TONER

Abstract

A toner comprising a toner particle comprising a binder resin and a wax, wherein the binder resin comprises a crystalline resin, wherein, when measuring the viscoelasticity of the toner, the temperature is increased from 30 °C to 100 °C at a rate of 2 °C / min to obtain a curve G'1(T) of the storage elasticity modulus G' versus temperature T; then the temperature is decreased from 100 °C to 30 °C at a rate of 2 °C / min to obtain a curve G'2(T); then the temperature is increased from 30 °C to 100 °C at a rate of 2 °C / min to obtain a curve G'3(T); the storage elasticity modulus at specific temperatures in each curve satisfies the following formulas. 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

BACKGROUND Area of ​​Technology

[0001] The present disclosure relates to toner for use in electrophotography, electrostatic recording, electrostatic printing and toner jet printing. Description of the relevant state of the art

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

[0003] To achieve low power consumption, it is important to melt toner at lower temperatures during the fusing step. Therefore, the toner's melting properties are improved by encapsulating a crystalline resin within a binder resin.

[0004] However, the toner, which comprises the crystalline resin, can have poor storage stability at high temperatures or can adhere strongly to a photosensitive element, resulting in image defects (fusion with a drum). Furthermore, the solidification of the molten toner during the fusing step can be slow, which can cause defects (the phenomenon of ejected paper sticking) due to the transfer of parts of the fused images to other recording media or adhesion of the fused images to each other when ejected recording media are stacked.

[0005] To suppress the phenomenon of paper sticking to the paper, the disclosed Japanese patent application No. 2019-194682, for example, discloses a toner comprising an amorphous polyester having an alkyl group with a certain number of carbon atoms at one end and a crystalline polyester composed of a certain number of carbon atoms.

[0006] Furthermore, the disclosed Japanese patent application No. 2019-056767 discloses a toner with a complex viscosity which, when measured by dynamic viscoelasticity measurement using various thermal methods, falls within a certain range.

[0007] The toners described in the aforementioned documents appear to be reasonably effective in suppressing the phenomenon of paper sticking to the ejected paper. However, according to the inventors' investigations, image defects (hereinafter referred to as double-sided printing defects) can occur during double-sided printing if part of the fixed image comes into contact with and is transferred to an element touching a recording medium in an electrophotographic device. SUMMARY

[0008] The present disclosure relates to a toner which exhibits excellent low-temperature fixability and heat-resistant storage stability, is resistant to fusion with a drum and can suppress double-sided printing errors.

[0009] The present disclosure relates to a toner comprising a toner particle comprising a binder resin and a wax, wherein the binder resin comprises a crystalline resin; when measuring the viscoelasticity of the toner, Step (i): The temperature is increased from 30 °C to 100 °C at a rate of 2 °C / min to obtain a curve G'1(T) of the storage elasticity modulus G' [Pa] versus temperature T [°C], Step (ii): After step (i), the temperature is reduced from 100 °C to 30 °C at a rate of 2 °C / min to obtain a curve G'2(T) of the storage elasticity modulus G' [Pa] versus temperature T [°C], Step (iii): After step (ii), the temperature is increased from 30 °C to 100 °C at a rate of 2 °C / min to obtain a curve G'3(T) of the storage elasticity modulus G' [Pa] versus temperature T [°C]; and where the storage elasticity modulus G' at 100 °C on curve G'1(T) is denoted by G'1(100) [Pa], the storage elasticity modulus G' at 70 °C on curve G'2(T) is denoted by G'2(70) [Pa], the storage elasticity modulus G' at 50 °C on curve G'3(T) is denoted by G'3(50) [Pa], and the storage elasticity modulus G' at 70 °C on curve G'3(T) is denoted by G'3(70) [Pa], G'1(100), G'2(70), G'3(50), and G'3(70) satisfy the following formulas (1) to (4). G'1(100)≤5.0×104Pa G'3(50)≤7.0×107Pa G'3(70)≤2.0×106Pa G'3(70) / G'2(70)≥10

[0010] The present disclosure can provide a toner that exhibits excellent low-temperature fixability and heat-resistant storage stability, is less prone to fusion with a drum, and can further suppress double-sided printing errors.

[0011] Features of the present disclosure will become apparent from the following description of embodiments. The following description of embodiments is illustrated by examples. DESCRIPTION OF THE EXECUTION FORMS

[0012] In the present disclosure, the expression "from XX to YY" or "XX to YY", which specifies a range of numbers, means a range of numbers that includes a lower bound and an upper bound, which are endpoints, unless otherwise specified. Likewise, the upper and lower bounds of each range of numbers may be combined arbitrarily when a range of numbers is described stepwise. Furthermore, in the present disclosure, descriptions such as "at least one selected from the group consisting of XX, YY, and ZZ" mean each of XX, YY, ZZ, the combination of XX and YY, the combination of XX and ZZ, the combination of YY and ZZ, and the combination of XX, YY, and ZZ. If XX is a group, it is permissible to select multiple elements from XX, and the same applies to YY and ZZ.

[0013] In the present disclosure, crystalline resin refers to a resin that exhibits a distinct endothermic peak upon differential scanning calorimetry (DSC). The “monomer unit” refers to the reacted form of a monomer substance in a polymer.

[0014] The toner of the present revelation is described in detail below.

[0015] The present disclosure relates to a toner comprising a toner particle comprising a binder resin and a wax, wherein the binder resin comprises a crystalline resin; when measuring the viscoelasticity of the toner, Step (i): The temperature is increased from 30 °C to 100 °C at a rate of 2 °C / min to obtain a curve G'1(T) of the storage elasticity modulus G [Pa] versus temperature T [°C], Step (ii): After step (i), the temperature is reduced from 100 °C to 30 °C at a rate of 2 °C / min to obtain a curve G'2(T) of the storage elasticity modulus G' [Pa] versus temperature T [°C], Step (iii): After step (ii), the temperature is increased from 30 °C to 100 °C at a rate of 2 °C / min to obtain a curve G'3(T) of the storage elasticity modulus G' [Pa] versus temperature T [°C]; and where the storage elasticity modulus G' at 100 °C on curve G'1(T) is denoted by G'1(100) [Pa], the storage elasticity modulus G' at 70 °C on curve G'2(T) is denoted by G'2(70) [Pa], the storage elasticity modulus G' at 50 °C on curve G'3(T) is denoted by G'3(50) [Pa], and the storage elasticity modulus G' at 70 °C on curve G'3(T) is denoted by G'3(70) [Pa], G'1(100), G'2(70), G'3(50), and G'3(70) satisfy the following formulas (1) to (4). G'1(100)≤5.0×104Pa G'3(50)≤7.0×107Pa G'3(70)≤2.0×106Pa G'3(70) / G'2(70)≥10

[0016] After extensive research, the inventors discovered that the aforementioned problems can be solved by controlling the viscoelasticity of a toner containing a crystalline resin within the specific range mentioned above. Specifically, this toner enables excellent low-temperature fixability and heat-resistant storage stability, suppressing double-sided printing errors and drum adhesion, while maintaining long-lasting durability even at low print volumes.

[0017] The background for the development of this toner is as follows: In the fixing step, toner is heated and melted, then cooled to solidify and form a fixed image. In double-sided printing, a fixed image formed on one side of the printing medium is reheated on the reverse side during the fusing step. If the elasticity of storage of the fixed image formed on one side is low, when the fixed image comes into contact with other components, such as transmission or transport elements, part of the fixed image can be transferred to these components during double-sided printing, resulting in poor image quality.

[0018] When a toner containing a crystalline resin is melted and then cooled during the fixing step, some of the crystalline resin may solidify without crystallizing. It is speculated that such crystalline resin likely acts as a plasticizer in the fixed image, which can apparently lead to the transfer of the fixed image to other components during double-sided printing. Although methods exist to further promote the crystallization of the crystalline resin, such as the addition of a nucleating agent, it is difficult to eliminate the uncrystallized crystalline resin component.

[0019] Accordingly, the inventors assumed that it was important to improve the strength of the fixed image, even in the presence of the uncrystallized crystalline resin. The inventors found that, as an indicator of fixed image strength, the storage elasticity modulus of a toner sample that had been melted and then solidified correlated closely with the strength of the fixed image. However, simply increasing the storage elasticity modulus of the toner impairs low-temperature fixability. As a result of the fabrication and extensive testing of various toner prototypes, it was found that toners with excellent low-temperature fixability and a high storage elasticity modulus at 70 °C exhibited a lower storage elasticity modulus at 70 °C when the temperature was decreased during the second temperature increase cycle than when it was increased.This finding led to the development of the toner described above.

[0020] The toner of the present disclosure has the following properties.

[0021] When measuring the viscoelasticity at 1% elongation of the toner, the following steps (i) to (iii) are performed. Step (i): The temperature is increased from 30 °C to 100 °C at a rate of 2 °C / min to obtain a curve G'1(T) of the storage elasticity modulus G' [Pa] versus temperature T [°C], Step (ii): After step (i), the temperature is reduced from 100 °C to 30 °C at a rate of 2 °C / min to obtain a curve G'2(T) of the storage elasticity modulus G' [Pa] versus temperature T [°C], Step (iii): After step (ii), the temperature is increased from 30 °C to 100 °C at a rate of 2 °C / min to obtain a curve G'3(T) of the storage elasticity modulus G' [Pa] versus temperature T [°C].

[0022] The storage elastic modulus G' at 100 °C is then given on curve G'1(T) as G'1(100) [Pa]. The storage elastic modulus G' at 70 °C is given on curve G'2(T) as G'2(70) [Pa]. The storage elastic modulus G' at 50 °C is given on curve G'3(T) as G'3(50) [Pa], and the storage elastic modulus G' at 70 °C is given on curve G'3(T) as G'3(70) [Pa].

[0023] 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)≤5.0×104Pa G'3(50)≤7.0×107Pa G'3(70)≤2.0×106Pa G'3(70) / G'2(70)≥10

[0024] By measuring the viscoelasticity of the toner described above, step (i) simulates the toner's behavior in the process where the toner is heated during the fusing step. Step (ii) simulates the toner's behavior in the process where the toner is cooled after heating and melting. Step (iii) simulates the behavior of a solidified, fixed image when reheated during double-sided printing.

[0025] The toner is defined by G'1(100) ≤ 5.0 × 10 4 Pa marked. Since G'1(100) is the storage elasticity modulus G' at 100 °C, the fulfillment of formula (1) indicates that the storage elasticity modulus of the toner becomes sufficiently low in the fusing step.

