying out the invention]

[0009] In this disclosure, descriptions of numerical ranges such as "XX or greater and YY or less" or "XX to YY" mean a numerical range that includes the lower and upper limits, unless otherwise specified. When numerical ranges are described in steps, the upper and lower limits of each numerical range can be any combination. In addition, in this disclosure, a description such as "at least one selected from the group consisting of XX, YY, and ZZ" means any of the following: XX, YY, ZZ, a combination of XX and YY, a combination of XX and ZZ, a combination of YY and ZZ, or a combination of XX, YY, and ZZ. Note that if XX is a group, multiple values ​​may be selected from XX, and the same applies to YY and ZZ.

[0010] Crystalline resins refer to resins that exhibit a clear endothermic peak in differential scanning calorimeter (DSC) measurements. A "monomer unit" refers to the reacted form of monomer substances within a polymer. The toner described in this disclosure is explained in detail below.

[0011] This disclosure relates to a toner having toner particles containing a binder resin and a wax, The binder resin contains a crystalline resin, In measuring the viscoelasticity of the toner, Step (i) The temperature is raised from 30°C to 100°C at a rate of 2°C / min to obtain the curve G'1(T) of the storage modulus G'[Pa] as a function of temperature T[°C]. Step (ii) After step (i), the temperature is lowered from 100°C to 30°C at a rate of 2°C / min to obtain the curve G'2(T) of the storage modulus G'[Pa] against temperature T[°C]. Step (iii) After step (ii), the temperature is raised from 30°C to 100°C at a rate of 2°C / min to obtain the curve G'3(T) of the storage modulus G'[Pa] against temperature T[°C]. When the storage modulus G' at 100°C in curve G'1(T) is G'1(100)[Pa], the storage modulus G' at 70°C in curve G'2(T) is G'2(70)[Pa], the storage modulus G' at 50°C in curve G'3(T) is G'3(50)[Pa], and the storage modulus G' at 70°C in curve G'3(T) is G'3(70)[Pa], The present invention relates to a toner in which G'1(100), G'2(70), G'3(50), and G'3(70) satisfy the following formulas (1) to (4). G'1(100)≦5.0×10 4 Pa ···(1) G'3(50)≧7.0×10 7 Pa ···(2) G'3(70)≧2.0×10 6 Pa ···(3) G'3(70) / G'2(70)≧10 ···(4)

[0012] As a result of diligent research by the present inventors, it has been found that the above problems can be solved by controlling the viscoelasticity of the toner to a specific range in a toner containing a crystalline resin. In other words, the above toner can achieve excellent low-temperature fixing properties and heat resistance, and can suppress image defects in double-sided printing and drum fusion during long-term durability at low print ratios.

[0013] The circumstances leading to the above-mentioned toner are as follows: The toner is heated and melted during the fixing process, then cooled and solidified to form the fixed image. When a fixed image is formed on one side of an image medium, it is subjected to heat again during the fixing process on the reverse side during double-sided printing. If the storage modulus of the fixed image formed on one side is low, a portion of the fixed image may transfer to other components such as transfer members or transport members when the fixed image comes into contact with other components during double-sided printing, resulting in image defects.

[0014] Toner containing crystalline resin may solidify in a state where some of the crystalline resin does not crystallize after being melted and cooled during the fixing process. Since such crystalline resin easily acts as a plasticizer in the fixed image, it is suspected that this may lead to the transfer of the fixed image to other components during double-sided printing. While there are measures to further promote the crystallization of the crystalline resin, such as adding materials that act as crystal nucleating agents, it is difficult to eliminate the non-crystallizing crystalline resin components.

[0015] Therefore, the inventors considered it important to improve the intensity of the fixed image even if uncrystallized crystalline resin was present. The inventors then found that the storage modulus of a toner sample that had been melted and then solidified corresponded well to the intensity of the fixed image, serving as an indicator of the strength of the fixed image. However, simply increasing the storage modulus of the toner would hinder low-temperature fixing performance. After prototyping and testing various toners, the inventors found that toners exhibiting excellent low-temperature fixing performance while having a high storage modulus at 70°C during the second heating stage had a lower storage modulus at 70°C during cooling than at the heating stage, leading to the toner described above.

[0016] The toner of this disclosure has the following characteristics: In viscoelasticity measurements of toner at a strain of 1%, Step (i) The temperature is increased from 30°C to 100°C at a rate of 2°C / min to obtain the curve G'1(T) of the storage modulus G'[Pa] as a function of temperature T[°C]. Step (ii) After step (i), the temperature is lowered from 100°C to 30°C at a rate of 2°C / min to obtain the curve G'2(T) of the storage modulus G'[Pa] as a function of temperature T[°C]. Step (iii) After step (ii), the temperature is raised from 30°C to 100°C at a rate of 2°C / min to obtain a curve G´3(T) of the storage modulus G´ [Pa] with respect to the temperature T [°C].

[0017] Then, the storage modulus G´ at 100°C in the curve G´1(T) is denoted as G´1(100) [Pa]. The storage modulus G´ at 70°C in the curve G´2(T) is denoted as G´2(70) [Pa]. Also, the storage modulus G´ at 50°C in the curve G´3(T) is denoted as G´3(50) [Pa], and the storage modulus G´ at 70°C in the curve G´3(T) is denoted as G´3(70) [Pa]. At this time, G´1(100), G´2(70), G´3(50), and G´3(70) satisfy the following formulas (1) to (4). G´1(100) ≤ 5.0×10 4 Pa ···(1) G´3(50) ≥ 7.0×10 7 Pa ···(2) G´3(70) ≥ 2.0×10 6 Pa ···(3) G´3(70) / G´2(70) ≥ 10 ···(4) That is.

[0018] In the viscoelasticity measurement of the toner, step (i) simulates the behavior of the toner being heated in the fixing process. Step (ii) simulates the behavior of the toner during the process of being heated and melted and then cooled. Step (iii) simulates the behavior of the solidified fixing image when reheated during double-sided printing.

[0019] The toner is characterized in that G´1(100) ≤ 5.0×10 4 Pa. Since G´1(100) is the storage modulus G´ at 100°C, satisfying formula (1) indicates that the storage modulus of the toner is sufficiently low in the fixing process. When G´1(100) is within the above range, excellent low-temperature fixing performance can be obtained. From the perspective of achieving both low-temperature fixing performance and hot offset resistance, preferably 1.0×10 3 Pa ≤ G´1(100) ≤ 5.0×l04 Pa is more like 1.0 × 10⁻⁶. 3 Pa≦G'1(100)≦2.0×10 4 It is Pa.

[0020] The value of G'1(100) can be controlled by the melting point and content of the crystalline resin. It can also be controlled by the glass transition temperature and softening point of resins other than crystalline resins, and by the melting point and content of the wax. The value of G'1(100) can be increased, for example, by reducing the content of crystalline resin or by increasing the glass transition temperature or softening temperature of resins other than crystalline resin. Conversely, the value of G'1(100) can be decreased, for example, by setting the melting point of the crystalline resin below 100°C and increasing its content. It can also be decreased by using resins other than crystalline resin that have a low softening temperature. Furthermore, it can be decreased by setting the melting point of the wax below 100°C and increasing its wax content.

[0021] The toner is characterized by satisfying equation (4) and having G'3(70) / G'2(70)≧10. Satisfying equation (4) indicates that there is a difference of 10 or more between the storage modulus of the toner during the cooling process after melting and the storage modulus during the subsequent heating process. The inventors of the present invention speculate that the mechanism by which the above-mentioned toner exhibits such behavior is as follows.

[0022] The above toner, after melting and then cooling, begins to crystallize near its crystallization temperature. The crystallization temperature can be measured by differential scanning calorimetry (DSC), as described later, at the peak top temperature of the exothermic peak associated with crystallization observed during cooling. As the crystallized resin begins to crystallize, the solid component in the toner increases, and the storage modulus of the toner also increases. At this time, it is thought that crystallization does not occur in the crystalline resin alone, but rather progresses while interacting with other molten binder resins in the surrounding area.

[0023] The inventors hypothesize that this interaction leads to a slower increase in the storage modulus compared to when there is no interaction with other binder resins. Therefore, G'2(70) becomes smaller. The slower increase in the storage modulus allows the crystalline resin to have a high molecular mobility, which makes it easier to achieve a molecular chain arrangement that is closer to the ideal crystalline state. As the fixed image solidifies through such a process becomes stronger, G'3(70) becomes larger, and the relationship G'3(70) / G'2(70)≧10 can be achieved.

[0024] Preferably, G'3(70) / G'2(70) ≥ 20, more preferably G'3(70) / G'2(70) ≥ 38, and even more preferably G'3(70) / G'2(70) ≥ 40. If G'3(70) / G'2(70) is less than 10, it is more likely to cause image defects during double-sided printing. Also, G'3(70) / G'2(70) is, for example, 10 to 100, preferably 20 to 90, more preferably 38 to 80, and even more preferably 40 to 75.

[0025] Methods for controlling the G'3(70) / G'2(70) ratio include, as will be explained later in the description of raw materials, introducing a structure with alkyl groups at the ends of the molecular chains of crystalline polyester resin. Other methods include introducing monomer units corresponding to linear aliphatic carboxylic acids into binder resins other than crystalline resins.

[0026] Furthermore, the toner satisfies equation (2), G'3(50)≧7.0×10 7 It is characterized by becoming Pa. When G'3(50) is within the above range, the heat resistance and storage properties of the toner are improved. Preferably, G'3(50) ≥ 9.0 × 10 7 Pa, and more preferably G'3(50)≧1.0×10 8 Pa is . G'3(50) is 7.0 × 10 7 If the Pa level is below a certain point, the heat resistance and storage properties of the toner will decrease.

[0027] Here, in toners containing crystalline resin, the longer the time elapsed since manufacturing, the more likely the crystalline resin within the toner is to crystallize. As a result, the value of G'1(50) tends to increase with longer storage times for the toner, making it difficult to accurately compare the heat resistance of the toner. Therefore, in this disclosure, the value of G'3(50) is adopted as an index that can evaluate heat resistance without substantially considering the effect of storage time. Note that the values ​​of G'1(100), G'2(T), and G'3(T) are not affected by the toner storage time. G'3(50) is, for example, 7.0 × 10 7 ~7.0×10 9 Pa is preferably 9.0 × 10 7 ~4.0×10 9 Pa is more like 1.0 × 10⁻⁶. 8 ~2.0×10 9 It is Pa.

[0028] Furthermore, the toner satisfies equation (3), G'3(70)≧2.0×10 6 It is characterized by being Pa. Since G'3(70) is within the above range, image defects during double-sided printing can be suppressed. Preferably, G'3(70) ≥ 5.0 × 10 6 Pa is Pa, and more preferably G'3(70)≧7.0×10 6 Pa is Pa. G'3(70) is 2.0 × 10 6 If the Pa level is less than Pa, image defects during double-sided printing cannot be suppressed. G'3(70) is, for example, 2.0 × 10 6 ~9.0×10 7 Pa is preferably 5.0 × 10 6 ~4.0×10 7 Pa is more like 7.0 × 10⁻⁶. 6 ~3.0×10 7 It is Pa.

[0029] The values ​​of G'3(50) and G'3(70) can be controlled by changing the melting point and content of the crystalline resin, the type of binder resin other than the crystalline resin, the glass transition temperature, the weight-average molecular weight of the THF-soluble component, and its content. G'3(50) can be increased, for example, by raising the glass transition temperature of the binder resin other than the crystalline resin, increasing the weight-average molecular weight of the binder resin, or decreasing the content of the crystalline resin. G'3(70) can be increased, for example, by introducing a structure having an alkyl group at the end of the molecular chain of a crystalline polyester resin, or by further incorporating an amorphous polyester resin into the binder resin and introducing an alkyl group at the end of its molecular chain.

[0030] Furthermore, with respect to the curve G'2(T), it is preferable that a minimum value exists in the range of 55.0 to 70.0°C in a graph where temperature T is the horizontal axis and the value d(logG'2(T)) / dT, obtained by differentiating LogG'2(T) with respect to temperature T, is the vertical axis. Furthermore, when the temperature at which the minimum value is obtained is denoted as temperature T2 (°C), it is preferable that d(logG'2(T2)) / dT is between -2.0 and -0.3.

[0031] In the graph above, the minimum value in the range of 55.0 to 70.0°C indicates that the storage modulus increases sharply in the range of 55.0 to 70.0°C during the cooling process after the toner has melted. This means that there is a point of addition. Also, d(logG'2(T2)) / dT indicates the magnitude of the change in storage modulus, and the larger its absolute value, the steeper the change. The fact that d(logG'2(T2)) / dT is in the range of -2.0 to -0.3 indicates that the storage modulus increases steeply during the cooling process after the toner has melted.

[0032] As the crystalline resin in the molten toner cools, it interacts with other binder resins, adopting a molecular chain arrangement that results in a near-ideal crystalline state. This makes it easier for the storage modulus to increase sharply in the range of 55.0 to 70.0°C. Therefore, it becomes easier to control the value of G'3(50) within this range.