[0026] G'1(100) within the above-mentioned range ensures excellent low-temperature fixability. From the perspective of achieving both low-temperature fixability and hot-offset resistance, it is preferred that 1.0 × 10 3 Pa ≤ G'1(100) ≤ 5.0 × 10 4 Pa and more preferably 1.0 × 10 3 Pa ≤ G'1(100) ≤ 2.0 × 10 4 Pa is.

[0027] 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 the resins used in addition to the crystalline resin, and the melting point and content of the wax.

[0028] The value of G'1(100) can be easily increased, for example, by reducing the crystalline resin content or by raising the glass transition point and softening point of resins used alongside the crystalline resin. The value of G'1(100) can also be easily decreased, for example, by setting the melting point of the crystalline resin at or below 100 °C or by increasing its content. The value of G'1(100) can also be easily decreased by using a resin with a low softening point alongside the crystalline resin. Furthermore, the value of G'1(100) can also be easily decreased by setting the melting point of the wax below 100 °C and increasing its wax content.

[0029] The toner is characterized by fulfilling formula (4), i.e., G'3(70) / G'2(70) ≥ 10. Fulfillment of formula (4) indicates that there is a 10-fold or greater difference between the storage elasticity modulus of the toner during the cooling process after melting and the storage elasticity modulus during the subsequent temperature increase process.

[0030] The inventors speculate that the toner exhibits this behavior according to the following mechanism.

[0031] When the toner is cooled after melting, it begins to crystallize near its crystallization temperature. The crystallization temperature can be measured by the peak temperature of an exothermic peak associated with crystallization, observed during temperature reduction using differential scanning calorimetry (DSC), as described below. As the crystalline resin begins to crystallize, the solid content of the toner increases, and its elastic modulus also increases. It is assumed that the crystalline resin does not crystallize spontaneously at this point, but rather crystallizes through interaction with other molten binder resins in its vicinity.

[0032] The inventors speculate that this interaction causes a slower increase in the storage elasticity modulus than would occur without interaction with other binder resins. This results in a smaller G'2(70). It is speculated that a slower increase in the storage elasticity modulus allows the crystalline resin to reach a state of high molecular mobility, making it easier to achieve a molecular chain arrangement that results in a crystalline state closer to the ideal. It is suggested that the solidified image produced by this process becomes strong, leading to a larger G'3(70), and that the ratio G'3(70) / G'2(70) ≥ 10 can be achieved.

[0033] Preferably, G'3(70) / G'2(70) ≥ 20, more preferred, G'3(70) / G'2(70) ≥ 38, and even more preferred, G'3(70) / G'2(70) ≥ 40. If G'3(70) / G'2(70) is less than 10, image defects are likely to occur in double-sided printing. Furthermore, G'3(70) / G'2(70) is, for example, 10 to 100, preferably 20 to 90, more preferred, 38 to 80, and even more preferred, 40 to 75.

[0034] As described below in the raw material section, one method for controlling the value of G'3(70) / G'2(70) is to introduce a structure having an alkyl group at the molecular chain end of the crystalline polyester resin. Another method is to introduce a monomer unit corresponding to a linear aliphatic carboxylic acid into a binder resin alongside the crystalline resin.

[0035] Furthermore, the toner is characterized by fulfilling formula (2), i.e., G'3(50) ≥ 7.0 × 10 7 Pa.

[0036] If G'3(50) is within the above-mentioned range, the heat-resistant storage stability of the toner is improved. Preferably, G'3(50) ≥ 9.0 × 10 7 Pa and more preferred is G'3(50) ≥ 1.0 × 10 8 Pa. If G'3(50) is less than 7.0 × 10 7 Pa is, the heat-resistant storage stability of the toner decreases.

[0037] In this context, it is more likely that in a toner containing crystalline resin, the crystalline resin in the toner will crystallize over time after the toner's manufacture. As a result, the numerical value of G'1(50) tends to increase with increasing storage time, making it impossible to accurately compare the heat-resistant storage stability of toners. For this reason, the present disclosure uses the value G'3(50) as an index by which heat-resistant storage stability can be assessed without significantly considering the influence of storage time. The value of G'1(100) and the values ​​of G'2(T) and G'3(T) are not affected by the storage time of the toner.

[0038] G'3(50) is, for example, 7.0 × 10 7 up to 7.0 × 10 9 Pa, preferably 9.0 × 10 7 up to 4.0 × 10 9 Pa, and preferably 1.0 × 10 8 up to 2.0 × 10 9 Pa.

[0039] Furthermore, the toner is characterized by fulfilling formula (3), i.e., G'3(70) ≥ 2.0 × 10 6 The presence of G'3(70) in this region can suppress image defects in double-sided printing. Preferably, G'3(70) ≥ 5.0 × 10 6 Pa and more preferred is G'3(70) ≥ 7.0 × 10 6 Pa. If G'3(70) is less than 2.0 × 10 6 If Pa is the case, image errors cannot be suppressed when printing on both sides of the screen.

[0040] G'3(70) is, for example, 2.0 × 10 6 up to 9.0 × 10 7 Pa, preferably 5.0 × 10 6 up to 4.0 × 10 7 Pa, and preferably 7.0 × 10 6 up to 3.0 × 10 7 Pa.

[0041] The values ​​of G'3(50) and G'3(70) can be controlled by changing the melting point and content of the crystalline resin and the type, glass transition point, weight mean molecular weight of the THF-soluble fraction and content of the binder resin that is not a crystalline resin.

[0042] G'3(50) can, for example, be easily increased by increasing the glass transition point of the binder resin that is not a crystalline resin, increasing the weight mean molecular weight of the binder resin, or decreasing the content of the crystalline resin.

[0043] G'3(70) can, for example, be easily increased by introducing a structure having an alkyl group at the molecular chain end of the crystalline polyester resin or by further introducing an amorphous polyester resin into the binder resin and introducing an alkyl group at the molecular chain end.

[0044] Furthermore, it is preferred that in a diagram of the curve G'2(T), in which a horizontal axis represents the temperature T and a vertical axis represents a value d(logG'2(T)) / dT obtained by differentiating logG'2(T) with respect to the temperature T, there is a minimum value in a range of 55.0 to 70.0 °C.

[0045] Furthermore, it is preferred that d(logG'2(T2)) / dT is -2.0 to -0.3, where the temperature at which the minimum value is observed is denoted by T2 (°C).

[0046] In the graph above, a minimum value in the range of 55.0 to 70.0 °C indicates that there is a point in this range where the storage elasticity modulus increases sharply in the process by which the toner is cooled after melting. Furthermore, d(logG'2(T2)) / dT indicates the magnitude of the change in the storage elasticity modulus, with a larger absolute value indicating a steeper change. The fact that d(logG'2(T2)) / dT is in the range of -2.0 to -0.3 indicates that the storage elasticity modulus increases sharply in the process by which the toner is cooled after melting.

[0047] A steep increase in the storage elasticity modulus in the range of 55.0 to 70.0 °C is made possible by achieving a molecular chain arrangement that results in a crystalline state closer to the ideal, as the crystalline resin in the molten toner interacts with other binder resins during cooling. This makes it easy to control the value of G'3(50) within the aforementioned range.

[0048] In the graph above, a minimum T2 value of 55 °C or higher increases the elastic modulus of the image, making it easier to further suppress image defects in double-sided printing. Additionally, a minimum T2 value of 70.0 °C or less facilitates the interaction of the crystalline resin with other binder resins, thus making it easier to suppress image defects in double-sided printing.

[0049] The minimum value T2 is preferably between 57.0 and 68.0°C. Furthermore, d(logG'2(T2)) / dT is more preferred -2.0 to -0.4, even more preferred -2.0 to -0.5 and still more preferred -1.3 to -0.5.

[0050] T2 can be modified by controlling the temperature at which the crystalline resin interacts with other binder resins. Specifically, the value of T2 can be lowered by decreasing the melting point of the crystalline resin or the glass transition point of the amorphous resin. The value of T2 can also be lowered by increasing the melting point of the crystalline resin or the glass transition point of the amorphous resin.

[0051] Regarding a method for controlling d(logG'2(T2)) / dT within the aforementioned range, the absolute value increases when the degree of interaction between the crystalline resin and the other binder resins is high, and decreases when the degree of interaction is low. d(logG'2(T2)) / dT can be controlled by changing the structure, melting point, or molecular weight of the crystalline resin, by changing the structure or softening point of the amorphous resin, or by changing the type or melting point of the wax. Furthermore, d(logG'2(T2)) / dT can also be controlled by adding a structure with an alkyl group to the molecular chain end of the crystalline or amorphous resin.

[0052] Next, the raw materials for the toner will be described in detail.

[0053] The toner particle comprises a binder resin. The binder resin comprises a crystalline resin. The crystalline resin can be any known crystalline resin that can be used in toner. Specific examples include crystalline polyester resin and crystalline vinyl resin. From the point of view of making it easier to maintain the interaction described above, the crystalline resin preferably comprises a crystalline polyester resin and is more preferably a crystalline polyester resin.

[0054] The crystalline polyester resin is preferably a condensation polymer of a monomer composition comprising (e.g., as major components) an aliphatic diol (e.g., having 2 to 22 carbon atoms) and an aliphatic dicarboxylic acid (e.g., having 2 to 22 carbon atoms). The term "major component" means that its proportion is 50 wt% or more of the monomer composition. It is preferably 50 to 100 wt% and more preferably 70 to 98 wt%.

[0055] The aliphatic diol, having 2 to 22 carbon atoms (preferably 2 to 12 carbon atoms), is not limited in particular, but is preferably a chain-like (more preferably a linear) aliphatic diol. Examples are 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.

[0056] Other polyhydric alcohol monomers besides the aliphatic diols mentioned above can also be used. Examples of dihydric alcohol monomers include aromatic alcohols such as polyoxyethylene-bisphenol A and polyoxypropylene-bisphenol A, 1,4-cyclohexanedimethanol, and the like.

[0057] Furthermore, among these polyhydric alcohol monomers, it is preferable to use trihydric or higher polyhydric alcohol monomers.

[0058] Among these polyhydric alcohol monomers, trihydric or higher polyhydric alcohol monomers 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, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane and trimethylolpropane.

[0059] Meanwhile, the aliphatic dicarboxylic acid compound having 2 to 22 carbon atoms (preferably 6 to 18 carbon atoms) is not limited, but is preferably a chain-like (more preferably a linear) aliphatic dicarboxylic acid. Specific examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic 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, as well as hydrolyzed lower alkyl esters and acid anhydrides thereof. More preferred examples include adipic acid, sebacic acid, and 1,10-decanedicarboxylic acid.

[0060] Other polycarboxylic acids besides the aliphatic dicarboxylic acid compounds mentioned above, which have 2 to 22 carbon atoms (hereinafter referred to as "other polycarboxylic acids"), can also be used.

[0061] Among the other polycarboxylic acid monomers, examples of dicarboxylic acids include aromatic carboxylic acids such as isophthalic acid and terephthalic acid; aliphatic carboxylic acids such as n-dodecyl succinic acid and n-dodecenyl succinic acid; and alicyclic carboxylic acids such as cyclohexanedicarboxylic acid, as well as their acid anhydrides and lower alkyl esters.

[0062] Furthermore, among other carboxylic acid monomers, examples of trivalent or higher-valent polycarboxylic acids include aromatic carboxylic acids such as 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid and pyromellitic acid, and aliphatic carboxylic acids such as 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid and 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, as well as their acid anhydrides and lower alkyl esters.

[0063] In addition to the monomers mentioned above, it is particularly preferred that the monomer composition forming the crystalline polyester resin comprises at least one selected from the group consisting of monohydric alcohols and monohydric carboxylic acids. In other words, the crystalline polyester resin preferably comprises a condensation polymer of a monomer composition comprising an aliphatic diol and an aliphatic dicarboxylic acid. 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 end of the molecular chain.

[0064] Using these monohydric alcohols and / or monohydric carboxylic acids, the molecular chain end of the crystalline polyester resin becomes an alkyl group. During the cooling process after the toner melts, this terminal alkyl group is more likely to interact 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 of the toner increase, making it easier to keep the values ​​of G'3(50) and G'3(70) within the ranges mentioned above. It is particularly preferred if the linear alkyl compound C comprises a monohydric carboxylic acid.

[0065] The monohydric alcohol is preferably a monohydric alcohol with 2 to 24 carbon atoms, more preferably with 16 to 24 carbon atoms, and particularly preferably with 18 to 22 carbon atoms. Furthermore, aliphatic monohydric alcohols are preferred, and linear aliphatic monohydric alcohols are more preferred.

[0066] 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. Of these, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, and lignoceryl alcohol are preferred.

[0067] The monovalent carboxylic acid is preferably a monovalent carboxylic acid with 2 to 24 carbon atoms, more preferably with 16 to 24 carbon atoms, and particularly preferably with 18 to 22 carbon atoms. Furthermore, aliphatic monovalent carboxylic acids are preferred, and linear aliphatic monovalent carboxylic acids are more preferred.

[0068] Examples of monovalent carboxylic acids include monocarboxylic acids such as benzoic acid, naphthalenic acid, salicylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, phenoxyacetic acid, biphenyl carboxylic acid, acetic acid, propionic acid, butyric acid, octanoic acid, decanoic acid, dodecanoic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, and lignoceric acid. Palmitic acid, stearic acid, arachidic acid, behenic acid, and lignoceric acid are particularly preferred.

[0069] The crystalline polyester resin preferably comprises a condensation polymer of an aliphatic diol having 2 to 22 carbon atoms and an aliphatic dicarboxylic acid having 2 to 22 carbon atoms. That is to say, the crystalline polyester resin preferably comprises a monomer unit corresponding to an aliphatic diol having 2 to 22 carbon atoms and a monomer unit corresponding to an aliphatic dicarboxylic acid having 2 to 22 carbon atoms.

[0070] The overall content ratio of the monomer unit corresponding to an aliphatic diol having 2 to 22 carbon atoms and the monomer unit corresponding to an aliphatic dicarboxylic acid having 2 to 22 carbon atoms in the crystalline polyester resin is, for example, 50 to 100 wt%, preferably 80 to 99 wt%, and more preferably 90 to 98 wt%. With respect to mol%, 90 to 99 mol% is preferred and 95 to 98 mol% is more preferred.

[0071] Furthermore, the crystalline polyester resin is preferably a condensation polymer with a main framework (of a different structure than the linear alkyl compound C condensed at the end) consisting of an aliphatic diol having 2 to 22 carbon atoms and an aliphatic dicarboxylic acid having 2 to 22 carbon atoms.

[0072] In the crystalline polyester resin, the content ratio of the structure in which the linear alkyl compound C is condensed at the end of the molecular chain is preferably 1 to 20 wt%, more preferably 2 to 15 wt%, and even more preferably 2 to 10 wt%. With respect to mol%, it is preferably 1 to 10 mol% and more preferably 2 to 5 mol%.

[0073] The number of carbon atoms in the aliphatic diol forming the main framework of the crystalline polyester resin is denoted by Cal, and the number of carbon atoms in the aliphatic dicarboxylic acid forming the main framework of the crystalline polyester resin is denoted by Cca. Additionally, the number of carbon atoms in the linear alkyl compound C condensed at the end of the crystalline polyester resin is denoted by Cend. In this case, it is preferable for the relationship Cend - (Cal + Cca) ≥ 8 to be satisfied.

[0074] Here, the number of carbon atoms refers to the component with the highest concentration (in moles) if the crystalline polyester resin comprises several aliphatic diols or aliphatic dicarboxylic acids forming its main framework. If the concentrations are equal, the number of carbon atoms refers to the component with the highest number of carbon atoms. The same applies to the number of carbon atoms in the linear alkyl compound C condensed at the end.

[0075] If Cend - (Cal + Cca) 8 or greater, this means that the total number of carbon atoms in the aliphatic diols or aliphatic dicarboxylic acids forming the main framework is less than the number of terminal carbon atoms. Fulfilling this relationship facilitates better crystallization of the crystalline polyester component forming the main framework during cooling and promotes stronger interaction between the terminal alkyl groups and other binder resins. As a result, the value of G'3(70) / G'2(70) and the absolute value of d(logG'2(T2)) / dT tend to increase, making them easier to control within the aforementioned ranges, which is desirable.

[0076] 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.

[0077] 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 still more preferably 80 to 90 °C.

[0078] The weight-average molecular weight Mwc of the THF-soluble fraction 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 still more preferably 18,000 to 30,000.

[0079] Crystalline polyester resins can be produced using conventional polyester synthesis methods. For example, the desired crystalline polyester resin can be obtained by subjecting the aforementioned carboxylic acid monomer and the alcohol monomer to an esterification or transesterification reaction, followed by a condensation polymerization reaction carried out according to a conventional procedure under reduced pressure or with the introduction of nitrogen gas.

[0080] The esterification or transesterification reaction can be carried out, if necessary, using a conventional esterification or transesterification catalyst, such as sulfuric acid, titanium butoxide, dibutyltin oxide, manganese acetate or magnesium acetate.

[0081] The condensation polymerization reaction can also be carried out using a well-known polymerization catalyst, such as titanium dioxide butoxide, dibutyltin oxide, tin acetate, zinc acetate, zinc disulfide, antimony trioxide, or germanium dioxide. In particular, the polymerization temperature and the amount of catalyst are not limited and can be appropriately determined.

[0082] In the esterification or transesterification reaction or the condensation polymerization reaction, all monomers can be added at once to increase the strength of the resulting crystalline polyester resin, or a process can be used in which a divalent monomer is reacted first and then a trivalent or higher monomer is added and reacted to reduce the amount of low molecular weight components.

[0083] From the perspective of achieving low-temperature fixability, suppressing image defects in double-sided printing, and charge stability, the content of crystalline resin (preferably a crystalline polyester resin) in the toner is preferably 1 to 30 wt%, based on the mass of the toner. This content is preferably 3 to 20 wt% and even more preferably 5 to 15 wt%.

[0084] Crystalline polyester resins can be used alone or in combination.

[0085] In addition to the crystalline resins mentioned above, the binder resin may also include other binder resins.

[0086] It is preferred that the binder resin comprises an amorphous resin. Furthermore, if an amorphous resin is used as the binder resin, known amorphous resins can be used.

[0087] Examples of amorphous resins include the following.

[0088] Polyvinyl chloride, phenolic resin, natural resin-modified phenolic resin, natural resin-modified maleic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumaron-indene resin, petroleum-based resin and vinyl resin.

[0089] It is preferred that at least one of these resins be 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.

[0090] An amorphous polyester resin is even more preferred. That is, it is preferred that the binder resin comprises an amorphous polyester resin. The use of an amorphous polyester resin makes the occurrence of the aforementioned interaction with the crystalline polyester resin more likely. This makes it easier to control the values ​​of G'3(70) / G'2(70), G'3(50), and G'3(70) within the aforementioned ranges.

[0091] Polyester resins typically used in toners can be suitable as amorphous polyester resins. Examples of monomers used in such polyester resins include polyhydric alcohols (dihydric, trihydric, or higher alcohols), polycarboxylic acids (dihydric, trihydric, or higher carboxylic acids), their anhydrides, or their lower alkyl esters.

[0092] The amorphous polyester resin is preferably a condensation polymer of a carboxylic acid and an alcohol, the latter being a polyhydric alcohol having an aromatic ring as its main component. With respect to the polyhydric alcohol with an aromatic ring, the aromatic diol content in the total alcohol forming the amorphous polyester resin is preferably 50 to 100 wt% or 80 to 99 wt%. In other words, the content of the monomer units corresponding to the aromatic diol among the monomer units corresponding to the total alcohol from which the amorphous polyester resin is formed is preferably 50 to 100 wt% or 80 to 99 wt%. In terms of mol%, 50 to 100 mol% is preferred and 80 to 99 mol% is more preferred.

[0093] Examples of such polyhydric alcohols include the following.

[0094] Examples of dihydric alcohols that have an aromatic ring include the following bisphenol derivatives.

[0095] 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)propane, etc.

[0096] Examples of 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-hexanetriol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolpropane, and trimethylolpropane. 1,3,5-Trihydroxymethylbenzene.

[0097] These polyhydric alcohols can be used alone or in combination.

[0098] Examples of polycarboxylic acids include the following.

[0099] Examples of dicarboxylic 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-dodecenyl succinic acid, isododecenyl succinic acid, n-dodecyl succinic acid, isododecyl succinic acid, n-octenyl succinic acid, n-octyl succinic acid, isooctenyl succinic acid, isooctyl succinic acid, anhydrides of these acids, and lower alkyl esters of these acids. Of these, maleic acid, fumaric acid, terephthalic acid, n-dodecenyl succinic acid, and adipic acid are preferred.