[0033] In the graph above, a minimum value T2 of 55°C or higher results in a higher elastic modulus of the image, making it easier to suppress image defects during double-sided printing. Additionally, a minimum value of 70.0°C or lower facilitates interaction between the crystalline resin and other binder resins, further reducing the likelihood of image defects during double-sided printing.

[0034] The minimum temperature T2 is more preferably 57.0 to 68.0°C. Furthermore, d(logG'2(T2)) / dT is more preferably -2.0 to -0.4, even more preferably -2.0 to -0.5, and even more preferably -1.3 to -0.5.

[0035] T2 can be changed by controlling the temperature at which the crystalline resin and other binder resins can interact. Specifically, the value of T2 can be lowered by lowering the melting point of the crystalline resin or lowering the glass transition temperature of the amorphous resin. Conversely, the value of T2 can be lowered by raising the melting point of the crystalline resin or raising the glass transition temperature of the amorphous resin.

[0036] One way to control d(logG'2(T2)) / dT within the above range is that a greater degree of interaction between the crystalline resin and other binder resins results in a larger absolute value, while a smaller degree of interaction results in a smaller absolute value. d(logG'2(T2)) / dT can be controlled by changing the structure, melting point, and molecular weight of the crystalline resin, changing the structure and softening point of the amorphous resin, or changing the type and melting point of the wax. Furthermore, d(logG'2(T2)) / dT can also be controlled by means of imparting an alkyl group to the molecular chain ends of the crystalline or amorphous resin.

[0037] Next, we will describe the raw materials of the toner in detail. The toner particles contain a binder resin. The binder resin contains a crystalline resin. Any known crystalline resin that can be used for toner can be used. Specifically, examples include crystalline polyester resin and crystalline vinyl resin. From the viewpoint of facilitating the aforementioned interactions, the crystalline resin preferably contains a crystalline polyester resin, and more preferably a crystalline polyester resin.

[0038] The crystalline polyester resin is preferably a condensed polymer of a monomer composition containing an aliphatic diol (for example, having 2 to 22 carbon atoms) and an aliphatic dicarboxylic acid (for example, having 2 to 22 carbon atoms) (for example, as main components). The main component means that its content is 50% by mass or more of the monomer composition. Preferably, it is 50 to 100% by mass, and more preferably 70 to 98% by mass.

[0039] The aliphatic diol having 2 to 22 carbon atoms (more preferably 2 to 12 carbon atoms) is not particularly limited, but it must be a linear aliphatic diol (more preferably a straight-chain aliphatic diol). These are preferred, and examples include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, 1,4-butanediol, 1,4-butadiene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, nonamethylene glycol, decamethylene glycol, dodecamethylene glycol, and neopentyl glycol. Among these, 1,6-hexanediol, 1,10-decanediol, and 1,12-dodecanediol are preferred examples.

[0040] Furthermore, polyhydric alcohol monomers other than the aliphatic diols mentioned above can also be used. Examples of dihydric alcohol monomers among these polyhydric alcohol monomers include aromatic alcohols such as polyoxyethylene-modified bisphenol A and polyoxypropylene-modified bisphenol A; and 1,4-cyclohexanedimethanol.

[0041] Furthermore, it is preferable to use polyhydric alcohol monomers with a valency of 3 or higher among the polyhydric alcohol monomers. Examples of polyhydric alcohol monomers with a valency of 3 or higher include aromatic alcohols such as 1,3,5-trihydroxymethylbenzene; and aliphatic alcohols such as pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, and trimethylolpropane.

[0042] On the other hand, the aliphatic dicarboxylic acid compound having 2 to 22 carbon atoms (more preferably 6 to 18 carbon atoms) is not particularly limited, but it is preferably a linear (more preferably straight-chain) aliphatic dicarboxylic acid. Specific examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, superiric acid, glutaconic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, maleic acid, fumaric acid, mesaconic acid, citraconic acid, and itaconic acid, and also includes hydrolyzed acid anhydrides or lower alkyl esters thereof. More preferably, adipic acid, sebacic acid, and 1,10-decanedicarboxylic acid are used.

[0043] Other polycarboxylic acids (hereinafter also referred to as "other polycarboxylic acids") besides the aliphatic dicarboxylic acid compounds with 2 to 22 carbon atoms mentioned above can also be used. Other polycarboxylic acid monomers include divalent carboxylic acids such as isophthalic acid and terephthalic acid; aliphatic carboxylic acids such as n-dodecylsuccinic acid and n-dodecenylsuccinic acid; and alicyclic carboxylic acids such as cyclohexanedicarboxylic acid. These also include their acid anhydrides or lower alkyl esters.

[0044] Furthermore, among other carboxylic acid monomers, polycarboxylic acids with a valency of 3 or higher include aromatic carboxylic acids such as 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalentricarboxylic acid, 1,2,4-naphthalentricarboxylic acid, and pyromellitic acid, as well as aliphatic carboxylic acids such as 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, and 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane. Derivatives such as acid anhydrides or lower alkyl esters of these compounds are also included.

[0045] The monomer composition forming the crystalline polyester resin is particularly preferably to contain, in addition to the above monomer, at least one selected from the group consisting of monohydric alcohols and monohydric carboxylic acids. That is, the crystalline polyester resin is an aliphatic diol and an aliphatic dicarboxylic acid. It is preferable that the monomer composition contains a condensed polymer. The crystalline polyester resin preferably has a structure in which at least one linear alkyl compound C, selected from the group consisting of monohydric alcohols and monohydric carboxylic acids, is condensed at the molecular chain end.

[0046] By using these monohydric alcohols and / or monohydric carboxylic acids, the molecular chain ends of the crystalline polyester resin become alkyl groups. During the cooling process after toner melting, these terminal alkyl groups readily interact with other binder resins. As a result, the G'3(70) / G'2(70) and d(logG'2(T2)) / dT values ​​of the toner become larger, making it easier to control the G'3(50) and G'3(70) values ​​within the aforementioned ranges. It is particularly preferable that the linear alkyl compound C contains a monohydric carboxylic acid.

[0047] The monohydric alcohol is preferably a monohydric alcohol having 2 to 24 carbon atoms, more preferably one having 16 to 24 carbon atoms, and particularly preferably one having 18 to 22 carbon atoms. Furthermore, an aliphatic monohydric alcohol is preferred, and more preferably a linear aliphatic monohydric alcohol.

[0048] Examples of monohydric alcohols include ethanol, n-butanol, isobutanol, sec-butanol, n-hexanol, n-octanol, lauryl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, lignoceryl alcohol, 2-ethylhexanol, decanol, cyclohexanol, benzyl alcohol, and dodecyl alcohol. Among these, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, and lignoceryl alcohol are preferred.

[0049] The monovalent carboxylic acid is preferably a monovalent carboxylic acid having 2 to 24 carbon atoms, more preferably 16 to 24 carbon atoms, and particularly preferably 18 to 22 carbon atoms. Furthermore, an aliphatic monovalent carboxylic acid is preferred, and more preferably a linear aliphatic monovalent carboxylic acid.

[0050] Examples of monovalent carboxylic acids include monocarboxylic acids such as benzoic acid, naphthalenecarboxylic acid, salicylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, phenoxyacetic acid, biphenylcarboxylic acid, acetic acid, propionic acid, butyric acid, octanoic acid, decanoic acid, dodecanoic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, and lignoceric acid. Among these, palmitic acid, stearic acid, arachidic acid, behenic acid, and lignoceric acid are preferred.

[0051] The crystalline polyester resin preferably contains a condensed polymer of an aliphatic diol having 2 to 22 carbon atoms and an aliphatic dicarboxylic acid having 2 to 22 carbon atoms. That is, the crystalline polyester resin preferably has monomer units corresponding to the aliphatic diol having 2 to 22 carbon atoms and monomer units corresponding to the aliphatic dicarboxylic acid having 2 to 22 carbon atoms. In crystalline polyester resins, the total content ratio of monomer units corresponding to aliphatic diols having 2 to 22 carbon atoms and monomer units corresponding to aliphatic dicarboxylic acids having 2 to 22 carbon atoms is, for example, 50 to 100% by mass, preferably 80 to 99% by mass, and more preferably 90 to 98% by mass. In mol%, 90 to 99 mol% is preferred, and 95 to 98 mol% is more preferred.

[0052] Furthermore, it is preferable that the crystalline polyester resin is a condensed polymer of an aliphatic diol having 2 to 22 carbon atoms and an aliphatic dicarboxylic acid having 2 to 22 carbon atoms, with the main skeleton (structure other than the linear alkyl compound C condensed at the ends) being composed of these two aliphatic diols. In crystalline polyester resins, the content of structures in which linear alkyl compound C at the molecular chain terminals is condensed is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, and 2 to 10% by mass. A percentage (%) is more preferable. In mol%, 1 to 10 mol% is preferred, and 2 to 5 mol% is more preferable.

[0053] Let Cal be the number of carbon atoms in the aliphatic diol constituting the main skeleton of the crystalline polyester resin, and Cca be the number of carbon atoms in the aliphatic dicarboxylic acid constituting the main skeleton of the crystalline polyester resin. Also, let Cend be the number of carbon atoms in the linear alkyl compound C condensed at the end of the crystalline polyester resin. In this case, it is preferable that the relationship Cend-(Cal+Cca)≧8 is satisfied.

[0054] Here, the number of carbon atoms for each component is determined by the number of carbon atoms of the component with the highest content (on a molar basis) if there are multiple aliphatic diols or aliphatic dicarboxylic acids that constitute the main skeleton of the crystalline polyester resin. If the content is the same, the number of carbon atoms of the component with the longer carbon count is used. The same applies to the number of carbon atoms of the linear alkyl compound C condensed at the end.

[0055] A Cend-(Cal+Cca) ratio of 8 or greater means that the total number of carbon atoms in the aliphatic diols and aliphatic dicarboxylic acids constituting the main skeleton is shorter than the number of carbon atoms at the terminals. When this relationship is satisfied, crystallization of the crystalline polyester component constituting the main skeleton is more likely to occur during cooling, and the terminal alkyl groups interact more easily with other binder resins. As a result, the values ​​of G'3(70) / G'2(70) and the absolute value of d(logG'2(T2)) / dT tend to be larger, making it easier to control within the aforementioned range, which is preferable.

[0056] Cend-(Cal+Cca) is, for example, 2 to 14, preferably 8 to 14, more preferably 8 to 12, and even more preferably 8 to 10.

[0057] The melting point Tc of the crystalline resin (preferably a crystalline polyester resin) is preferably 70 to 100°C, more preferably 80 to 100°C, even more preferably 80 to 95°C, and even more preferably 80 to 90°C. The weight-average molecular weight Mwc of the THF-soluble component of the crystalline resin (preferably a crystalline polyester resin) is preferably 10,000 to 100,000, more preferably 16,000 to 100,000, even more preferably 18,000 to 50,000, and even more preferably 18,000 to 30,000.

[0058] Crystalline polyester resins can be produced according to conventional polyester synthesis methods. For example, a desired crystalline polyester resin can be obtained by esterifying or transesterifying the aforementioned carboxylic acid monomer and alcohol monomer, and then carrying out a condensation polymerization reaction under reduced pressure or by introducing nitrogen gas according to a conventional method.

[0059] The above esterification or transesterification reactions can be carried out using conventional esterification or transesterification catalysts such as sulfuric acid, titanium butoxide, dibutyltin oxide, manganese acetate, or magnesium acetate, as needed.

[0060] Furthermore, the above condensation polymerization reaction can be carried out using conventional polymerization catalysts, such as known catalysts like titanium butoxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, and germanium dioxide. The polymerization temperature and catalyst amount are not particularly limited and can be determined as appropriate.

[0061] In esterification, transesterification, or condensation polymerization reactions, methods such as charging all monomers at once to increase the strength of the resulting crystalline polyester resin, or first reacting divalent monomers and then adding trivalent or higher monomers to reduce the amount of low molecular weight components, may be used.

[0062] The content of crystalline resin (preferably crystalline polyester resin) in the toner is preferably 1 to 30% by mass, based on the mass of the toner, from the viewpoint of achieving both low-temperature fixability, suppression of image defects during double-sided printing, and electrostatic stability. More preferably, the content is 3 to 20% by mass, and even more preferably 5 to 15% by mass. Crystalline polyester resins may be used alone or in combination with other materials.

[0063] The binder resin may contain other binder resins in addition to the crystalline resins mentioned above. The binder resin preferably contains an amorphous resin. If an amorphous resin is further included as the binder resin, any known amorphous resin can be used.

[0064] Examples of amorphous resins include the following: Polyvinyl chloride, phenolic resin, natural resin-modified phenolic resin, natural resin-modified maleic acid resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumarone-indene resin, petroleum-based resin, vinyl-based resin. Among these, it is preferable to include at least one resin selected from the group consisting of a hybrid resin in which a vinyl resin and a polyester resin are bonded, a polyester resin, and a vinyl resin.

[0065] More preferably, the binder resin is amorphous polyester resin. That is, it is preferable that the binder resin contains amorphous polyester resin. By using amorphous polyester resin, the above-mentioned interactions with crystalline polyester resin become easier to occur. Therefore, it becomes easier to control the values ​​of G'3(70) / G'2(70), G'3(50), and G'3(70) within the above-mentioned range.