[0100] Examples of trivalent or higher-valent carboxylic acids, their anhydrides, and their lower alkyl esters include the following: 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetramethylenecarboxylic acid, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, Empol trimeric acid, their anhydrides, and their lower alkyl esters.

[0101] Of these, 1,2,4-benzenetricarboxylic acid (trimellitic acid) or its derivatives, such as its anhydrides, are preferred due to their low cost and ease of reaction control.

[0102] These polyhydric carboxylic acids can be used alone or in combination.

[0103] The polycarboxylic acid of the amorphous polyester resin preferably comprises a monomer unit corresponding to a linear aliphatic dicarboxylic acid.

[0104] If the amorphous polyester resin comprises a monomer unit corresponding to a linear aliphatic dicarboxylic acid, interaction with the alkyl group at the molecular chain end of the crystalline polyester resin is further facilitated. This makes it easier to control the values ​​of G'3(70) / G'2(70), G'3(50), and G'3(70) within the ranges mentioned above.

[0105] Among these, linear aliphatic dicarboxylic acids with 4 to 12 carbon atoms are preferred. Examples include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid.

[0106] The content of the monomer unit corresponding to a linear aliphatic dicarboxylic acid in the total amount of carboxylic acids from which the amorphous polyester is formed is preferably 1 to 50 mol%. This content is more preferably 10 to 50 mol% and even more preferably 15 to 40 mol%. With respect to mass percentage, 1 to 20 mass percentage and 3 to 15 mass percentage are preferred.

[0107] Furthermore, the amorphous polyester resin preferably has a molecular chain end 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).

[0108] If a carboxyl group is present at the molecular chain end of the amorphous polyester resin prior to condensation with the monomer, which has 6 to 24 carbon atoms, a condensation reaction with the linear alkyl monoalcohol occurs.

[0109] If a hydroxy group is present at the molecular chain end of the amorphous polyester resin prior to condensation with the monomer, which has 6 to 24 carbon atoms, a condensation reaction with the linear alkyl monocarboxylic acid occurs.

[0110] If the amorphous polyester resin has a structure at the molecular chain end formed by the condensation of 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, it is more likely that this structure will interact with the alkyl group at the end of the crystalline polyester resin.

[0111] As a result, the interaction between the crystalline polyester resin and the amorphous polyester resin is enhanced during the cooling process after melting. This makes it easier to control the values ​​of G'3(70) / G'2(70), G'3(50), and G'3(70) within the ranges mentioned above. This leads to improved fixation strength after the toner solidifies and further enhances the suppression of image defects in double-sided printing, which is desirable.

[0112] Examples of aliphatic linear monocarboxylic acids, which have 6 to 24 carbon atoms, include hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, stearic acid, arachidic acid, behenic acid and lignoceric acid.

[0113] Examples of aliphatic linear monoalcohols, which have 6 to 24 carbon atoms, include n-hexanol, n-octanol, lauryl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol and lignoceryl alcohol.

[0114] More preferably, at least one compound selected from the group consisting of linear alkyl monocarboxylic acids having 16 to 24 carbon atoms and linear aliphatic monoalcohols having 16 to 24 carbon atoms is selected. It is preferred that the linear alkyl compound A comprises an aliphatic linear monocarboxylic acid. Particularly preferred are aliphatic linear monocarboxylic acids having 16 to 24 carbon atoms, and among these, linear aliphatic monocarboxylic acids having 18 to 24 carbon atoms are preferred.

[0115] The amorphous polyester resin in which the linear alkyl compound A mentioned above is condensed is referred to as amorphous polyester resin A. The binder resin preferably comprises amorphous polyester resin A.

[0116] In amorphous polyester resin A, the content ratio of the structure in which linear alkyl compound A is condensed at the molecular chain end is preferably 0.5 to 15 wt%, more preferably 1 to 10 wt%, and even more preferably 1 to 5 wt%. With respect to mol%, the content ratio is preferably 1 to 15 mol%, more preferably 2 to 10 mol%.

[0117] The number of carbon atoms in linear alkyl compound A at the molecular chain end of the amorphous polyester is denoted by Aend. Similarly, the number of carbon atoms in linear alkyl compound C at the molecular chain end of the crystalline polyester resin is denoted by Cend. In this case, it is preferred that the following relationships are satisfied. Cend≥16 −4≤Cend−Aend≤6

[0118] If Cend - Aend satisfies the above relationship, this means that the number of carbon atoms at the molecular chain ends of the crystalline polyester resin and the amorphous polyester resin are close to each other. As a result, the previously mentioned interaction between the alkyl groups at the ends of the crystalline and amorphous polyester resins is more effective, which is desirable. This makes it 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.

[0119] Cend - Aend can be, for example, -4 to 22 and more, preferably -2 to 4.

[0120] Cend is more preferred in the 16 to 24 age group and even more preferred in the 18 to 22 age group.

[0121] Furthermore, it is preferred that Aend satisfies the condition Aend ≥ 16. For example, Aend is 6 to 26, preferably 16 to 24, and more preferably 16 to 22.

[0122] For Cend and Aend: If there are several linear alkyl compounds C, each carbon number refers to the carbon number of the component with the highest content (in moles); if the contents are equal, the carbon number refers to the component with the largest carbon number.

[0123] There are no particular restrictions on the process for producing polyester resin, and known methods can be used. For example, the aforementioned polyhydric alcohol and polycarboxylic acid are added simultaneously and polymerized by an esterification reaction or a transesterification reaction and a condensation reaction to produce a polyester resin. The polymerization temperature is also not particularly limited, but is preferably in the range of 180 to 290 °C. Polymerization catalysts such as titanium-based catalysts, tin-based catalysts, zinc acetate, antimony trioxide, and germanium dioxide can be used in the polymerization of polyester resin.

[0124] The polyester resin is preferably one produced by condensation polymerization using at least one titanium-containing catalyst and one tin-containing catalyst.

[0125] The softening point Tm of the amorphous polyester resin A is preferably 80 to 150 °C or 85 to 105 °C.

[0126] The weight-average molecular weight Mwa of the THF-soluble fraction of the amorphous polyester resin A is preferably 3000 to 1,000,000, 3000 to 20,000 or 4000 to 8000.

[0127] A single amorphous resin or several amorphous resins can be used.

[0128] To easily control the G'1(100), G'3(50) and G'3(70) values ​​of the toner within the ranges mentioned above, it is preferred to use several amorphous polyesters with softening points that differ by 20 to 60 °C. Even more preferably, it is preferred to use several amorphous polyesters with softening points that differ by 35 to 60 °C.

[0129] The amorphous resin preferably comprises, in addition to the amorphous polyester resin A, an amorphous polyester resin B that differs from amorphous polyester resin A. The softening point Tm of the 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 the amorphous polyester resin A.

[0130] The mass ratio of the low melting point amorphous polyester resin A to the high melting point amorphous polyester resin B is preferably 30 / 70 to 90 / 10 and more preferably 50 / 50 to 80 / 20.

[0131] The amorphous polyester resin B can be a condensation polymer of a carboxylic acid and an alcohol, in addition to the monoalcohol and the monocarboxylic acid in the amorphous polyester resin A described above.

[0132] The alcohol preferably comprises an aromatic diol. The content of the aromatic diol in the total alcohol forming the amorphous polyester resin B is preferably 80 to 100 mol%, more preferably 90 to 100 mol%. Furthermore, its mass percentage is preferably 80 to 100 mass%, more preferably 90 to 100 mass%.

[0133] The carboxylic acid is preferably at least one selected from the group consisting of adipic acid, maleic acid, fumaric acid, and terephthalic acid. Amorphous polyester resin B is preferably crosslinked with a trivalent carboxylic acid such as trimellitic acid or trimellitic anhydride.

[0134] The glass transition temperature (TgB) of the amorphous polyester resin B, measured with a differential dynamic calorimeter, is preferably between 50.0 and 70.0 °C and more preferably between 54.0 and 60.0 °C.

[0135] The weight-average molecular weight Mwb of the amorphous polyester resin B is preferably 20,000 to 300,000, 50,000 to 200,000 or 80,000 to 150,000.

[0136] The softening point Tm of the amorphous polyester resin B is preferably 120 to 170 °C and more preferably 130 to 160 °C.

[0137] The content ratio of amorphous polyester resin A in the amorphous resin is, for example, 50.0 to 95.0 wt% or 60.0 to 80.0 wt%.

[0138] The content ratio of amorphous polyester resin B in the amorphous resin is, for example, 5.0 to 50.0 mass-% or 20.0 to 40.0 mass-%.

[0139] The content ratio of the amorphous polyester resin A, based on the mass of the toner particles, can be, for example, 20.0 to 80.0 wt%, 30.0 to 70.0 wt% or 40.0 to 60.0 wt%.

[0140] The content ratio of the amorphous polyester resin B, based on the mass of the toner particle, can be, for example, 5.0 to 45.0 wt%, 10.0 to 35.0 wt% or 17.0 to 28.0 wt%.

[0141] Furthermore, if the amorphous polyester resin comprises an amorphous polyester resin A having a structure in which the linear alkyl compound A mentioned above is condensed at the end of the molecular chain, it is preferred that the following is satisfied. That is, the weight-average molecular weight of the THF-soluble fraction of the amorphous polyester resin A is denoted by Mwa, and the weight-average molecular weight of the THF-soluble fraction of the crystalline polyester resin is denoted by Mwc. In this case, Mwa / Mwc is, for example, 0.65 or less, and it is preferred that the relationship Mwa / Mwc ≤ 0.50 is satisfied.

[0142] It is preferred that the Mwa / Mwc ratio satisfies the above relationship, as charge stability during shelf-life pressure is improved, although the mechanism is unclear. More preferred is Mwa / Mwc ≤ 0.4. Mwa / Mwc is preferably 0.10 to 0.50 and more preferably 0.20 to 0.40.

[0143] The binder resin can be a vinyl resin. Examples of vinyl resins that can be used as binder resins include polymers of vinyl monomers containing ethylene unsaturated bonds. An ethylene unsaturated bond is a carbon-carbon double bond capable of radical polymerization, and examples include a vinyl group, a propenyl group, an acryloyl group, and a methacryloyl group.

[0144] Examples of vinyl monomers are listed below.

[0145] Styrene and styrene-based monomers such as 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;

[0146] Acrylic acid; and acrylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate and phenyl acrylate;

[0147] Methacrylic acid; and methacrylic acid esters such as 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; and furthermore

[0148] Acrylonitrile, methacrylonitrile, acrylamide, etc.

[0149] Other examples include acrylic and methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate, and polymerizable monomers containing a hydroxyl group, such as 4-(1-hydroxy-1-methylbutyl)styrene and 4-(1-hydroxy-1-methylhexyl)styrene. These can be used alone or in combination.

[0150] Among these, it is preferred to use monomers that are condensates of acrylic acid or methacrylic acid with alcohols 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.

[0151] In addition to those mentioned above, various polymerizable monomers capable of vinyl polymerization can be used in combination with the vinyl resin as needed.

[0152] Examples of such polymerizable monomers are listed below.

[0153] 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, vinylhexyl ketone, and methyl isopropenyl ketone; N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, and N-vinylpyrrolidone; vinylnaphthalenes; unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, and mesaconic acid; unsaturated dibasic acid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride and alkenyl succinic anhydride;Semiesters of unsaturated basic acids such as methyl maleate semiesters, ethyl maleate semiesters, butyl maleate semiesters, methyl citraconate semiesters, ethyl citraconate semiesters, butyl citraconate semiesters, methyl itaconate semiesters, methyl alkenyl succinate semiesters, methyl fumarate semiesters, and methyl mesaconate semiesters; 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; anhydrides of such α,β-unsaturated acids and lower fatty acids; and polymerizable monomers with a carboxyl group, such as alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, their anhydrides, and their monoesters.

[0154] Furthermore, if necessary, the vinyl resin can be a polymer cross-linked with a cross-linkable polymerizable monomer, such as those mentioned below as examples.

[0155] Examples of such crosslinkable polymerizable monomers include the following monomers.

[0156] Aromatic divinyl compounds; alkyl chain-linked diacrylate compounds; alkyl chain-linked diacrylate compounds comprising ether bonds; aromatic group and chain-linked diacrylate compounds comprising ether bonds; polyester-type diacrylates; and polyfunctional crosslinking agents.

[0157] Examples of such aromatic divinyl compounds include divinylbenzene and divinylnaphthalene.

[0158] 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 compounds in which the acrylate in the above-mentioned compounds is replaced by methacrylate.

[0159] The vinyl resin can also be a copolymer of monomers comprising at least one polymerizable monomer selected from the vinyl monomers listed above, 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 proportion of crosslinkable polymerizable monomer in the monomers can be approximately 0.5 to 5.0 wt%.

[0160] The vinyl resin can also be a resin produced using a polymerization initiator. For efficiency, the polymerization initiator should be used in an amount of 0.05 to 10.00 parts by mass per 100.00 parts by mass of polymerizable monomers. Examples of such polymerization initiators are listed below.

[0161] 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-cyclohexanecarbonitrile), 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-butyl peroxide, tert-butyl cumyl peroxide, dicumyl peroxide, α,α'-bis(tert-butylperoxyisopropyl)benzene, isobutyl peroxide and octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-trioyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, dimethoxyisopropyl peroxydicarbonateDi(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-Butylperoxyisopropylcarbonate, di-tert-butyl peroxyisophthalate, tert-butylperoxyallyl carbonate, tert-amylperoxy-2-ethylhexanoate, di-tert-butylperoxyhexahydroterephthalate and di-tert-butylperoxyazelate.,

[0162] The vinyl resin and polyester resin used to form the hybrid resin in which the vinyl resin and polyester resin are bound can be the same as the vinyl resin and polyester resin used as the amorphous resin described above.

[0163] A hybrid resin formed from a vinyl resin and a polyester resin can, for example, be obtained by polymerization using a compound that can react with monomers that produce both resins (hereinafter referred to as the “bireactive compound”).

[0164] Examples of bireactive 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 preferred.

[0165] When using a hybrid resin formed from a vinyl resin and a polyester resin, the content ratio of vinyl resin in the hybrid resin is preferably 10 wt% or more, 20 wt% or more, 40 wt% or more, 60 wt% or more or 80 wt% or more and preferably 100 wt% or less or 90 wt% or less.

[0166] Furthermore, the binder resin can also comprise a polymer having a structure resulting from the reaction of a vinyl resin component with a hydrocarbon compound. Among these, the binder resin preferably comprises a graft polymer formed by grafting a vinyl monomer onto a polyolefin. The vinyl monomer preferably comprises styrene, (meth)acrylonitrile, and at least one selected from the group consisting of acrylic esters. The binder resin can also comprise a graft polymer formed by grafting a styrene-acrylic resin onto a polyolefin.

[0167] When the binder resin includes such a graft polymer, compatibility between the wax and the resin is enhanced, making it easier to suppress poor charging and component contamination due to poor wax dispersion. The content of the graft polymer, formed by grafting a vinyl monomer onto a polyolefin, is preferably 1.0 to 15.0 wt%, based on the mass of the toner, and more preferably 2.0 to 10.0 wt%.

[0168] A wax content within the range mentioned above facilitates uniform dispersion of the wax within the binder resin. The polyolefin is not limited, as long as it is a polymer or copolymer of an unsaturated hydrocarbon, and various polyolefins can be used. Polyethylene-based and polypropylene-based polyolefins are particularly preferred. Multiple polyolefins can also be used.

[0169] The vinyl monomer can be selected from the monomers that can be used for the vinyl resin described above.

[0170] Graft polymers in which vinyl monomers are grafted onto polyolefins can be obtained by known methods, such as the reactions mentioned above between these polymers or the reactions between the monomers of one polymer and the monomers of another polymer. Other resins

[0171] The binder resin may comprise resins other than those listed above, provided that the effects of the present disclosure are not impaired, for purposes such as improving pigment dispersibility. Examples of such resins are listed below.

[0172] Polyvinyl chloride, phenolic resin, natural resin-modified phenolic resin, natural resin-modified maleic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumaron-indene resin and petroleum-based resin.

[0173] The content of the binder resin is preferably 70 to 98 wt% and more preferably 80 to 95 wt%, based on the mass of the toner. wax

[0174] The toner particle contains wax. The wax can be selected for optimal use in combination with the crystalline resin. Examples of waxes are listed below.

[0175] Hydrocarbon waxes such as microcrystalline wax, paraffin waxes and Fischer-Tropsch waxes; oxides of hydrocarbon waxes or their block copolymers such as oxidized polyethylene wax; waxes with fatty acid esters such as carnauba wax as a major component; and partially or completely deoxidized fatty acid esters such as deoxidized carnauba wax.

[0176] Further examples are listed below. Saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassidic acid, eleostearic acid, and parinaric 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; saturated fatty acid bisamides such as methylenebis(stearamide), ethylenebis(capramide), ethylenebis(lauramide), and hexamethylenebis(stearamide); unsaturated fatty acid amides such as ethylene bis(oleamide), hexamethylene bis(oleamide), N,N'-dioleyladipamide and N,N'-dioleyl sebacate;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 obtained by grafting aliphatic hydrocarbon waxes with vinyl monomers such as styrene and acrylic acid; partial esters of fatty acids and polyhydric alcohols such as behenic monoglyceride; and methyl ester compounds containing hydroxyl groups, obtained by hydrogenation of vegetable oils and fats.

[0177] The wax preferably comprises at least one wax from the group consisting of ester waxes and hydrocarbon waxes, more preferably hydrocarbon waxes, and even more preferably Fischer-Tropsch waxes. The melting point of the wax is preferably 75 to 120 °C, more preferably 84 to 120 °C, and even more preferably 88 to 110 °C. It is more preferred that the difference between the melting point Tc of the crystalline resin and the melting point of the wax is within 10 °C.

[0178] If the wax contains hydrocarbon wax, it is more likely that the hydrocarbon wax, along with the crystalline resin, will interact with the binder resin during cooling after melting, as described above. The increase in the storage elastic modulus during cooling is more gradual than if the wax does not contain hydrocarbon wax, making it easier to control the G'3(70) / G'2(70) value more effectively.

[0179] Furthermore, the number of carbon atoms corresponding to a peak recognized as the maximum peak when the wax is analyzed by gas chromatography-mass spectrometry (GC / MS) is denoted by Wmax. In this case, Wmax - Aend is, for example, 12 to 42, and it is preferred that Wmax and Aend satisfy the relationships Aend ≥ 16 and 16 ≤ Wmax - Aend ≤ 30.

[0180] If Wmax - Aend is within this range, it is easier to increase the value of G'3(70), and image defects in double-sided printing can be suppressed more effectively. It is assumed that the crystalline polyester resin is more likely to shift during the cooling process after melting, resulting in a larger G'3(70).

[0181] More preferred is 20 ≤ Wmax - Aend ≤ 30 and even more preferred is 20 ≤ Wmax - Aend ≤ 25.

[0182] The wax content, based on the mass of the toner, is preferably 2.0 to 30.0 wt%, more preferably 4.0 to 20.0 wt% and even more preferably 4.0 to 10.0 wt%. Inorganic filler particles

[0183] The toner particles can include inorganic filler particles as needed, for example to adjust viscoelasticity.

[0184] Preferred inorganic filler particles include silicon dioxide, titanium oxide, aluminum oxide, metal titanates such as strontium titanate and calcium titanate, calcium carbonate and kaolin.

[0185] The inorganic filler particles are preferably treated with a fatty acid. Surface treatment of the filler particles with a fatty acid is preferred because it allows the filling effect to develop more effectively due to the interaction with the alkyl groups of the crystalline resin via the fatty acid.

[0186] The number-mean diameter of the primary particles of the inorganic filler particles incorporated into the toner particles is preferably 0.15 to 0.45 µm and more preferably 0.20 to 0.40 µm. The number-mean diameter of the primary particles of the inorganic filler particles can be measured using known methods, such as a scanning electron microscope.

[0187] The content ratio of the inorganic filler particles, based on the mass of the toner particles, is preferably 0 to 20 wt% and more preferably 0 to 7 wt%. dye

[0188] The toner particles may optionally contain a dye. Examples of dyes are listed below.

[0189] Black dyes include carbon black and those tinted black with yellow, magenta, and cyan dyes. While pigments can be used alone as a dye, using a combination of dyes and pigments is preferable for improving the clarity of full-color images in terms of image quality.

[0190] Pigments for magenta toner can be illustrated by 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, 37, 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 and 282; CI Pigment Violet 19; and CI Vat Red 1, 2, 10, 13, 15, 23, 29 and 35.