[0066] As the amorphous polyester resin, polyester resins commonly used in toners can be suitably used. Examples of monomers used in the polyester resin include polyhydric alcohols (dihydric or trihydric or higher alcohols), polyhydric carboxylic acids (dihydric or trihydric or higher carboxylic acids), their acid anhydrides, or their lower alkyl esters.

[0067] The amorphous polyester resin is preferably a condensation polymer of an alcohol and a carboxylic acid, with a polyhydric alcohol having an aromatic ring as the main component. With respect to the polyhydric alcohol having an aromatic ring, it is preferable that the content of aromatic diols in the total alcohol constituting the amorphous polyester resin is 50 to 100% by mass and 80 to 99% by mass. That is, it is preferable that the content of monomer units corresponding to aromatic diols among the monomer units corresponding to the total alcohol constituting the amorphous polyester resin is 50 to 100% by mass and 80 to 99% by mass. In mol%, it is preferably 50 to 100 mol%, and more preferably 80 to 99 mol%.

[0068] Examples of such polyhydric alcohols include the following: Examples of dihydric alcohols having an aromatic ring include the following bisphenol derivatives. Polyoxypropylene(2,2)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene(3.3)-2,2-bis(4-hydroxyphenyl)propane, polyoxyethylene(2.0)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene(2.0)-polyoxyethylene(2.0)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene(6)-2,2-bis(4-hydroxyphenyl) (Loxyphenyl) Propane, etc.

[0069] Other polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, and 1,3,5-trihydroxymethylbenzene. These polyhydric alcohols can be used individually or in combination.

[0070] Examples of polycarboxylic acids include the following: Examples of divalent carboxylic acids include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, malonic acid, n-dodecenylsuccinic acid, isododecenylsuccinic acid, n-dodecylsuccinic acid, isododecylsuccinic acid, n-octenylsuccinic acid, n-octylsuccinic acid, isooctenylsuccinic acid, isooctylsuccinic acid, anhydrides of these acids, and lower alkyl esters thereof. Of these, maleic acid, fumaric acid, terephthalic acid, n-dodecenylsuccinic acid, and adipic acid are preferably used.

[0071] Examples of trivalent or higher carboxylic acids, their acid anhydrides, or their lower alkyl esters include the following: 1,2,4-Benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalentricarboxylic acid, 1,2,4-naphthalentricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra(methylenecarboxy)methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, empol trimeric acid, their acid anhydrides, or their lower alkyl esters.

[0072] Of these, 1,2,4-benzenetricarboxylic acid (trimellitic acid) or its acid anhydride derivatives are preferred because they are inexpensive and easy to control the reaction. These polycarboxylic acids can be used individually or in combination.

[0073] The polycarboxylic acid in the amorphous polyester resin preferably contains monomer units corresponding to linear aliphatic dicarboxylic acids. When amorphous polyester resins have monomer units corresponding to linear aliphatic dicarboxylic acids, they interact more readily with alkyl groups at the molecular chain ends of crystalline polyester resins. Therefore, it becomes easier to control the values ​​of G'3(70) / G'2(70), G'3(50), and G'3(70) within the aforementioned ranges.

[0074] Among these, linear aliphatic dicarboxylic acids having 4 to 12 carbon atoms are preferred. Examples include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dodecanediic acid.

[0075] In the total carboxylic acids constituting the amorphous polyester, it is preferable that the content of monomer units corresponding to linear aliphatic dicarboxylic acids is 1 to 50 mol%. More preferably... The concentration is 10-50 mol%, more preferably 15-40 mol%. In terms of mass%, 1-20 mass% and 3-15 mass% are preferred.

[0076] Furthermore, it is preferable that the amorphous polyester resin is a resin having molecular chain ends condensed with at least one linear alkyl compound A selected from the group consisting of aliphatic linear monocarboxylic acids (e.g., having 6 to 24 carbon atoms) and aliphatic linear monoalcohols (e.g., having 6 to 24 carbon atoms).

[0077] If a carboxyl group is present at the molecular chain end of the amorphous polyester resin before the monomer having 6 to 24 carbon atoms is condensed, a condensation reaction with a linear alkyl monoalcohol occurs. If a hydroxyl group is present at the molecular chain terminus of the amorphous polyester resin before the monomer having 6 to 24 carbon atoms is condensed, a condensation reaction with a linear alkyl monocarboxylic acid occurs.

[0078] When an amorphous polyester resin has a structure in which one or more monomers selected from the group consisting of aliphatic linear monocarboxylic acids having 6 to 24 carbon atoms and aliphatic linear monoalcohols having 6 to 24 carbon atoms are condensed at the molecular chain ends, this structure readily interacts with the alkyl groups at the ends of crystalline polyester resins.

[0079] As a result, the interaction between the crystalline polyester resin and the amorphous polyester resin becomes stronger during the cooling process after melting. Therefore, it becomes easier to control the values ​​of G'3(70) / G'2(70), G'3(50), and G'3(70) within the ranges mentioned above. Consequently, the image intensity after the toner has solidified is improved, and the effect of suppressing image defects during double-sided printing is enhanced, which is preferable.

[0080] Examples of aliphatic linear monocarboxylic acids with 6 to 24 carbon atoms include hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, stearylic acid, arachidic acid, behenic acid, and lignoceric acid.

[0081] Examples of aliphatic linear monoalcohols with 6 to 24 carbon atoms include n-hexanol, n-octanol, lauryl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, and lignoceryl alcohol.

[0082] More preferably, it is at least one selected from the group consisting of linear alkyl monocarboxylic acids having 16 to 24 carbon atoms and aliphatic linear monoalcohols having 16 to 24 carbon atoms. Linear alkyl compound A preferably contains an aliphatic linear monocarboxylic acid. Particularly preferred is an aliphatic linear monocarboxylic acid having 16 to 24 carbon atoms, and among these, an aliphatic linear monocarboxylic acid having 18 to 24 carbon atoms is preferred.

[0083] The amorphous polyester resin obtained by condensing the linear alkyl compound A described above is referred to as amorphous polyester resin A. It is preferable that the binder resin contains amorphous polyester resin A. In amorphous polyester resin A, the content of the structure in which linear alkyl compound A at the molecular chain terminals is condensed is preferably 0.5 to 15% by mass, more preferably 1 to 10% by mass, and even more preferably 1 to 5% by mass. In mol%, it is preferably 1 to 15 mol%, and more preferably 2 to 10 mol%.

[0084] Let Aend be the number of carbon atoms in linear alkyl compound A at the end of the amorphous polyester molecular chain. Also, let Cend be the number of carbon atoms in linear alkyl compound C at the end of the molecular chain of the crystalline polyester resin. In this case, Cend ≥ 16 -4 ≤ Cend - Aend ≤ 6 It is preferable that the relationship is satisfied.

[0085] When Cend-Aend satisfies the above relationship, it means that the number of carbon atoms at the end of the molecular chain of the crystalline polyester resin and the number of carbon atoms at the end of the molecular chain of the amorphous polyester resin are close. As a result, the interaction between the alkyl groups at the ends of the crystalline polyester resin and amorphous polyester resin is more effective, which is preferable. Therefore, it becomes easier to control the values ​​of G'3(70) / G'2(70), G'3(50), G'3(70), and d(logG'2(T2)) / dT within the ranges mentioned above.

[0086] Cend-Aend may be, for example, -4 to 22, and more preferably -2 to 4. Cend is more preferably 16 to 24, and even more preferably 18 to 22.

[0087] Furthermore, it is preferable that Aend ≥ 16. Aend is, for example, 6 to 26, preferably 16 to 24, and more preferably 16 to 22. Regarding Cend and Aend, if there are multiple linear alkyl compound Cs, the number of carbon atoms for each is determined by the number of carbon atoms of the component with the highest content (on a molar basis). If the content is the same, the number of carbon atoms of the component with the longest carbon count is used.

[0088] The method for producing the polyester resin is not particularly limited, and known methods can be used. For example, the polyhydric alcohol and polyhydric carboxylic acid mentioned above are charged simultaneously, and polymerization is carried out via an esterification reaction or transesterification reaction and a condensation reaction to produce the polyester resin. The polymerization temperature is not particularly limited, but a range of 180°C to 290°C is preferred. When polymerizing the polyester resin, polymerization catalysts such as titanium-based catalysts, tin-based catalysts, zinc acetate, antimony trioxide, and germanium dioxide can be used.

[0089] The polyester resin is preferably obtained by condensation polymerization using at least one of a titanium-based catalyst and a tin-based catalyst.

[0090] The softening point Tm of amorphous polyester resin A is preferably 80 to 150°C, or 85 to 105°C. The weight-average molecular weight Mwa of the THF-soluble component of amorphous polyester resin A is preferably 3,000 to 1,000,000, 3,000 to 20,000, or 4,000 to 8,000.

[0091] The amorphous resin can be used alone or in combination with other amorphous resins. It is preferable to use multiple amorphous polyesters with a softening point difference of 20 to 60°C, as this makes it easier to control the toner's G'1(100), G'3(50), and G'3(70) within the above-mentioned ranges. More preferably, it is preferable to use multiple amorphous polyesters with a softening point difference of 35 to 60°C.

[0092] The amorphous resin preferably includes amorphous polyester resin B, which is different from amorphous polyester resin A, in addition to amorphous polyester resin A. The softening point Tm of amorphous polyester resin B is preferably 20 to 60°C higher, and more preferably 35 to 60°C higher, than the softening point Tm of amorphous polyester resin A. The mass ratio of amorphous polyester resin A, which has a low softening point, to amorphous polyester resin B, which has a high softening point, is preferably 30 / 70 to 90 / 10, and more preferably 50 / 50 to 80 / 20.

[0093] Amorphous polyester resin B can be a condensation polymer of an alcohol other than the monoalcohol and monocarboxylic acid in amorphous polyester resin A described above, and a carboxylic acid.

[0094] The alcohol preferably contains an aromatic diol. The aromatic diol content in the total alcohol constituting amorphous polyester resin B is preferably 80 to 100 mol%, and more preferably 90 to 100 mol%. In terms of mass%, it is preferably 80 to 100% by mass, and more preferably 90 to 100% by mass. The carboxylic acid is preferably at least one selected from the group consisting of adipic acid, maleic acid, fumaric acid, and terephthalic acid. The amorphous polyester resin B is preferably crosslinked with a trivalent carboxylic acid such as trimellitic acid or trimellitic anhydride.

[0095] The glass transition temperature (TgB) of amorphous polyester resin B, as measured by a differential scanning calorimetry analyzer, is preferably 50.0°C to 70.0°C, and more preferably 54.0°C to 60.0°C. The weight-average molecular weight Mwb of amorphous polyester resin B is preferably 20,000 to 300,000, 50,000 to 200,000, or 80,000 to 150,000. The softening point Tm of amorphous polyester resin B is preferably 120 to 170°C, and more preferably 130 to 160°C.

[0096] Examples of amorphous resins include the content of amorphous polyester resin A being 50.0 to 95.0% by mass and 60.0 to 80.0% by mass. Examples of amorphous resins include the content of amorphous polyester resin B at 5.0-50.0% by mass and 20.0-40.0% by mass. Examples of amorphous polyester resin A content based on the mass of toner particles include 20.0-80.0% by mass, 30.0-70.0% by mass, and 40.0-60.0% by mass. Based on the mass of toner particles, the content of amorphous polyester resin B can be, for example, 5.0-45.0% by mass, 10.0-35.0% by mass, or 17.0-28.0% by mass.

[0097] Furthermore, if the amorphous polyester resin contains amorphous polyester resin A having a structure in which the above-mentioned linear alkyl compound A is condensed at the molecular chain end, it is preferable that the following conditions are met. That is, let Mwa be the weight-average molecular weight of the THF-soluble component of the amorphous polyester resin A, and let Mwc be the weight-average molecular weight of the THF-soluble component of the crystalline polyester resin. In this case, it is preferable that Mwa / Mwc is, for example, 0.65 or less, and that the relationship Mwa / Mwc ≤ 0.50 is met.

[0098] When Mwa / Mwc satisfies the above relationship, although the mechanism is unknown, it is preferable because the electrostatic stability during durable printing is further improved. More preferably, Mwa / Mwc ≤ 0.4. Mwa / Mwc is preferably 0.10 to 0.50, and more preferably 0.20 to 0.40.

[0099] The binder resin may contain a vinyl resin. Examples of vinyl resins that can be used as a binder resin include polymers of vinyl monomers containing ethylenically unsaturated bonds. Ethylenelycol unsaturated bonds refer to carbon-carbon double bonds that can be radically polymerized, and examples include vinyl groups, propenyl groups, acryloyl groups, and methacryloyl groups.

[0100] Examples of vinyl monomers include the following: Styrene monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, and p-nitrostyrene; Acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, and other acrylic acid esters; Methacrylic acid esters such as methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, and diethylaminoethyl methacrylate; Also, acrylonitrile, methacrylonitrile, acrylamide, etc. Furthermore, polymerizable monomers having a hydroxyl group, such as acrylic acid or methacrylic acid esters like 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate, and 4-(1-hydroxy-1-methylbutyl)styrene and 4-(1-hydroxy-1-methylhexyl)styrene. These can be used individually or in combination.