[0191] Colorants for magenta toners can be illustrated by the following examples: oil-soluble colorants such as CI Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109 and 121; CI Disperse Red 9; CI Solvent Violet 8, 13, 14, 21 and 27; and CI Disperse Violet 1 as well as 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 and 40 as well as CI Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27 and 28.

[0192] Pigments for cyan toners can be illustrated by the following examples: CI Pigment Blue 2, 3, 15:2, 15:3, 15:4, 16, and 17; CI Vat Blue 6; CI Acid Blue 45; and copper phthalocyanine pigments having at least one and no more than five phthalimidomethyl groups substituted on the phthalocyanine backbone. CI Solvent Blue 70 is an example of a dye for cyan toners.

[0193] Pigments for yellow toners can be illustrated by the following examples: 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 and 185, as well as CI Vat Yellow 1, 3 and 20. CI Solvent Yellow 162 is an example of a dye for yellow toners.

[0194] These dyes can be used alone, in mixtures, or even in the form of a solid solution. Dyes are selected based on hue, color saturation, brightness, lightfastness, overhead transparency, and dispersibility in toner.

[0195] The dye content is preferably 0.1 to 30.0 parts by mass per 100 parts by mass of the binder resin. Load control device

[0196] The toner particle may optionally include a charge control agent. While known charge control agents can be used, metal compounds of aromatic carboxylic acids are particularly preferred because they are colorless, enable rapid toner charging, and can stably maintain a constant charge level.

[0197] Negative charge regulators include metal salicylate compounds, metal naphthoate compounds, metal dicarboxylic acid compounds, polymer compounds having a sulfonic acid or carboxylic acid group in a side chain, polymer compounds having a sulfonic acid salt or sulfonic acid ester in a side chain, polymer compounds having a carboxylic acid salt or carboxylic acid ester in a side chain, boron compounds, urea compounds, silicon compounds and calixarenes.

[0198] The charge control agent can be added internally or externally to the toner particles. The concentration 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. External additive

[0199] The toner may include an external additive. For example, the toner can be produced by adding an external additive to a toner particle. Preferred external additives are inorganic fine particles such as silicon dioxide, titanium dioxide, aluminum oxide, and metal titanates. The inorganic fine particles used as external additives are preferably hydrophobized with a water-repellent agent such as a silane compound, silicone oil, or a mixture thereof.

[0200] To improve flowability, inorganic fine particles with a BET-specific surface area of ​​50 to 400 m² are used. 2 / g preferred. To stabilize shelf life, inorganic fine particles with a BET-specific surface area of ​​10 to 50 m² are used. 2 / g preferred. To achieve both improved flowability and stabilized shelf life, inorganic fine particles with a BET-specific surface area within the ranges mentioned above can be used in combination. A known mixer, such as a Henschel mixer, can be used to mix the toner particle and external additives.

[0201] The concentration 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. developer

[0202] While toner can be used as a single-component developer, it is preferable to mix it with a magnetic carrier to create a two-component developer, as this produces stable images over a long period. In other words, a two-component developer comprising toner and a magnetic carrier, where the toner is the toner described above, is more preferred.

[0203] Examples of magnetic supports include well-known supports such as iron powder or surface-oxidized iron powder; metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium and rare earth elements, their alloying particles or their oxide particles; magnetic materials such as ferrite; and magnetic material-dispersed resin supports (so-called resin supports) comprising the magnetic material and a binder resin that holds the magnetic material in a dispersed state.

[0204] When toner is mixed with a magnetic carrier to produce a two-component developer, the toner content ratio in the two-component developer is preferably from 2.0 to 15.0 wt% and more preferably from 4.0 to 13.0 wt%. Methods for producing toner

[0205] There are no particular restrictions on a method for manufacturing toner, and conventional manufacturing processes such as suspension polymerization, emulsion aggregation, melt kneading and dissolution suspension can be used.

[0206] The procedure for producing toner using the melt kneading powdering process is described below. Raw material mixing step

[0207] In the raw material mixing step, the materials that will form the toner particles, such as a binder resin comprising a crystalline resin and, if required, an amorphous resin, wax, and, if required, other components such as a dye and a charge control agent, are weighed, mixed, and blended in predetermined quantities. Examples of mixing equipment include double cone mixers, V-mixers, drum mixers, super mixers, Henschel mixers, Nauta mixers, and the Mechano Hybrid (manufactured by Nippon Coke and Engineering Co., Ltd.). Melting and kneading step

[0208] Next, the mixed materials are melt-kneaded to disperse the wax and other components in the binder resin. Batch kneaders, such as pressure kneaders and Banbury mixers, as well as continuous kneaders, can be used in the melt-kneading process. Single- or twin-screw extruders are commonly used due to their advantage of continuous production. Examples include the KTK twin-screw extruder (manufactured by Kobe Steel, Ltd.), the TEM twin-screw extruder (manufactured by Toshiba Machine Co., Ltd.), the PCM kneader (manufactured by Ikegai Iron Works Co., Ltd.), a twin-screw extruder (KCK Corporation), the Co-Kneader (manufactured by Buss AG), and the Kneedex (manufactured by Nippon Coke and Engineering Co., Ltd.). Additionally, the resin composition obtained by melt-kneading can be rolled using a twin-roll mill or similar equipment and cooled with water or a similar cooling agent in a subsequent cooling step.

[0209] In the melt kneading step, the melt kneading is preferably carried out using a twin-screw extruder.

[0210] The kneading temperature is preferably 110 to 160 °C, more preferably 110 to 150 °C. The screw speed during kneading can be adjusted appropriately depending on the equipment used, but is not limited; for example, 200 to 300 rpm is preferred. Cooling step

[0211] The cooling procedure is not particularly limited. Examples of suitable methods include rolling the kneaded resin composition between two rollers or drums, followed by cooling with a steel belt cooler (manufactured by Nippon Steel Conveyor Co., Ltd.), or rolling while cooling with a press roller and a drum equipped with an internal cooling mechanism, such as a belt drum flaker (manufactured by Nippon Coke and Engineering Co., Ltd.). In the cooling step, rolling while cooling with a belt drum flaker is preferred. Pulverization step

[0212] The cooled resin composition is then pulverized to the desired particle diameter in the pulverization step. In this step, the material is coarsely pulverized using a pulverizer such as a crusher, hammer mill, or spring mill, and then finely pulverized using a fine pulverizer such as the Cryptron System (manufactured by Kawasaki Heavy Industries Co., Ltd.), Super Rotor (manufactured by Nisshin Engineering Co., Ltd.), Turbo Mill (manufactured by Turbo Kogyo Co., Ltd.), or an air jet system. Classification step

[0213] If required, classification can then be carried out using a classifier or sieve, such as Elbow Jet of an inertial classification system (manufactured by Nitetsu Mining Co., Ltd.), Turboplex of a centrifugal classification system (manufactured by Hosokawa Micron Corporation), TSP Separator (manufactured by Hosokawa Micron Corporation) or Faculty (manufactured by Hosokawa Micron Corporation) to obtain toner particles. External addition step

[0214] The resulting toner particles can be used as is. Toner can also be obtained by externally adding an additive to the surface of the toner particles. Examples of methods for adding external additives include mixing the classified toner with a predetermined amount of various known external additives and stirring and mixing using a mixer such as a double-cone mixer, V-mixer, drum mixer, supermixer, Henschel mixer, Nauta mixer, Mechano Hybrid (manufactured by Nippon Coke and Engineering Co., Ltd.), or Nobilta (manufactured by Hosokawa Micron Corporation) as the external addition device. Glowing step

[0215] In toner production, the melt-kneaded product obtained after the melt-kneading step is preferably annealed by holding it for 10 minutes or longer at a temperature 5 °C or more above the melting point of the crystalline resin. Annealing can be carried out after the melt-kneading and cooling steps, but is preferably carried out before the cooling step.

[0216] Methods for measuring various physical properties of toner and raw materials are described below. <Messung des Speicherelastizitätsmoduls G' durch Messung der Tonerviskoelastizität>

[0217] The measuring instrument used is a rotary plate rheometer “ARES” (manufactured by TA Instruments). The sample is prepared by pressing the toner into a disc with a diameter of 8 mm and a thickness of 2.0 ± 0.3 mm (20 MPa for 30 seconds) using a tablet press in an environment at 25 °C.

[0218] The sample is mounted on a parallel plate, and the temperature is increased from room temperature (25 °C) to 80 °C over a period of 15 minutes to deform the sample. After cooling to the viscoelasticity measurement starting temperature, the measurement is initiated, and the complex viscosity is measured. In this case, the sample is adjusted so that the initial normal force is zero. Furthermore, as described below, the influence of the normal force on subsequent measurements can be eliminated by enabling automatic tension adjustment.

[0219] Measurements were carried out under the following conditions. (1) A parallel plate with a diameter of 8 mm is used. (2) The frequency is set to 6.28 rad / sec (1.0 Hz). (3) The initial strain is set to 0.01%. (4) The measurement interval (step time) is set to 15 s.

[0220] The measurement is performed under the set conditions of the following automatic adjustment mode settings. Thus, the measurement is performed in automatic strain adjustment mode (Auto Strain). (5) The maximum strain (Max Applied Strain) is set to 1.0%. (6) The maximum torque (Max Allowed Torque) is set to 150.0 g·cm and the minimum torque (Min Allowed Torque) to 0.2 g·cm. (7) The automatic strain adjustment is set to 20.0% of the current strain. The measurement is performed in automatic tension adjustment mode. (8) The automatic tension direction is set to compression. (9) The initial static force is set to 10.0 g and the auto tension sensitivity is set to 40.0 g. (10) In the operating conditions for automatic tensioning (Auto Tension), the sample modulus is 1.0 × 10 3 Pa or larger.

[0221] Step (i): Measurements are carried out while the temperature is increased from 30 °C to 100 °C at a rate of 2 °C / min in order to obtain a curve G'1(T) of the storage elasticity modulus G' [Pa] versus the temperature T [°C].

[0222] Step (ii): After step (i), measurements are carried out while the temperature is reduced from 100 °C to 30 °C at a rate of 2 °C / min in order to obtain a curve G'2(T) of the storage elasticity modulus G' [Pa] against the temperature T [°C].

[0223] Step (iii): After step (ii) the temperature is increased from 30 °C to 100 °C at a rate of 2 °C / min in order to obtain a curve G'3(T) of the storage elasticity modulus G' [Pa] against the temperature T [°C].