[0101] In particular, it is preferable to use monomers that are condensates of acrylic acid or methacrylic acid with an alcohol having 6 to 22 carbon atoms, such as n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, and stearyl methacrylate.

[0102] In addition to the above, various polymerizable monomers capable of vinyl polymerization may be used in combination with the vinyl resin as needed.

[0103] Examples of polymerizable monomers include the following: Unsaturated monoolefins such as ethylene, propylene, butylene, and isobutylene; unsaturated polyenes such as butadiene and isoprene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide, and vinyl fluoride; vinyl esters such as vinyl acetate, vinyl propionate, and vinyl benzoate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and methyl isopropenyl ketone; N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, and N-vinylpyrrolidone; vinylnaphthalenes; and compounds such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, and mesaconic acid. Unsaturated dibasic acids; unsaturated dibasic acid anhydrides such as maleic anhydride, citraconic acid anhydride, itaconic acid anhydride, and alkenyl succinic acid anhydride; half-esters of unsaturated basic acids such as methyl maleate half-ester, ethyl maleate half-ester, butyl maleate half-ester, methyl citraconic acid half-ester, ethyl citraconic acid half-ester, butyl citraconic acid half-ester, methyl itaconic acid half-ester, alkenyl succinic acid half-ester, methyl fumarate half-ester, and methyl mesaconate half-ester; unsaturated basic acid esters such as dimethyl maleic acid and dimethyl fumaric acid; acid anhydrides of α,β-unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, and cinnamic acid; and the combination of the α,β-unsaturated acid with lower fatty acids. Water compounds; polymerizable monomers having a carboxyl group, such as alkenylmalonic acid, alkenyl glutaric acid, alkenyl adipic acid, their acid anhydrides, and their monoesters.

[0104] Furthermore, the vinyl resin may be a polymer crosslinked with a crosslinkable polymerizable monomer, as exemplified below, if necessary. Examples of the crosslinkable polymerizable monomer include the following: Aromatic divinyl compounds; diacrylate compounds linked by alkyl chains; diacrylate compounds linked by alkyl chains containing ether bonds; diacrylate compounds linked by chains containing aromatic groups and ether bonds; polyester-type diacrylates; polyfunctional crosslinking agents.

[0105] Examples of the aromatic divinyl compound include divinylbenzene and divinylnaphthalene. Examples of diacrylate compounds linked by alkyl chains include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and variations of these compounds in which the acrylate is replaced with methacrylate.

[0106] Furthermore, the vinyl resin may be a copolymer of monomers comprising at least one polymerizable monomer selected from the above vinyl monomers, and at least one crosslinkable polymerizable monomer selected from the group consisting of divinylbenzene, divinylnaphthalene, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,5-pentanediol dimethacrylate, 1,6-hexanediol dimethacrylate, and neopentyl glycol dimethacrylate. The content of the crosslinkable polymer in the monomer should be approximately 0.5% to 5.0% by mass.

[0107] The vinyl resin may be a resin produced using a polymerization initiator. From the viewpoint of efficiency, the polymerization initiator is preferably used in an amount of 0.05 parts by mass or more and 10.00 parts by mass or less per 100.00 parts by mass of polymerizable monomer. The following are examples of polymerization initiators.

[0108] 2,2'-Azobisisobutyronitrile, 2,2'-Azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-Azobis(2,4-dimethylvaleronitrile), 2,2'-Azobis(2-methylbutyronitrile), dimethyl-2,2'-Azobisisobutyrate, 1,1'-Azobis(1-cyclohexanecarbonitrate), 2-Carbamoylazoisobutyronitrile, 2,2'-Azobis(2,4,4-trimethylpentane), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2'-Azobis(2-methylpropane), Ketone peroxides such as methyl ethyl ketone peroxide, acetylacetone peroxide, and cyclohexanone peroxide, 2 ,2-bis(tert-butylperoxy)butane, tert-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-tert-butylperoxide, tert-butylcumylperoxide, dicumylperoxide, α,α'-bis(tert-butylperoxyisopropyl)benzene, isobutylperoxide, octanoylperoxide, decanoylperoxide, lauroylperoxide, 3,5,5-trimethylhexanoylperoxide, benzoylperoxide, m-trioylperoxide, diisopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, Di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, dimethoxyisopropyl peroxydicarbonate, di(3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxyisobutyrate, tert-butyl peroxyneodecanoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxylaurate, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, di-tert-butyl peroxyisophthalate, tert-butyl peroxyallyl carbonate, tert-amyl peroxy-2-ethylhexanoate, di-tert-butyl peroxyhexahydroterephthalate, di-tert-butyl peroxyazelate.

[0109] The vinyl resin and polyester resin used to form the hybrid resin, which is a combination of vinyl resin and polyester resin, can be the same as those used for the amorphous resin described above.

[0110] One method for producing a hybrid resin in which vinyl resin and polyester resin are bonded together is to polymerize using a compound that can react with either of the monomers that make up both resins (hereinafter referred to as "dual-reactive compound").

[0111] Examples of both reactive compounds include fumaric acid, acrylic acid, methacrylic acid, citraconic acid, maleic acid, and dimethyl fumarate. Of these, fumaric acid, acrylic acid, and methacrylic acid are preferably used.

[0112] When a hybrid resin is used in which vinyl resin and polyester resin are bonded, the content of vinyl resin in the hybrid resin is preferably 10% by mass or more, 20% by mass or more, 40% by mass or more, 60% by mass or more, 80% by mass or more, and preferably 100% by mass or less, or 90% by mass or less.

[0113] Furthermore, the binder resin may also contain polymers having a structure formed by the reaction of vinyl resin components and hydrocarbon compounds. Among these, it is preferable that the binder resin contains a graft polymer in which vinyl monomers are graft polymerized onto polyolefins. The vinyl monomers preferably include at least one selected from the group consisting of acrylic acid esters, styrene, and (meth)acrylonitrile. The binder resin may also contain a graft polymer in which styrene acrylic resin is grafted onto polyolefins.

[0114] When the binder resin contains the graft polymer, the compatibility between the wax and the resin is promoted, making it easier to suppress static charge defects and material contamination caused by poor wax dispersion. The content of the graft polymer, in which vinyl monomers are graft polymerized onto polyolefin, is preferably 1.0 to 15.0% by mass, and more preferably 2.0 to 10.0% by mass, based on the mass of the toner.

[0115] When the content is within the above range, the dispersion of wax in the binder resin tends to be uniform. The polyolefin is not particularly limited as long as it is a polymer or copolymer of unsaturated hydrocarbons, and various polyolefins can be used. Polyethylene-based and polypropylene-based polyolefins are particularly preferred. Multiple types of these may be used. The vinyl monomer should be selected from the monomers that can be used in the vinyl resins mentioned above.

[0116] Graft polymers, obtained by graft polymerization of vinyl monomers onto polyolefins, can be acquired by known methods, such as the reactions of these polymers with each other or the reactions of monomers from one polymer with those from the other.

[0117] <Other resins> The binder resin may contain resins other than those described above, to the extent that they do not impair the effects of the present disclosure, for purposes such as improving pigment dispersibility.

[0118] Examples of such resins include the following: Polyvinyl chloride, phenolic resin, natural resin-modified phenolic resin, natural resin-modified maleic acid resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumarone-indene resin, petroleum-based resin.

[0119] The binder resin content is preferably 70-98% by mass, and more preferably 80-95% by mass, based on the mass of the toner.

[0120] <wax> Toner particles contain wax. The wax should be selected and used in combination with the crystalline resin to ensure optimal performance. Examples of waxes include:

[0121] Hydrocarbon waxes such as microcrystalline wax, paraffin wax, and Fischer-Tropsch wax; oxides of hydrocarbon waxes such as oxidized polyethylene wax or block copolymers thereof; waxes mainly composed of fatty acid esters such as carnauba wax; and deoxidized fatty acid esters such as deoxidized carnauba wax, which have been partially or completely deoxidized.

[0122] Furthermore, the following can be listed: Saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid, and parinalic acid; saturated alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melissyl alcohol; polyhydric alcohols such as sorbitol; esters of fatty acids such as palmitic acid, stearic acid, behenic acid, and montanic acid with alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melissyl alcohol; fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide; methylenebisstearate amide, ethylenebiscaprate amide, ethylenebislaurate amide, hexamethylene Saturated fatty acid bisamides such as bis-stearamide; unsaturated fatty acid amides such as ethylenebisoleamide, hexamethylenebisoleamide, N,N'dioleyladipamide, and N,N'dioleylsebacamide; aromatic bisamides such as m-xylenebis-stearamide and N,N'distearylisophthalamide; fatty acid metal salts (commonly known as metal soaps) such as calcium stearate, calcium laurate, zinc stearate, and magnesium stearate; waxes grafted onto aliphatic hydrocarbon waxes with vinyl monomers such as styrene or acrylic acid; partially esterified fatty acids and polyhydric alcohols such as behenic acid monoglyceride; and methyl ester compounds having hydroxyl groups obtained by hydrogenation of vegetable oils.

[0123] The wax preferably contains at least one selected from the group consisting of ester waxes and hydrocarbon waxes, more preferably a hydrocarbon wax, and even more preferably a Fischer-Tropsch wax. The melting point of the wax is preferably 75°C to 120°C, more preferably 84°C to 120°C, and even more preferably 88°C to 110°C. Furthermore, the difference between the melting point Tc of the crystalline resin and the melting point of the wax is more preferably within 10°C.

[0124] When the wax contains hydrocarbon wax, the hydrocarbon wax is more likely to interact with the binder resin along with the crystalline resin during cooling after melting. Compared to when the wax does not contain hydrocarbon wax, the increase in storage modulus during cooling becomes more gradual, making it easier to control the G'3(70) / G'2(70) value to a higher level.

[0125] Furthermore, when the wax is analyzed by gas chromatography-mass spectrometry (GC / MS), the number of carbon atoms corresponding to the peak detected as the maximum peak is defined as Wmax. In this case, Wmax-Aend is, for example, between 12 and 42, and it is preferable that Wmax and Aend satisfy the relationships Aend ≥ 16 and 16 ≤ Wmax-Aend ≤ 30.

[0126] When Wmax-Aend satisfies this range, the value of G'3(70) can be increased more easily, and image defects during double-sided printing can be suppressed more effectively. This is thought to be because, during the cooling process after melting the crystalline polyester resin, the crystalline polyester resin moves more easily in a way that increases the value of G'3(70). More preferably, 20 ≤ Wmax-Aend ≤ 30, and even more preferably, 20 ≤ Wmax-Aend ≤ 25.

[0127] The wax content is preferably 2.0 to 30.0% by mass, more preferably 4.0 to 20.0% by mass, and even more preferably 4.0 to 10.0% by mass, based on the mass of the toner.

[0128] <Inorganic filler particles> The toner particles may contain inorganic filler particles as needed, such as for adjusting viscoelasticity. Preferred inorganic filler particles include silica, titanium oxide, aluminum oxide, metal titanates such as strontium titanate and calcium titanate, calcium carbonate, and kaolin.

[0129] It is preferable that the inorganic filler particles are treated with fatty acids. Surface treatment of the filler particles with fatty acids is preferable because it allows the filler effect to be expressed more effectively by interacting with the alkyl group of the crystalline resin via the fatty acids.

[0130] The number-average diameter of the primary inorganic filler particles embedded in the toner particles is preferably 0.15 to 0.45 μm, and more preferably 0.20 to 0.40 μm. The number-average diameter of the primary inorganic filler particles can be measured using known means such as a scanning electron microscope.

[0131] The content of inorganic filler particles, based on the mass of toner particles, is preferably 0 to 20% by mass, and more preferably 0 to 7% by mass.

[0132] <Coloring agent> Toner particles may contain colorants as needed. Examples of colorants include: Examples of black colorants include carbon black; and black produced by mixing yellow, magenta, and cyan colorants. While pigments may be used alone as colorants, it is preferable to use dyes and pigments in combination to improve clarity, which enhances the image quality of full-color images.

[0133] Examples of pigments for magenta toner include the following: CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 3 7, 38, 39, 40, 41, 48:2, 48:3, 48:4, 49, 50, 51, 52, 53, 54, 55, 57:1, 58, 60, 63, 64, 68, 81:1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 147, 150, 163, 184, 202, 206, 207, 209, 238, 269, 282; CI Pigment Violet 19; CI Bat Red 1, 2, 10, 13, 15, 23, 29, 35.

[0134] Examples of dyes used for magenta toner include the following: Oil-soluble dyes such as CI Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; CI Disperse Red 9; CI Solvent Violet 8, 13, 14, 21, 27; CI Disperse Violet 1; basic dyes such as CI Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; CI Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.

[0135] Examples of pigments used for cyan toner include the following: CI Pigment Blue 2, 3, 15:2, 15:3, 15:4, 16, 17; CI Bat Blue 6; CI Acid Blue 45; copper phthalocyanine pigments with 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton. CI Solvent Blue 70 is a dye used for cyan toner.

[0136] Examples of pigments for yellow toner include the following: CI Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; CI Bat Yellow 1, 3, 20. CI Solvent Yellow 162 is a dye used for yellow toner.

[0137] These colorants can be used individually, in combination, or even in solid solution form. The colorants are selected based on their hue angle, saturation, brightness, lightfastness, OHP transparency, and dispersibility in toner. The coloring agent content is preferably 0.1 to 30.0 parts by mass per 100 parts by mass of the binder resin.

[0138] <Charge control agent> The toner particles may contain a charge control agent as needed. While known charge control agents can be used, aromatic carboxylic acid metal compounds are particularly preferred, as they are colorless, have a fast toner charging speed, and can stably maintain a constant charge level.

[0139] Examples of negative charge control agents include salicylate metal compounds, naphthoate metal compounds, dicarboxylic acid metal compounds, polymer compounds having sulfonic acid or carboxylic acid as a side chain, polymer compounds having sulfonate salts or sulfonic acid esters as a side chain, polymer compounds having carboxylate salts or carboxylic acid esters as a side chain, boron compounds, urea compounds, silicon compounds, and calixarenes.

[0140] The charge control agent may be added internally or externally to the toner particles. The content of the charge control agent is preferably 0.2 to 10.0 parts by mass, and more preferably 0.5 to 10.0 parts by mass, per 100 parts by mass of the binder resin.

[0141] <External additives> Toner may contain external additives. For example, toner particles may be made by adding external additives. Preferred external additives are inorganic fine particles such as silica, titanium dioxide, aluminum oxide, and metal titanate salts. The inorganic fine particles used as external additives are preferably hydrophobized with a hydrophobic agent such as a silane compound, silicone oil, or a mixture thereof.

[0142] As an external additive for improving liquidity, a BET specific surface area of ​​50m² is used. 2 / g~400m 2 Inorganic fine particles of / g are preferred, and for durability stabilization, a BET specific surface area of ​​10m² is desirable. 2 / g~50m 2 It is preferable that the inorganic fine particles weigh / g. To achieve both improved fluidity and stable durability, inorganic fine particles with a BET specific surface area within the above range may be used in combination. Mixing of the toner particles and external additives can be done using a known mixer such as a Henschel mixer. The proportion of the external additive is preferably 0.1 to 10.0 parts by mass, and more preferably 2.0 to 7.0 parts by mass, per 100 parts by mass of toner particles.

[0143] <Developer> Toner can be used as a one-component developer, but it is preferable to mix it with a magnetic carrier and use it as a two-component developer, as this allows for stable images over a long period of time. In other words, a two-component developer containing toner and a magnetic carrier is preferable, where the toner is the toner described above.

[0144] Examples of magnetic carriers include, for example, iron powder or iron powder with an oxidized surface; metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, and rare earth elements, their alloy particles or oxide particles; magnetic materials such as ferrite; and magnetic material dispersion resin carriers (so-called resin carriers) containing the magnetic material and a binder resin that holds the magnetic material in a dispersed state. These are generally known examples. When toner is mixed with a magnetic carrier and used as a two-component developer, the toner content in the two-component developer is preferably 2.0% by mass or more and 15.0% by mass or less, and more preferably 4.0% by mass or more and 13.0% by mass or less.

[0145] <Toner manufacturing method> The method for manufacturing the toner is not particularly limited, and conventionally known manufacturing methods such as suspension polymerization, emulsification and agglutination, melt-kneading, and dissolution-suspension can be employed. The following describes the toner manufacturing procedure using the melt-kneading-and-grinding method.

[0146] <Raw material mixing process> In the raw material mixing process, predetermined amounts of materials constituting toner particles are weighed, blended, and mixed. These materials include, for example, binder resins containing crystalline resin and, if necessary, amorphous resin, wax, and, if necessary, other components such as colorants and charge control agents. Examples of mixing equipment include double-con mixers, V-type mixers, drum-type mixers, super mixers, Henschel mixers, Nauta mixers, and Mechanohybrid (manufactured by Nippon Coke Industries Co., Ltd.).

[0147] <Melting and mixing process> Next, the mixed materials are melt-kneaded to disperse wax and other substances in the binder resin. In the melt-kneading process, batch-type kneaders such as pressure kneaders and Banbury mixers, as well as continuous-type kneaders, can be used, and single-screw or twin-screw extruders are the mainstream due to their advantage of being able to produce continuously. For example, KTK twin-screw extruders (manufactured by Kobe Steel, Ltd.), TEM twin-screw extruders (manufactured by Toshiba Machine Co., Ltd.), PCM kneaders (manufactured by Ikegai Iron Works, Ltd.), twin-screw extruders (manufactured by KCK Co., Ltd.), and Co. Ni Examples include der (manufactured by Buss Co., Ltd.) and Nidex (manufactured by Nippon Coke Industries Co., Ltd.). Furthermore, the resin composition obtained by melt-kneading may be rolled with two rolls or the like and cooled with water in a cooling process.

[0148] In the melt-kneading process, it is preferable to use a twin-screw extruder for melt-kneading. The mixing temperature is preferably 110 to 160°C, more preferably 110 to 150°C. The screw rotation speed during mixing is not particularly limited and can be appropriately changed depending on the apparatus, but for example, 200 to 300 rpm is preferred.

[0149] <Cooling process> The means of the cooling process are not particularly limited. Examples include rolling the kneaded resin composition with twin-screw rollers or a drum and then cooling it with a steel belt cooler (manufactured by Nippon Steel Conveyor Co., Ltd.), or rolling while cooling with a drum equipped with press rollers and an internal cooling mechanism, such as a belt drum flaker (manufactured by Nippon Coke Co., Ltd.). In the cooling process, rolling while cooling with a belt drum flaker is preferred.

[0150] <Grinding process> Next, the cooled resin composition is pulverized to the desired particle size in a pulverization process. In the pulverization process, the material is coarsely pulverized using a pulverizer such as a crusher, hammer mill, or feather mill, and then further finely pulverized using a fine pulverizer such as a Kryptron system (manufactured by Kawasaki Heavy Industries), Super Rotor (manufactured by Nisshin Engineering Co., Ltd.), Turbo Mill (manufactured by Turbo Industries Co., Ltd.), or an air jet type pulverizer.

[0151] <Classification process> Subsequently, the toner particles can be obtained by classifying or sieving them using classifiers or sieving machines such as the inertial classifier Elbow Jet (manufactured by Nippon Steel Mining Co., Ltd.), the centrifugal classifier Turboplex (manufactured by Hosokawa Micron Corporation), the TSP separator (manufactured by Hosokawa Micron Corporation), or the Faculty (manufactured by Hosokawa Micron Corporation), as needed.

[0152] <External addition process> The obtained toner particles may be used as toner as is. Alternatively, toner may be obtained by externally adding an additive to the surface of the toner particles. As a method for externally adding an additive, a predetermined amount of classified toner and various known external additives is mixed together, and the mixture is stirred and mixed using a mixing device such as a double-con mixer, V-type mixer, drum-type mixer, super mixer, Henschel mixer, Nauta mixer, Mechanohybrid (manufactured by Nippon Coke Industries Co., Ltd.), or Novilta (manufactured by Hosokawa Micron Corporation) as an external additive machine.

[0153] <Annealing Process> In toner manufacturing, it is preferable to perform annealing on the molten mixture obtained after the melt-kneading process, holding it at a temperature of 5°C or higher above the melting point of the crystalline resin for 10 minutes or more. Annealing may be performed after the melt-kneading and cooling process, but it is preferable to perform it before the cooling process.

[0154] The following describes methods for measuring various physical properties of toner and raw materials. <Measurement of storage modulus G' by viscoelasticity measurement of toner> The measuring device used is the rotating flat plate rheometer "ARES" (TA INSTRUMENT A tablet manufactured by Company S will be used. As the measurement sample, a sample will be used in which toner is pressure-molded into a disc shape with a diameter of 8 mm and a thickness of 2.0 ± 0.3 mm using a tablet molding machine at a temperature of 25°C (at 20 MPa for 30 seconds). The sample is mounted on a parallel plate, heated from room temperature (25°C) to 80°C for 15 minutes to set its shape, then cooled to the temperature at which viscoelasticity measurement begins, and the measurement is started to determine the complex viscosity. Set the measurement sample so that the initial normal force is 0. Furthermore, as described below, the effect of the normal force can be canceled in subsequent measurements by enabling automatic tension adjustment (Auto Tension Adjustment ON).

[0155] The measurement will be performed under the following conditions. (1) Use a parallel plate with a diameter of 8 mm. (2) The frequency shall be 6.28 rad / sec (1.0 Hz). (3) The initial applied strain shall be set to 0.01%. (4) The measurement interval (Steptime) shall be 15 seconds. The measurement will be performed under the following automatic adjustment mode settings: Measurement will be performed in automatic strain adjustment mode (Auto Strain). (5) Set Max Applied Strain to 1.0%. (6) The maximum torque (Max Allowed Torque) is set to 150.0 g·cm, and the minimum torque (Min Allowed Torque) is set to 0.2 g·cm. (7) Set the Strain Adjustment to 20.0% of Current Strain. For measurement, use the Auto Tension mode. (8) Set Auto Tension Direction to Compression. (9) Set the initial static force to 10.0g and the auto tension sensitivity to 40.0g. (10) The operating conditions for Auto Tension are: Sample Modulus is 1.0 × 10 3 It is Pa or higher.

[0156] Step (i) Measurements are taken while increasing the temperature from 30°C to 100°C at a rate of 2°C / min to obtain the curve G'1(T) of the storage modulus G'[Pa] as a function of temperature T[°C]. Step (ii) After step (i), measurements are taken while the temperature is lowered from 100°C to 30°C at a rate of 2°C / min to obtain the curve G'2(T) of the storage modulus G'[Pa] as a function of temperature T[°C]. Step (iii) After step (ii), the temperature is raised from 30°C to 100°C at a rate of 2°C / min to obtain the curve G'3(T) of the storage modulus G'[Pa] as a function of temperature T[°C].

[0157] The measurement results of the storage modulus G' obtained from the above measurements are plotted as temperature on the x-axis and the common logarithm of the storage modulus G', LogG', on the y-axis, creating a temperature-storage modulus plot. After plotting, the points are smoothly connected to obtain a temperature-storage modulus curve. Next, the slope of the obtained temperature-storage modulus curve is determined, and the differential curve obtained by differentiating the common logarithm LogG' with respect to temperature is graphed. This allows us to obtain a graph where G'(T) is the storage modulus of the toner at temperature T (°C), with temperature T on the horizontal axis and the value d(logG'(T)) / dT, obtained by differentiating LogG'(T) with respect to temperature T, on the vertical axis. Using the procedure described above, a graph is obtained with respect to the curve G'2(T) where the horizontal axis is temperature T and the vertical axis is the value d(logG'2(T)) / dT, which is the derivative of LogG'2(T) with respect to temperature T.

[0158] The obtained temperature T is plotted on the horizontal axis, and the value obtained by differentiating LogG'2(T) with respect to temperature T, d(logG'2(T)) / dT, is plotted on the vertical axis. The minimum value within the range of 50.0 to 70.0°C is identified, and the temperature at which this minimum value occurs is defined as temperature T2(°C). If multiple minimum values ​​exist within the range of 50.0°C to 70.0°C, the smallest and most minimal value is selected as the minimum value, and its temperature is chosen as T2. The value of d(logG'2(T2)) / dT is then obtained. Additionally, we obtain the values ​​of G'1(100), G'3(50), G'3(70), and G'3(70) / G'2(70).

[0159] If it is difficult to smoothly connect the temperature-storage modulus plots, the measured values ​​may be smoothed to make them easier to connect. For smoothing, a simple moving average method using plots of three points before and after the current point can be used.

[0160] <Method for separating each material from toner> By utilizing the differences in the solubility of each material contained in the toner in the solvent, it is possible to separate the materials from the toner. First separation: The toner is dissolved in methyl ethyl ketone (MEK) at 23°C to separate the soluble components (amorphous resin) from the insoluble components (crystalline resin, wax, colorants, inorganic filler particles, etc.). Second separation: The insoluble components (crystalline resin, wax, colorant, inorganic filler particles, etc.) obtained in the first separation are dissolved in MEK at 100°C, separating the soluble components (crystalline resin, wax) from the insoluble components (colorant, inorganic filler particles, etc.). Third separation: The soluble components (crystalline resin, wax) obtained in the second separation are dissolved in chloroform at 23°C, and the soluble components (crystalline resin) and insoluble components (wax) are separated.

[0161] (Measurement of the content of crystalline resin, amorphous resin, and inorganic filler particles in the binder resin of toner) In each separation step obtained through the above separation process, the mass of soluble and insoluble components is measured to calculate the content of crystalline resin and amorphous resin in the binder resin of the toner.

[0162] (Calculation of monomer unit content ratios for amorphous polyester resin A, amorphous polyester resin B, and crystalline polyester resin) The content of constituent monomers in amorphous polyester resin A, amorphous polyester resin B, and crystalline polyester resin is calculated using NMR and the following method. Weigh out 5 mg of the resin to be measured and dissolve it in deuterated THF or deuterated chloroform. 1 1H-NMR measurements are performed, and the composition ratio is calculated from the integrated values ​​of each peak. The specific instrument conditions are as follows.