[0224] The measurement results for the storage elasticity modulus G', obtained from the above measurement, are represented as a temperature-storage elasticity modulus curve, with temperature on the horizontal axis and the common logarithm logG' of the storage elasticity modulus G' on the vertical axis. The temperature-storage elasticity modulus curve is obtained by smoothly connecting the points.

[0225] Next, the slope of the obtained temperature-residual elasticity modulus curve is determined, and a differential curve is plotted, represented by differentiating the common logarithm logG' with respect to temperature. In this way, if the toner's residual elasticity modulus at a temperature T (°C) is denoted by G'(T), a graph can be obtained 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.

[0226] The same procedure is applied to the curve G'2(T) to obtain a diagram with temperature T on the horizontal axis and the value d(logG'2(T)) / dT, obtained by differentiating logG'2(T) with respect to temperature T, on the vertical axis.

[0227] In the diagram with the measured temperature T on the horizontal axis and the value d(logG'2(T)) / dT, obtained by differentiating logG'2(T) with respect to the temperature T on the vertical axis, the minimum value is identified in the range of 50.0 to 70.0 °C, and the temperature at which this minimum value is obtained is determined as temperature T2 (°C). If there are multiple minimum values ​​in the range of 50.0 to 70.0 °C, the smallest and lowest value is determined as the minimum value, and the corresponding temperature is selected as T2. The value of d(logG'2(T2)) / dT is then obtained.

[0228] The values ​​of G'1(100), G'3(50), G'3(70) and G'3(70) / G'2(70) are also obtained.

[0229] If it is difficult to smoothly connect the points in the temperature-residual elasticity modulus diagrams, the measured values ​​can be smoothed to make it easier to connect the points smoothly. The smoothing method used is the simple motion averaging method, based on plotting three points before and after the point. Methods for separating materials from toner

[0230] Materials encompassed by the toner can be separated from the toner by exploiting the difference in the solubility of each material in the solvent.

[0231] First separation: The toner is dissolved in methyl ethyl ketone (MEK) at 23 °C, and a soluble fraction (amorphous resin) and an insoluble fraction (crystalline resin, wax, dye, inorganic filler particles, etc.) are separated.

[0232] Second separation: The insoluble fraction obtained in the first separation (crystalline resin, wax, dye, inorganic filler particles, etc.) is dissolved in MEK at 100 °C, and a soluble fraction (crystalline resin, wax) and an insoluble fraction (dye, inorganic filler particles, etc.) are separated.

[0233] Third separation: The soluble fraction (crystalline resin, wax) obtained in the second separation is dissolved in chloroform at 23 °C, and a soluble fraction (crystalline resin) and an insoluble fraction (wax) are separated.

[0234] Measurement of the content of crystalline resin, amorphous resin and inorganic filler particles in the binder resin of the toner.

[0235] The masses of the soluble and insoluble fractions are measured in each separation step to calculate the content of crystalline resin and amorphous resin in the binder resin of the toner.

[0236] Calculation of the content ratio of the monomer units in amorphous polyester resin A, amorphous polyester resin B and crystalline polyester resin

[0237] The content of the constituent monomers in amorphous polyester resin A, amorphous polyester resin B and crystalline polyester resin is calculated using NMR in the following way.

[0238] A total of 5 mg of the resin to be measured is weighed out and dissolved in deuterated THF or deuterated chloroform. A 1H-NMR measurement is performed, and the composition ratio is calculated from the integrated value of each peak. Specific instrument conditions are described below. Measurement conditions -Measuring device: JNM-ECA400FT-NMR (JEOL) -Measuring core: 1H -Solvent: deuterated THF or deuterated chloroform -Measurement frequency: 400 MHz -Pulse width: 5.0 µs -Frequency range: 10,500 Hz -Number of accumulations: 64 -Measurement temperature: Room temperature

[0239] Aend, Cend, Cal and Cca can be calculated from the results obtained.

[0240] Methods for measuring melting points and endothermic peaks of toner, resin, etc.

[0241] The melting points and endothermic peaks of toner, resin, etc. are measured using a DSC Q1000 (manufactured by TA Instruments) under the following conditions. -Heating rate: 10 °C / min -Starting temperature: 20 °C -Final temperature: 180 °C

[0242] The melting points of indium and zinc are used for temperature correction of the instrument detector, and the heat of fusion of indium is used for calorimetry value correction. Specifically, a 5 mg sample is weighed and placed in an aluminum pan for differential scanning calorimetry. An empty silver pan is used as a reference. The peak temperature of the maximum endothermic peak during the initial temperature rise is taken as the melting point. The maximum endothermic peak refers to the peak with the highest endothermic value if there are multiple peaks. The endothermic value of this maximum endothermic peak is then determined. The assignment of each peak can be determined by performing DSC measurements on each individual material separated from the toner described above. The melting point Tc of the crystalline resin and the melting point Tw of the wax can also be obtained.

[0243] Method for measuring the glass transition temperature of toner, resin, etc.

[0244] As with the measurements of the melting point, endothermic peaks, and endothermic quantity of toner and resin described above, measurements are performed using a DSC Q1000 (manufactured by TA Instruments) under the following conditions. Measurements are carried out in a measuring range of 20 to 180 °C at a temperature rise rate of 10 °C / min. During the measurement, the resin temperature is first raised to 200 °C and held for 10 minutes, then lowered to 20 °C, and then raised again. During this second temperature rise process, the specific heat change is measured in the temperature range of 20 to 100 °C. The intersection of the line midway between the baselines before and after the specific heat change and the differential thermal curve is taken as the glass transition temperature (Tg) of the toner, resin, etc. Method for measuring the resin softening point (Tm)

[0245] The softening point of a resin is measured using a constant-load extrusion capillary rheometer, "Flow Tester CFT-500D Flow Property Evaluation Device" (manufactured by Shimadzu Corporation), according to the manual supplied with the device. With this instrument, a constant load is applied to the sample from above using a piston, while the sample, which has been loaded into the cylinder, is heated and melted. The molten sample is then extruded from a nozzle at the bottom of the cylinder, producing a flow curve that shows the relationship between the amount of piston movement and the temperature.

[0246] The "melting point in the 1 / 2 method," described in the manual provided with the "Flow Tester CFT-500D Flow Property Evaluation Device," is used as the softening point. The melting point in the 1 / 2 method is calculated as follows.

[0247] First, half the difference between the piston drop at the point where the outflow ends (outflow endpoint, Smax) and the piston drop at the point where the outflow begins (minimum point, Smin) is calculated (this is assumed to be X; X = (Smax - Smin) / 2). The temperature on the flow curve when the piston drop is the sum of X and Smin is the melting temperature according to the 1 / 2 method.

[0248] The sample is prepared by compressing 1.0 g of resin at 10 MPa for 60 seconds using a tablet press (e.g., NT-100H, manufactured by NPa System Co., Ltd.) at 25 °C to form a cylinder with a diameter of 8 mm. Specific measurement procedures are performed according to the manual provided with the instrument.

[0249] The measurement conditions for the CFT-500D are as follows: -Test mode: Temperature rise method -Starting temperature: 50 °C -Final temperature: 200 °C -Measurement interval: 1.0 °C -Temperature increase rate: 4.0 °C / min -Piston cross-sectional area: 1,000 cm² 2 -Test load (piston load): 10.0 kgf (0.9807 MPa) -Preheating time: 300 sec. -Diameter of die hole: 1.0 mm -Die length: 1.0 mm

[0250] Method for determining the number of carbon atoms for the maximum peak of wax

[0251] The number of carbon atoms for the maximum peak of wax is measured as follows. Thermal desorption is performed using the ATD (Auto Thermal Desorption) method. The following measuring instrument is used. Thermal desorption device: TurboMatrix ATD (PerkinElmer Corp.) GC / MS: TRACE DSQ (Thermo Fisher Scientific Inc.) Preparation of a glass tube containing an internal standard

[0252] A glass tube for the thermal desorption apparatus is prepared in advance by layering 10 mg of Tenax TA adsorbent between glass wool, and conditioning is carried out at 300 °C for 3 hours under an inert atmosphere. A total of 5 µl of a 100 ppm methanol solution of deuterated n-hexadecane (n-hexadecane D34) is then adsorbed onto the Tenax TA to create a glass tube containing an internal standard.

[0253] Deuterated n-hexadecane, which has a different retention time, is used as an internal standard to distinguish the peak from the peak of wax-encased n-hexadecane, as mentioned above. All volatile component concentrations are converted to deuterated n-hexadecane. The procedure for converting the volatile component concentrations is described below. Measurement of wax

[0254] A total of 1 mg of weighed wax is wrapped in aluminum foil, baked at 300 °C, and placed in a prepared tube containing an internal standard. The sample is covered with a Teflon cap (registered trademark) for thermal desorption and placed in the thermal desorption unit. This sample is measured under the following conditions, and the retention time of the volatile components of the internal standard is calculated.

[0255] Conditions of the thermal desorption device -Tube temperature: 200 °C -Transfer temperature: 300 °C Valve temperature: 300 °C -Column pressure: 150 kPa -Inlet flow rate: 25 ml / min. -Outlet distribution: 10 ml / min. -Secondary adsorption tube material: Tenax TA -Retention time: 10 min. -Secondary adsorption tube temperature during desorption: -30 °C -Secondary adsorption tube temperature: 300 °C

[0256] GC / MS conditions -Column: Ultraalloy (metal column) UT-5 (inner diameter 0.25 mm, liquid phase 0.25 µm, length 30 m) -Column temperature rise conditions: 60 °C (holding time 3 min), temperature rise from 60 °C to 350 °C (temperature rise rate 20.0 °C / min), 350 °C (holding time 10 min)

[0257] The transfer line of the thermal desorption device is directly connected to the GC column; the GC injection port is not used. analysis

[0258] Among all peaks after the retention time of n-hexadecane, with the exception of the peak of deuterated n-hexadecane, which serves as an internal standard, the maximum peak is identified from the peaks obtained by the above-mentioned processes and the corresponding number Wmax of carbon atoms is calculated.