[0163] (Measurement conditions) Measuring device JNM-ECA400FT-NMR(JEOL) Measured radionuclides: 1 H Solvent: Deuterated THF or deuterated chloroform Measurement frequency: 400MHz Pulse width: 5.0 μs Frequency range: 10500Hz Total number of times: 64 Measurement temperature: room temperature From the obtained results, Aend, Cend, Cal, and Cca can be calculated.

[0164] <Method for measuring the melting point and endothermic peak of toners and resins, etc.> The melting point and endothermic peak of toners and resins are measured using DSC Q1000(TA Measurements will be taken using a device manufactured by Instruments Inc. under the following conditions. Heating rate: 10℃ / min Measurement start temperature: 20℃ Measurement end temperature: 180℃

[0165] The temperature correction for the device's detection unit uses the melting points of indium and zinc, and the heat of heat correction uses the heat of fusion of indium. Specifically, 5 mg of the sample is accurately weighed and placed in an aluminum pan. The sample is then placed in the container, and differential scanning calorimetry (DSC) is performed. A silver pan is used as the reference. The peak temperature of the maximum endothermic peak during the first heating process is defined as the melting point. The maximum endothermic peak is the peak with the largest amount of heat absorbed when there are multiple peaks. Furthermore, the amount of heat absorbed at this maximum endothermic peak is determined. The assignment of each peak can be determined by performing DSC measurements on each individual material separated from the toner as described above. Furthermore, the melting point Tc of the crystalline resin and the melting point Tw of the wax can be obtained.

[0166] <Method for measuring the glass transition temperature of toners and resins> The melting point of the toner and resin mentioned above, as well as the measurement of the endothermic peak and endothermic amount, are measured using DSC, similar to the same method. Measurements are performed using a Q1000 (manufactured by TA Instruments) under the following conditions: Measurements are taken within the measurement range of 20 to 180°C at a heating rate of 10°C / min. During the measurement, the resin is first heated to 200°C and held for 10 minutes, then cooled to 20°C, and then heated again. During this second heating process, the specific heat change is obtained in the temperature range of 20 to 100°C. The intersection point of the line midway between the baseline before and after the specific heat change and the differential thermal curve is defined as the glass transition temperature (Tg) of the toner and resin.

[0167] <Method for measuring the softening point (Tm) of resin> The softening point of the resin is measured using a constant-load extrusion type capillary rheometer, the "Flow Characteristics Evaluation Device Flow Tester CFT-500D" (manufactured by Shimadzu Corporation), according to the manual included with the device. With this device, a constant load is applied from the top of the sample by a piston, the sample filled in the cylinder is heated and melted, and the molten sample is extruded from a die at the bottom of the cylinder. A flow curve showing the relationship between the piston descent amount and temperature can be obtained. Furthermore, the softening point will be the "melting temperature using the 1 / 2 method" as described in the manual included with the "Flow Characteristics Evaluation Device Flow Tester CFT-500D". The melting temperature using the 1 / 2 method is calculated as follows:

[0168] First, we calculate half the difference between the piston's descent at the end of the outflow (the end of the outflow, let's call it Smax) and the piston's descent at the start of the outflow (the lowest point, let's call it Smin) (let's call this X; X = (Smax - Smin) / 2). Then, the temperature of the flow curve when the piston's descent is the sum of X and Smin is the melting temperature using the 1 / 2 method. The sample used for measurement is a cylindrical shape with a diameter of approximately 8 mm, obtained by compressing 1.0 g of resin at 10 MPa for 60 seconds in a tablet molding compressor (e.g., NT-100H, manufactured by NPA Systems Co., Ltd.) at 25°C. Specific procedures for measurement should be followed according to the manual provided with the device. The measurement conditions for the CFT-500D are as follows: Test mode: Temperature increase method Starting temperature: 50℃ Achieved temperature: 200℃ Measurement interval: 1.0℃ Heating rate: 4.0℃ / min Piston cross-sectional area: 1,000 cm² 2 Test load (piston load): 10.0 kgf (0.9807 MPa) Preheating time: 300 seconds Die hole diameter: 1.0mm Die length: 1.0mm

[0169] <Method for identifying the number of carbon atoms in the maximum peak of a wax wax> The number of carbon atoms at the maximum peak of the wax is measured as follows. Note that thermal desorption is performed using ATD. The method is performed using the Auto Thermal Desorption (AVM) method. The following measuring devices are used: Thermal desorption device: TurboMatrixATD (manufactured by PerkinElmer) GC / MS: TRACE DSQ (manufactured by Thermo Fisher Scientific)

[0170] (Preparation of glass tubes containing internal standards) A glass tube for a thermal desorption apparatus is prepared by sandwiching 10 mg of TenaxTA adsorbent between glass wool. This tube is then conditioned at 300°C for 3 hours under an inert atmosphere. Subsequently, 5 μL of a 100 ppm methanol solution of deuterated n-hexadecane (n-hexadecane D34) is adsorbed onto the TenaxTA to create a glass tube containing an internal standard. Furthermore, to distinguish the peak from the n-hexadecane contained in the wax as described above, deuterated n-hexadecane with different retention times was used as an internal standard. All volatile component concentrations are shown as converted values ​​using deuterated n-hexadecane. The conversion method for volatile component concentrations is shown below.

[0171] (Wax measurement) Wrap 1 mg of weighed wax in aluminum foil that has been preheated to 300°C, and place it in the special tube prepared in (Preparation of glass tube containing internal standard substance). Cover this sample with a Teflon® cap for the thermal desorption apparatus and set it in the thermal desorption apparatus. Measure this sample under the following conditions and calculate the retention time due to the volatile components of the internal standard substance.

[0172] (Thermal desorption equipment conditions) Tube temperature: 200℃ Transfer temperature: 300℃ Valve temperature: 300℃ Column pressure: 150kPa Inlet split: 25ml / min. Outlet split: 10 ml / min. Secondary adsorption tube material: TenaxTA Holding time: 10min. Secondary adsorption tube temperature during desorption: -30℃ Secondary adsorption tube desorption temperature: 300℃

[0173] (GC / MS conditions) Column: Ultraalloy (metal column) UT-5 (inner diameter 0.25 mm, liquid phase 0.25 μm, length 30 m) Column heating conditions: 60°C (holding time 3 minutes), heating from 60°C to 350°C (heating rate 20.0°C / min), 350°C (holding time 10 minutes) Furthermore, the transfer line of the thermal desorption unit and the GC column are directly connected, and the GC inlet is not used.

[0174] (analysis) From the peaks obtained in the above procedure, excluding the peak of the internal standard substance, deuterated n-hexadecane, identify the peak that is the largest among all peaks after the retention time of n-hexadecane, and determine the corresponding carbon number Wmax.

[0175] <Method for measuring the weight-average molecular weight (Mw) of THF-soluble components in resins, etc., using gel permeation chromatography (GPC)> The weight-average molecular weight (Mw) of the tetrahydrofuran (THF)-soluble component in resins and other materials is measured using gel permeation chromatography (GPC) as follows. First, the toner is dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. The resulting solution is then filtered through a solvent-resistant membrane filter, "Myshoridisk" (manufactured by Tosoh Corporation), with a pore diameter of 0.2 μm, to obtain the sample solution. The sample solution is adjusted so that the concentration of THF-soluble components is 0.8% by mass. This sample solution is then used for measurement under the following conditions. Equipment: HLC8320 GPC (Detector: RI) (Manufactured by Tosoh Corporation) Columns: Shodex LF-404, LF-404 double column (manufactured by Showa Denko Corporation) Eluent: Tetrahydrofuran (THF) Flow rate: 1.0ml / min Oven temperature: 40.0℃ Sample injection volume: 0.10 ml To calculate the molecular weight of the sample, a molecular weight calibration curve prepared using standard polystyrene resin (for example, "EasiVial PS-H Polystyrene," manufactured by Agilent) is used.

[0176] <Method for measuring the weight-average particle size (D4) of toner particles> The volume-average particle size (Dv) (weight-average particle size (D4)) of toner is calculated as follows. The measuring device used is the "CDA-1000X" particle counting analyzer (manufactured by Sysmex Corporation), which employs the pore electrical resistance method and is equipped with a 100 μm aperture tube. The included dedicated software, "CDA-1000X" (manufactured by Sysmex Corporation), is used to set the measurement conditions and analyze the measurement data. For the electrolytic aqueous solution used in the measurement, for example, "Cellpack" (manufactured by Sysmex Corporation) can be used. Before performing the measurements and analysis, the following settings were configured for the dedicated software. In the "Measurement Condition Settings" screen of the dedicated software, set the total count to 50,000, the number of repeated measurements to 1, and the measurement mode to total count (unlimited). The specific measurement method is as follows:

[0177] (1) Place approximately 150 ml of the electrolytic solution into a dedicated glass round-bottom beaker, set it on the sample stage, and stir with the stirring propeller at 500 rpm. Then, click "Blank Check Measurement" in the dedicated software to start the measurement and confirm that the count is less than 500. If the count is 500 or more, repeat the washing of the beaker and aperture. (2) Place 30 ml of the electrolytic aqueous solution into a 100 ml flat-bottomed glass beaker. Add 0.3 ml of a diluted solution of "Contaminon N" (a 10% by mass aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments, consisting of a nonionic surfactant, anionic surfactant, and organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) diluted three times by mass with deionized water as a dispersant. (3) Prepare an "Ultrasonic Dispension System Tetra150" (manufactured by Nikko Bios Co., Ltd.) ultrasonic disperser with an electrical output of 120W, which incorporates two oscillators with an oscillation frequency of 50kHz with a phase difference of 180 degrees. Add 3.3L of deionized water to the water tank of the ultrasonic disperser, and add 2ml of Contaminon N to this water tank. (4) Place the beaker from (2) into the beaker fixing hole of the ultrasonic disperser and operate the ultrasonic disperser. Then, adjust the height of the beaker so that the resonance state of the liquid surface of the electrolytic solution inside the beaker is maximized. (5) While irradiating the electrolytic aqueous solution in the beaker described in (4) with ultrasound, add 10 mg of toner in small amounts and disperse it. Continue the ultrasonic dispersion treatment for another 60 seconds. During ultrasonic dispersion, adjust the water temperature in the tank as appropriate so that it is between 10°C and 40°C. ru. (6) Using a pipette, the electrolytic aqueous solution (5) containing the dispersed toner is dropped into the round-bottom beaker (1) placed in the sample stand, and the concentration is adjusted to 6%. The measurement is then continued until the number of particles measured reaches 50,000. (7) The measurement data is analyzed using the dedicated software attached to the device to calculate the volume-average particle size (Dv) (weight-average particle size (D4)). [Examples]

[0178] The basic structure and features of this disclosure have been described above; however, the disclosure will now be explained in detail based on examples. Nevertheless, this disclosure is not limited thereto. In the following formulations, parts are measured by mass unless otherwise specified.

[0179] <Example of manufacturing crystalline resin 1> • Ethylene glycol (49 mol%; 20.1 parts by mass) Dodecanedioic acid (48 mol%; 73.1 parts by mass) ·Behenic acid (3 mol%; 6.8 parts by mass) • Tin 2-ethylhexanoate: 0.5 parts by mass The above materials were weighed into a reaction vessel equipped with a condenser, stirrer, nitrogen inlet tube, and thermocouple. Next, the flask was purged with nitrogen gas, and the temperature was gradually increased while stirring. The reaction was carried out at 140°C with stirring for 3 hours. 0.5% by mass of tin 2-ethylhexanoate was added relative to the total mass of monomers, and then the above materials were added. The pressure in the reaction vessel was reduced to 8.3 kPa, and the reaction was carried out for 4 hours while maintaining the temperature at 200°C. After that, the pressure in the reaction vessel was gradually released to return to atmospheric pressure to obtain crystalline resin 1. The physical properties are shown in Table 1.

[0180] <Examples of manufacturing crystalline resins 2-9> In the example of producing crystalline resin 1, the reaction was carried out in the same manner except that the materials used were changed to those shown in Table 1 and the parts by mass were changed so that the mol% was as shown in Table 1, and crystalline resins 2 to 9 were obtained. The physical properties are shown in Table 1.

[0181] [Table 1]

[0182] The values ​​for each material in Table 1 are in mol%. Tc indicates the melting point. The abbreviations in Table 1 are as follows. The numbers in parentheses represent the number of carbon atoms in the linear alkyl compound. EG: Ethylene glycol HG:1,6-Hexanediol TDD: 1,14-tetradecanediol TDA: Tetradecanoic acid (14) HDA: Hexadecanoic acid (16) SA: Stearic acid (18) BA: Behenic acid (22)

[0183] <Example of Amorphous Resin A1 Production> The following materials were added to a reaction vessel equipped with a reflux condenser, stirrer, thermometer, and nitrogen inlet tube under a nitrogen atmosphere. Polyoxyethylene (2.0)-2,2-bis(4-hydroxyphenyl)propane: 72.6 parts by mass (49.0 mol%) Terephthalic acid: 21.4 parts by mass (40.0 mol%) ·Adipic acid: 4.2 parts by mass (9.0 mol%) Stearic acid: 1.8 parts by mass (2.0 mol%) Titanium tetrabutoxide: 2.0 parts by mass Next, the flask was purged with nitrogen gas, and the temperature was gradually increased while stirring. The mixture was then stirred at 200°C and allowed to react for 2 hours while distilling off the water produced. Furthermore, the pressure in the reaction vessel was reduced to 8.3 kPa and maintained for 1 hour, after which it was cooled to 180°C and returned to atmospheric pressure (first reaction step). Subsequently, the above materials were added, the pressure in the reaction vessel was reduced to 8.3 kPa, and the reaction was carried out for 4 hours while maintaining the temperature at 150°C. The reaction was then stopped by lowering the temperature (second reaction step), yielding amorphous resin 1. The glass transition temperature (Tg) of the amorphous resin was 53°C, and the softening point was 92°C. The physical properties are shown in Table 2.

[0184] <Production Examples of Amorphous Resin A2-11> In the production example of amorphous resin A1, the materials used were changed to those shown in Table 2, and the reaction was carried out in the same manner except that the parts by mass were changed so that the mol% would be as described in Table 2, and amorphous resins A2 - A8 were obtained. The physical properties are shown in Table 2.

[0185] <(0000900)>

Table 2

[0186] The numerical values of each material in Table 2 indicate mol%. Mwa indicates the weight-average molecular weight. Tg indicates the glass transition temperature, and Tm indicates the softening point. The abbreviations are as follows. The numerical values in parentheses are the number of carbon atoms of the linear alkyl compound. BPA-PO: Polyoxypropylene (2.0)-2,2-bis(4-hydroxyphenyl)propane BPA-EO: Polyoxyethylene (2.0)-2,2-bis(4-hydroxyphenyl)propane TPA: Terephthalic acid <00009-10>AA: Adipic acid SA: Stearic acid (18) BA: Behenic acid (22) LA: Lignoceric acid (24) TDl: Tetradecanol (14)

[0187] <Production Example of Amorphous Resin B1> · Bisphenol A propylene oxide adduct (average addition mole number 2.0 mol) : 72.6 parts by mass (50.0 mol%) · Terephthalic acid: 13.2 parts by mass (25.0 mol%) · Adipic acid: 7.0 parts by mass (15.0 mol%) · Titanium tetrabutoxide (esterification catalyst): 0.5 parts by mass The above materials were weighed into a reaction vessel equipped with a condenser, a stirrer, a nitrogen inlet tube, and a thermocouple. Next, after replacing the inside of the flask with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 2 hours while stirring at a temperature of 200 °C. Furthermore, the pressure inside the reaction vessel was reduced to 8.3 kPa and maintained for one hour, then cooled to 160°C and returned to atmospheric pressure. • Trimellitus anhydride: 6.7 parts by mass (10.0 mol%) Subsequently, the above materials were added, the pressure in the reaction vessel was reduced to 8.3 kPa, and the reaction was allowed to proceed while maintaining the temperature at 200°C. After confirming that the softening point reached the temperature shown in Table 3, the temperature was lowered to stop the reaction, and amorphous polyester resin B1 was obtained. The physical properties are shown in Table 3.

[0188] [Table 3]

[0189] Mwb represents the weight-average molecular weight. Tg represents the glass transition temperature, and Tm represents the softening point. The abbreviations are as follows: BPA-PO: Polyoxypropylene (2.0)-2,2-bis(4-hydroxyphenyl)propane TPA: Terephthalic acid AA: Adipic acid TMA: Trimellitus anhydride

[0190] <Example of manufacturing graft polymer resin C1> Polyethylene (Mw: 1400, Mn: 850, endothermic peak at 100°C according to DSC) 20 parts by mass • Styrene 59 parts by mass • n-butyl acrylate 18.5 parts by mass • Acrylonitrile 2.5 parts by mass The above raw materials were placed in an autoclave, the system was purged with nitrogen, and then maintained at 180°C while heating and stirring. 50 parts by mass of a xylene solution of 2% by mass di-tert-butyl peroxide were continuously added dropwise to the system for 5 hours. After cooling, the solvent was separated and removed to obtain graft polymer resin C1 having a structure in which vinyl resin components and hydrocarbon compounds are bonded. Graft polymer resin C1 has a softening point (Tm) of 110°C and a glass transition temperature (Tg) of 64°C. It was found that the molecular weight of the THF-soluble fraction determined by GPC was 7,400 in terms of weight average molecular weight (Mw). No peak corresponding to the starting polyethylene was observed.

[0191] <Wax> The following waxes were used.

[0192]

Table 4

[0193] <Production Example of Toner Particles 1> · Crystalline resin 1: 9 parts by mass · Amorphous resin A1: 52 parts by mass · Amorphous resin B1: 23 parts by mass · Graft polymer resin C1: 5 parts by mass · Wax 1: 5 parts by mass · Colorant 1: 5 parts by mass (Cyan pigment manufactured by Dainichi Seika: Pigment Blue 15:3) The above materials were mixed using a Henschel mixer (Model FM-75, manufactured by Nippon Coke & Engineering Co., Ltd.) at a rotation speed of 25 s-1 for 5 minutes, and then kneaded using a twin-screw kneader (Model PCM-30, manufactured by Ikegai Corporation) at a screw rotation speed of 250 rpm and a discharge temperature of 130 °C with the temperature set at 120 °C.

[0194] The obtained resin composition was cooled to room temperature and coarsely pulverized to 1 mm or less using a hammer mill to obtain a coarsely pulverized product. The obtained coarsely pulverized product was finely pulverized using a mechanical pulverizer (Model T-250, manufactured by Freund Turbo Co., Ltd.). Furthermore, classification was performed using a Faculity F-300 (manufactured by Hosokawa Micron Corporation) to obtain toner particles 1 having a weight average particle diameter (D4) of 6.0 μm, an average circularity of 0.965, and an average domain number diameter of 0.20 μm. The operating conditions were a classification rotor rotation speed of 130 s -1 and a dispersion rotor rotation speed of 120 s. -1 This was used as the standard.

[0195] <Production Examples of Toner Particles 2 to 26> In the example of manufacturing toner particle 1, the manufacturing process was carried out in the same manner except that the type and amount of crystalline resin added, the types and amounts of amorphous resins A and B added, and the type of wax were changed as shown in Table 5, and toner particles 2 to 26 were obtained.

[0196] [Table 5]

[0197] <Example of Toner 1 manufacturing> • Toner particles: 1.99 parts by mass • Silica particles 1 (fumed silica with a number average diameter of 30 nm, treated with silicone oil), 1.0 parts by mass The above ingredients were mixed in a Henschel FM-10C mixer (manufactured by Mitsui Miike Chemical Machinery) at a rotation speed of 30 seconds. -1 The mixture was then mixed for a rotation time of 5 minutes to obtain toner 1. The viscoelasticity of the obtained toner was measured using the method described above and is shown in Table 6.

[0198] [Table 6]

[0199] In the table, T2 is the local minimum (°C) on a graph where temperature T is on the horizontal axis and the value obtained by differentiating LogG'2(T) with respect to temperature T, d(logG'2(T)) / dT, is on the vertical axis. In the table, for example, an entry like 7.0E+03 means 7.0 × 10 3 This indicates that...

[0200] <Manufacturing examples for toners 2-26> In the manufacturing example of toner 1, the toner particles were changed to toner particles 2 to 26, respectively, and the same manufacturing procedure was followed to obtain toners 2 to 26. The physical properties are shown in Table 6.

[0201] <Manufacturing example of magnetic carrier 1> • Number-average particle size 0.30 μm, magnetization strength 65 Am under a magnetic field of (1000 / 4π (kA / m)) 2 Magnetite 1 ( / kg) • Number-average particle size 0.50 μm, magnetization strength 65 Am under a magnetic field of (1000 / 4π (kA / m)) 2 Magnetite 2 ( / kg) To each of the above materials, 4.0 parts of a silane compound (3-(2-aminoethylaminopropyl)trimethoxysilane) was added, and the mixture was rapidly mixed and stirred in a container at over 100°C to treat the respective fine particles.

[0202] • Phenolic: 10% by mass Formaldehyde solution: 6% by mass (40% formaldehyde by mass, 10% methanol by mass, 50% water by mass) • Magnetite treated with the above silane compound 1:58 mass% • Magnetite treated with the above silane compound: 2:26% by mass Place 100 parts of the above material, 5 parts of 28% by mass ammonia aqueous solution, and 20 parts of water into a flask. The mixture was heated to 85°C over 30 minutes while stirring and maintaining the temperature, and the polymerization reaction was carried out for 3 hours to cure the resulting phenolic resin. The cured phenolic resin was then cooled to 30°C, water was added, the supernatant was removed, the precipitate was washed with water, and then air-dried. Next, it was dried under reduced pressure (5 mmHg or less) at a temperature of 60°C to obtain spherical magnetic carrier 1 in the form of a dispersed magnetic material. The volume-based 50% particle size (D50) of magnetic carrier 1 was 34.2 μm.

[0203] <Example of manufacturing a two-component developer 1> 92.0 parts of magnetic carrier 1 were mixed with 8.0 parts of toner 1 using a V-type mixer (V-20, manufactured by Seishin Corporation) to obtain a two-component developer 1.

[0204] <Manufacturing examples of two-component developers 2-26> In the example of manufacturing two-component developer 1, toners 2 to 26 were used to obtain two-component developers 2 to 26.

[0205] <Example 1> [Low temperature fixation] The evaluation was performed using the two-component developer 1 described above. As the image forming apparatus, a modified Canon imageRUNNER ADVANCE C5870 digital commercial printer was used, and a two-component developer 1 was placed in the cyan developer unit. The modifications to the apparatus included allowing free setting of the fixing temperature, process speed, DC voltage VDC of the developer carrier, charging voltage VD of the electrostatic latent image carrier, and laser power. For image output evaluation, a solid-tone image (FFh image) with the desired image ratio was output, and the VDC, VD, and laser power were adjusted so that the amount of toner on the FFh image on the paper was as desired, and the low-temperature fixing performance was evaluated. FFh is a hexadecimal value representing 256 gradations, where 00h is the first gradation (white area) of the 256 gradations, and FFh is the 256th gradation (solid area).

[0206] The evaluation was conducted based on the following evaluation method, and the results are shown in Table 7. ·Paper: GFC-081 (81.0g / m 2 ) (Sold by Canon Marketing Japan Inc.) • Toner amount on paper: 0.80 mg / cm² 2 (Adjusted by the DC voltage VDC of the developer carrier, the charging voltage VD of the electrostatic latent image carrier, and the laser power) • Evaluation image: Place a 2cm x 5cm image in the center of the A4 paper shown above. • Test environment: Low temperature and low humidity environment: Temperature 15°C / Humidity 10%RH (hereinafter referred to as "L / L") Fixing temperature: 140℃ Process speed: 320 mm / sec

[0207] The above evaluation images were output, and the low-temperature fixability was assessed. The value of the image density reduction rate was used as the evaluation index for low-temperature fixability. The image density reduction rate was determined using an X-Rite color reflectance densitometer (500 series: manufactured by X-Rite). First, the image density of the central area was measured. Next, a pressure of 4.9 kPa (50 g / cm³) was applied to the area where the image density was measured. 2The image was fixed using Silbon paper under a load of ) and rubbed (5 times back and forth), and the image density was measured again. The percentage decrease in image density before and after friction was calculated using the following formula. The obtained percentage decrease in image density was evaluated according to the following evaluation criteria. Image density reduction rate = (Image density before friction - Image density after friction) / (Image density before friction) × 100 We considered anything with a rank of C or higher to be good. (Evaluation Criteria) A: Image density reduction rate less than 1.0% B: Image density reduction rate of 1.0% or more and less than 3.0% C: Image density reduction rate of 3.0% or more and less than 8.0% D: Image density reduction rate of 8.0% or more

[0208] [Heat-resistant storage stability] 5g of toner was placed in a 100mL plastic cup and left in a temperature and humidity-controlled constant temperature bath (50°C, 54%) for 72 hours. After standing, the toner's cohesiveness was evaluated. Cohesiveness was evaluated by shaking the toner after standing using a Hosokawa Micron PT-X powder tester with an amplitude of 0.5mm for 10 seconds through a mesh with a mesh size of 150μm. As an evaluation index, the percentage of toner remaining on the mesh was calculated from the mass of toner on the mesh before and after shaking, and a rank of C or higher was considered good. (Evaluation Criteria) A: Survival rate less than 2.0% B: Survival rate between 2.0% and less than 5.0% C: Survival rate between 5.0% and less than 10.0% D: Survival rate 10.0% or more

[0209] [Image defects when printing on both sides] The low-temperature fixation performance was evaluated using the same image forming apparatus as described above, based on the following evaluation method. To more clearly demonstrate the effects of this disclosure, evaluations were performed in a high-temperature and high-humidity environment than the normal operating environment. The results are shown in Table 7. ·Paper:mondi Color Copy(300g / m 2 ) (Sold by Mondi) • Toner amount on paper: 0.80 mg / cm² 2 (Adjusted by the DC voltage VDC of the developer carrier, the charging voltage VD of the electrostatic latent image carrier, and the laser power) • Evaluation image: A 25cm wide x 20cm high FFH image is placed on both sides of the A3 paper shown above, with a 5mm margin from the leading edge in the transport direction. • Test environment: High temperature and high humidity environment: Temperature 35℃ / Humidity 80%RH Fixing temperature: 160℃ Process speed: 320 mm / sec • Number of prints: 10,000 Images 9000 to 10000 were used for evaluation, and the whiteness of the white areas of the output images and the evaluation paper were measured using a "REFLECTMETER MODEL TC-6DS" (manufactured by Tokyo Denshoku Co., Ltd.). The difference between the worst values ​​of the whiteness of the evaluation paper and the white areas of the output images was defined as the haze density (%), and image defects during double-sided printing were evaluated. An amber filter was used. A rank of C or higher was considered good. (Evaluation Criteria) A: The haze density of all evaluated images is less than 1.0%. B: The haze density of all evaluated images is between 1.0% and less than 2.0%. C: The percentage of evaluation images with a haze density of 2.0% or higher is less than 2.0% of the evaluation images. D: The proportion of evaluation images with a haze density of 2.0% or higher is 2.0% or higher compared to the images being evaluated.

[0210] [Drum fusion] The same image forming apparatus as described above for low-temperature fixation was used, and the results were evaluated based on the following evaluation method. The results are shown in Table 7. ·Paper:CS-068(68.0g / m 2 ) (Sold by Canon Marketing Japan Inc.) • Toner amount on paper: 0.80 mg / cm² 2 (Adjusted by the DC voltage VDC of the developer carrier, the charging voltage VD of the electrostatic latent image carrier, and the laser power) • Evaluation image: Place the FFH image on one side of the above A4 paper so that the image print ratio is 40%. • Test environment: High temperature and high humidity environment: Temperature 35℃ / Humidity 80%RH Fixing temperature: 160℃ Process speed: 320 mm / sec • Number of prints: 100,000 After continuous output was completed, the surface of the electrostatic latent image carrier was observed using a digital high-definition microscope VQ-7000 (manufactured by Keyence Corporation) (magnification 300x). Locations where toner fusion occurred in the field of view were marked, their area was calculated, and the area ratio of fusion in the field of view was determined. This was done for 20 fields of view across the entire electrostatic latent image carrier, and the average value was taken as the fusion occurrence rate. This evaluation was performed three times, and a rank was determined from the average value. The ranking of the evaluation was done as follows. The evaluation results are shown in Table 7. Rank C or higher was judged to be good. (Evaluation Criteria) A: Fusion occurrence rate less than 1.0% B: Fusion occurrence rate of 1.0% or more and less than 5.0% C: Fusion occurrence rate 5.0% or more and less than 10.0% D: Fusion occurrence rate of 10.0% or higher

[0211] [Charge stability] The same image forming apparatus as described above for low-temperature fixation was used, and the results were evaluated based on the following evaluation method. The results are shown in Table 7. ·Paper:CS-068(68.0g / m 2 ) (Sold by Canon Marketing Japan Inc.) • Amount of toner on paper: 0.40 mg / cm² 2 (Adjusted by the DC voltage VDC of the developer carrier, the charging voltage VD of the electrostatic latent image carrier, and the laser power) • Evaluation image: The FFH image is placed on one side of the above A4 paper so that the image print ratio is 2%. • Test environment: High temperature and high humidity environment: Temperature 30℃ / Humidity 80%RH Fixing temperature: 160℃ Process speed: 320 mm / sec Under the above conditions, 3000 images were printed. After leaving them for one day, one identical evaluation image was printed. The image density of the obtained image was measured and compared with the image density of the first image printed before the one-day waiting period to determine the rate of change in image density as follows. Image density change rate (%) = │1-(Image density after standing) / (Image density of the first image before standing)│×100 The evaluation was conducted according to the following criteria. A rank of C or higher was considered good. (Evaluation Criteria) A: Image density change rate is less than 2.0%. B: Image density change rate is 2.0% or more and less than 5.0%. C: Image density change rate is 5.0% or more and less than 10.0%. D: Image density change rate is 10.0% or higher.

[0212] <Examples 2-21 and Comparative Examples 1-5> The evaluation was carried out in the same manner as in Example 1, except that two-component developers 2 to 26 were used instead of two-component developer 1. The evaluation results are shown in Table 7.

[0213] [Table 7] In the table, "Percentage of 2% or more" indicates the percentage of evaluated images with a haze density of 2.0% or higher out of the total number of evaluated images.

[0214] This disclosure relates to the following configuration. (Composition 1) A toner having toner particles containing a binder resin and wax, The binder resin contains a crystalline resin, In measuring the viscoelasticity of the toner, Step (i) The temperature is raised from 30°C to 100°C at a rate of 2°C / min to obtain the curve G'1(T) of the storage modulus G'[Pa] as a function of temperature T[°C]. Step (ii) After step (i), the temperature is lowered from 100°C to 30°C at a rate of 2°C / min to obtain the curve G'2(T) of the storage modulus G'[Pa] against temperature T[°C]. Step (iii) After step (ii), the temperature is raised from 30°C to 100°C at a rate of 2°C / min to obtain the curve G'3(T) of the storage modulus G'[Pa] against temperature T[°C]. When the storage modulus G' at 100°C in curve G'1(T) is G'1(100)[Pa], the storage modulus G' at 70°C in curve G'2(T) is G'2(70)[Pa], the storage modulus G' at 50°C in curve G'3(T) is G'3(50)[Pa], and the storage modulus G' at 70°C in curve G'3(T) is G'3(70)[Pa], A toner characterized in that G'1(100), G'2(70), G'3(50), and G'3(70) satisfy the following formulas (1) to (4). G'1(100)≦5.0×10 4 Pa ···(1) G'3(50)≧7.0×10 7 Pa ···(2) G'3(70)≧2.0×10 6 Pa ···(3) G'3(70) / G'2(70)≧10 ···(4) (Configuration 2) With respect to the curve G'2(T), in a graph where the temperature T is on the horizontal axis and the value d(logG'2(T)) / dT obtained by differentiating LogG'2(T) with respect to the temperature T is on the vertical axis, A minimum value exists in the range of 55.0 to 70.0°C. When the temperature at which this minimum value is obtained is denoted as temperature T2 (°C), The toner described in Configuration 1, wherein d(logG'2(T2)) / dT is between -2.0 and -0.3. (Composition 3) The aforementioned binder resin further contains amorphous polyester resin A, The amorphous polyester resin A has molecular chain ends formed by condensation of at least one linear alkyl compound A selected from the group consisting of aliphatic linear monocarboxylic acids and aliphatic linear monoalcohols. Let the number of carbon atoms in the linear alkyl compound A be Aend. When the wax is analyzed by GC / MS, the number of carbon atoms corresponding to the peak detected as the maximum peak is denoted as Wmax. The Aend and the Wmax are Aend ≥ 16 16 ≤ Wmax - Aend ≤ 30 A toner according to configuration 1 or 2 that satisfies the relationship. (Composition 4) The crystalline resin includes a crystalline polyester resin. The toner according to configuration 1 or 2, wherein the crystalline polyester resin has a structure in which at least one linear alkyl compound C selected from the group consisting of monohydric alcohols and monohydric carboxylic acids is condensed at the end of the molecular chain. (Composition 5) The aforementioned binder resin further contains amorphous polyester resin A, The toner according to configuration 4, wherein the amorphous polyester resin A has molecular chain ends condensed with at least one linear alkyl compound A selected from the group consisting of aliphatic linear monocarboxylic acids and aliphatic linear monoalcohols. (Composition 6) Let the number of carbon atoms in the linear alkyl compound A be Aend. When the number of carbon atoms in the linear alkyl compound C is denoted as Cend, The Aend and the Cend are Cend ≥ 16 -4 ≤ Cend - Aend ≤ 6 The toner described in configuration 5 satisfies the relationship. (Composition 7) The crystalline polyester resin comprises a condensate polymer of a monomer composition containing an aliphatic diol and an aliphatic dicarboxylic acid. When the number of carbon atoms in the aliphatic diol in the crystalline polyester resin is Cal, the number of carbon atoms in the aliphatic dicarboxylic acid is Cca, and the number of carbon atoms in the linear alkyl compound C is Cend, The Cal, the Cca and Cend are, A toner described in any of configurations 4 to 6 that satisfies the relationship Cend-(Cal+Cca)≧8. (Composition 8) The toner according to configuration 5 or 6, wherein the linear alkyl compound A has an aliphatic linear monocarboxylic acid. (Composition 9) When the weight-average molecular weight of the THF-soluble component of the amorphous polyester resin A is Mwa, and the weight-average molecular weight of the THF-soluble component of the crystalline polyester resin is Mwc, The toner according to configuration 5, 6, or 8, wherein Mwa and Mwc satisfy Mwa / Mwc ≤ 0.50.

Claims

1. A toner having toner particles containing a binder resin and wax, The binder resin contains a crystalline resin, In measuring the viscoelasticity of the toner, Step (i) The temperature is raised from 30°C to 100°C at a rate of 2°C / min to obtain the curve G' of the storage modulus G' [Pa] against temperature T [°C]. １ (T) obtained, Step (ii) After step (i), the temperature is cooled from 100°C to 30°C at a rate of 2°C / min to obtain the curve G' of the storage modulus G' [Pa] against temperature T [°C]. ２ (T) obtained, Step (iii) After step (iii), the temperature is raised from 30°C to 100°C at a rate of 2°C / min to obtain the curve G' of the storage modulus G' [Pa] against temperature T [°C]. ３ (T) obtained, The curve G' １ The storage modulus G' at 100 °C in (T) is taken as G' １ (100) [Pa], and the curve G' ２ The storage modulus G' at 70 °C in (T) is taken as G' ２ (70) [Pa], and the curve G' ３ The storage modulus G' at 50 °C in (T) is taken as G' ３ (50) [Pa], and the curve G' ３ The storage modulus G' at 70 °C in (T) is taken as G' ３ When (70) [Pa], The G' １ (100), the G' ２ (70), the G' ３ (50) and G' ３ A toner characterized in that (70) satisfies the following formulas (1) to (4). G´ １ (100)≦5.0×10 ４ Pa・・・(1) G´ ３ (50)≧7.0×10 ７ Pa・・・(2) G´ ３ (70)≧2.0×10 ６ P... (3) G´ ３ (70) / G´ ２ (70)≧10 ・・・(4)

2. The aforementioned curve G' ２ With respect to (T), the temperature T is used as the horizontal axis, and LogG' ２ The value obtained by differentiating (T) with respect to the temperature T is d(log G'). ２ In a graph with (T) / dT as the vertical axis, A minimum value exists in the range of 55.0 to 70.0°C. When the temperature at which this minimum value is obtained is denoted as temperature T2 (°C), d(logG') ２ The toner according to claim 1, wherein (T2) / dT is between -2.0 and -0.

3.

3. The aforementioned binder resin further contains amorphous polyester resin A, The amorphous polyester resin A has molecular chain ends formed by condensation of at least one linear alkyl compound A selected from the group consisting of aliphatic linear monocarboxylic acids and aliphatic linear monoalcohols. Let the number of carbon atoms in the linear alkyl compound A be Aend. When the wax is analyzed by GC / MS, the number of carbon atoms corresponding to the peak detected as the maximum peak is denoted as Wmax. The Aend and the Wmax are, End ≥ 16 16≦Wmax-Aend≦30 The toner according to claim 1 or 2, which satisfies the relationship.

4. The crystalline resin includes a crystalline polyester resin. The toner according to claim 1 or 2, wherein the crystalline polyester resin has a structure in which at least one linear alkyl compound C selected from the group consisting of monohydric alcohols and monohydric carboxylic acids is condensed at the end of the molecular chain.

5. The aforementioned binder resin further contains amorphous polyester resin A, The amorphous polyester resin A is a molecular chain powder formed by the condensation of at least one linear alkyl compound A selected from the group consisting of aliphatic linear monocarboxylic acids and aliphatic linear monoalcohols. The toner according to claim 4, having an end.

6. Let the number of carbon atoms in the linear alkyl compound A be Aend. When the number of carbon atoms in the linear alkyl compound C is denoted as Cend, Aend and Cend are Cend ≥ 16 -4≦Cend-Aend≦6 The toner according to claim 5, which satisfies the relationship.

7. The crystalline polyester resin comprises a condensate polymer of a monomer composition containing an aliphatic diol and an aliphatic dicarboxylic acid. When the number of carbon atoms in the aliphatic diol in the crystalline polyester resin is Cal, the number of carbon atoms in the aliphatic dicarboxylic acid is Cca, and the number of carbon atoms in the linear alkyl compound C is Cend, The Cal, the Cca and Cend are, The toner according to claim 4, satisfying the relationship Cend - (Cal + Cca) ≥ 8.

8. The toner according to claim 5, wherein the linear alkyl compound A has an aliphatic linear monocarboxylic acid.

9. When the weight-average molecular weight of the THF-soluble component of the amorphous polyester resin A is Mwa, and the weight-average molecular weight of the THF-soluble component of the crystalline polyester resin is Mwc, The toner according to claim 5, wherein Mwa and Mwc satisfy Mwa / Mwc ≤ 0.50.

Images