[0259] Method for measuring the weight-mean molecular weight (Mw) of THF-soluble fractions, such as resins, using gel permeation chromatography (GPC)

[0260] The weight-mean molecular weight (Mw) of fractions soluble in tetrahydrofuran (THF), such as resins, is measured using gel permeation chromatography (GPC) as follows. First, toner is dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. The resulting solution is then filtered through a solvent-resistant Myshori Disc membrane filter (manufactured by Tosoh Corporation) with a pore size of 0.2 µm to obtain a sample solution. The sample solution is adjusted so that the concentration of the components soluble in THF is 0.8 wt%. Measurements are then performed using this sample solution under the following conditions. -Device: HLC8320 GPC (Detector: RI) (manufactured by Tosoh Corporation) -Column: Shodex LF-404, LF-404 (manufactured by Showa Denko KK) -Eluent: Tetrahydrofuran (THF) -Flow rate: 1.0 ml / min Oven temperature: 40.0 °C -Sample injection volume: 0.10 ml

[0261] To calculate the molecular weight of the sample, a molecular weight calibration curve is used, which was created using standard polystyrene resins (e.g., “EasiVial PS-H Polystyrene”, manufactured by Agilent Technologies, Inc.). Method for measuring the weight-mean particle diameter (D4) of toner

[0262] The volume-averaged particle diameter (Dv) (weight-averaged particle diameter (D4)) of the toner is calculated as follows. The measuring device used is a CDA-1000X particle counting and analysis instrument with a 100 µm aperture tube, employing a pore resistance method (commercially available from Sysmex Corporation). The measurement conditions are set, and the measurement data are analyzed using the included dedicated CDA-1000X software (commercially available from Sysmex Corporation).

[0263] For example, “Cellpack” (commercially available from Sysmex Corporation) can be used as the aqueous electrolyte solution for the measurement.

[0264] Here, the dedicated software is configured as follows before the measurement and analysis are carried out.

[0265] On the "Measurement Conditions Setting" screen of the dedicated software, the total count is set to 50,000, the number of repeat measurements to 1, and the measurement mode to the total count (without limit).

[0266] One specific measurement method is as follows. (1) 150 ml of an aqueous electrolyte solution are placed in a special round-bottomed glass beaker, which is placed on a sample table, and stirred with a stirring propeller at 500 rpm. The user then clicks on "Blankcheck Measurement" in the special software to start the measurement and confirms that the count is below 500. If the count is 500 or more, the beaker and aperture are washed repeatedly. (2) 30 ml of the aqueous electrolyte solution are placed in a 100 ml flat-bottomed glass beaker. 0.3 ml of a dilute solution prepared by diluting ‘Contaminon N’ (a 10% aqueous solution of a neutral cleaning agent with a pH of 7 for washing precision instruments, consisting of a non-ionic surfactant, an anionic surfactant and an organic builder, commercially available from Wako Pure Chemical Industries, Ltd.) with three times its weight of deionized water is added as a dispersant. (3) An ultrasonic disperser with an electrical power of 120 W, “Ultrasonic Dispensing System Tetra150” (commercially available from Nikkaki Bios Co., Ltd.), which has two oscillators with a oscillation frequency of 50 kHz and phases shifted by 180 degrees, is prepared. 3.3 L of deionized water are placed in a water tank of the ultrasonic disperser, and 2 ml of Contaminon N are added to this water tank. (4) The beaker in (2) is inserted into a beaker mounting opening of the ultrasonic disperser, and the ultrasonic disperser is put into operation. Then the height position of the beaker is adjusted so that the resonance state of the liquid surface of the electrolyte-water solution in the beaker is maximized. (5) While ultrasonic waves are emitted onto the aqueous electrolyte solution in the beaker in (4), 10 mg of the toner are gradually added and dispersed. The ultrasonic dispersion treatment is then continued for a further 60 seconds. During ultrasonic dispersion, the water temperature in the water tank is adjusted appropriately to be between 10 °C and 40 °C. (6) The aqueous electrolyte solution in (5), in which the toner, dispersed using a pipette, is added dropwise to the round-bottomed beaker in (1), which has been placed in the sample rack, and the measurement concentration is adjusted to 6%. The measurement is then carried out until the number of measured particles reaches 50,000. (7) The measurement data are analyzed using the enclosed dedicated software and the volume-averaged particle diameter (Dv) (weight-averaged particle diameter (D4)) is calculated. EXAMPLES

[0267] The basic configuration and features of the present disclosure have been described above. The following examples will explain the present disclosure in more detail. However, the present disclosure is by no means limited to these examples. In the following formulations, parts are by mass unless otherwise stated.

[0268] Production example of 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

[0269] The materials listed above were weighed into a reaction vessel equipped with a condenser, a stirrer, a nitrogen supply line, and a thermocouple. A flask was then purged with nitrogen gas, and the temperature was gradually increased while stirring. The reaction was carried out for 3 hours at 140 °C with stirring.

[0270] Tin 2-ethylhexanoate was added at a mass percentage of 0.5 wt% relative to the total mass of the monomers, followed by the addition of the materials listed above. The pressure in the reaction vessel was reduced to 8.3 kPa, and the reaction was carried out for 4 hours at a temperature of 200 °C. The pressure in the reaction vessel was then gradually reduced to atmospheric pressure, yielding the crystalline resin 1. The physical properties are shown in Table 1. Production example of crystalline resins 2 to 9

[0271] Crystalline resins 2 to 9 were obtained by carrying out the reaction in the same way as in the preparation example for crystalline resin 1, except that the materials used were changed to those in Table 1 and the mass fractions were changed so that the mol% was as specified in Table 1.

[0272] The physical properties are listed in Table 1. [Table 1] Crystalline resin no. Alcohol component Carboxylic acid component Physical properties EC HG TDD Adipic acid Octanoic acid Decanedioic acid Dodecanedioic acid Tetradecanedioic acid TDA HDA SA BA Tc(°C) MWC 1 49 - - - - - 48 - - - - 3 87 22000 2 - 49 - - 49 - - - - - - 2 82 20000 3 49 - - - - 49 - - - - - 2 84 26000 4 49 - - - 48 - - - - - 3 - 78 21000 5 49 - - - - - 48 - - 3 - - 86 23000 6 49 - - - - - 48 - 3 - - - 84 23000 7 - 50 - - - - 50 - - - - - 72 16000 8 - - 50 - - - - 50 - - - - 92 18000 9 50 - - 50 - - - - - - - - 65 17000 The numerical values ​​for each material in Table 1 represent mol%. Tc denotes the melting point.

[0273] The abbreviations in Table 1 are as follows. The number in parentheses indicates the number of carbon atoms in the linear alkyl compound. EC: 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) Production example for amorphous resin A1

[0274] The following materials were placed in a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer and a nitrogen supply 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

[0275] Next, a flask was purged with nitrogen gas, followed by a gradual increase in temperature with stirring. Stirring continued at 200 °C for 2 hours, during which time the water formed was distilled off. The pressure in the reaction vessel was then reduced to 8.3 kPa and maintained at this temperature for 1 hour, followed by cooling to 180 °C and a return to atmospheric pressure (first reaction step).

[0276] The materials listed above were then added, the pressure in the reactor was reduced to 8.3 kPa, and the reaction was continued for 4 hours while maintaining a temperature of 150 °C. The reaction was then stopped by lowering the temperature (second reaction step), yielding amorphous resin 1. The amorphous resin had a glass transition temperature (Tg) of 53 °C and a softening point of 92 °C. The physical properties are shown in Table 2. Production example of amorphous resins A2 to A11

[0277] Amorphous resins A2 to A11 were obtained by carrying out the reaction in the same way as in the preparation example of amorphous resin A1, except that the materials used were changed to those shown in Table 2 and the mass fractions were changed so that the mol% were as shown in Table 2.

[0278] The physical properties are shown in Table 2. [Table 2] BPA-PO (2.0) BPA-EO (2.0) AA TPA Hexanoic acid Tetradecanoic acid Hexadecanoic acid SA BA LA TDI Mwa Tg(°C) Tm(°C) A1 49 - 9 40 - - - 2 - - 6500 53 92 A2 49 - 9 40 - - - - 2 - 5000 52 95 A3 49 - 8 40 - - - 3 - - 7000 53 94 A4 49 - 8,5 40 - - 2,5 - - - 5500 52 91 A5 49 - 5 42 - - - - - 4 9800 50 90 A6 49 - 5 42 - 4 - - - - 9800 50 93 A7 49 - 3 42 6 - - - - 12000 56 101 A8 50 - 2 48 - - - - - 13000 61 112 A9 50 - 12 38 - - - - - 15000 47 122 A10 - 50 2 48 - - - - - 11000 54 96 A11 - 49,5 0 49 - 1,5 - - - - - 17000 54 97

[0279] The numerical values ​​for each material in Table 2 are given in mol%. Mwa denotes the weight-average molecular weight. Tg denotes the glass transition temperature and Tm denotes the softening point. The abbreviations are as follows. The numbers in parentheses indicate the number of carbon atoms in 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 AA: Adipic acid SA: Stearic acid (18) BA: Behenic acid (22) LA: Lignoceric acid (24) TD1: Tetradecanol (14)

[0280] Production example of amorphous resin B1 - Bisphenol-A-propylene oxide adduct (average number of moles added: 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 supply line, and a thermocouple. A flask was then purged with nitrogen gas, and the temperature was gradually increased while stirring. The reaction was continued for 2 hours at 200 °C with stirring.

[0281] The pressure in the reaction vessel was then reduced to 8.3 kPa and maintained for 1 hour, followed by cooling to 160 °C and return to atmospheric pressure. - Trimellitic acid anhydride: 6.7 parts by weight (10.0 mol%)

[0282] The materials listed above were then added, the pressure in the reaction vessel was reduced to 8.3 kPa, and the reaction was carried out while maintaining a temperature of 200 °C. Once it was confirmed that the softening point had reached the temperature shown in Table 3, the temperature was lowered to stop the reaction, yielding amorphous polyester resin B1.

[0283] The physical properties are shown in Table 3. [Table 3] Amorphous resin B BPA-PO(2.0) AA TPA TMA Mwb Tg(°C) Tm(°C) Amorphous resin B1 50 15 25 10 120000 58 145

[0284] Mwb denotes the weight-average molecular weight. Tg denotes the glass transition temperature and Tm denotes the softening point.

[0285] Abbreviations are as follows: BPA-PO: Polyoxypropylene (2,0)-2,2-bis(4-hydroxyphenyl)propane TPA: Terephthalic acid AA: Adipic acid TMA: Trimellitic anhydride

[0286] Production example of graft polymer resin C1 - Polyethylene (Mw: 1400, Mn: 850, endothermic DSC peak at 100 °C): 20 parts by mass - Styrene: 59 parts by mass - n-Butyl acrylate: 18.5 parts by mass - Acrylonitrile: 2.5 parts by mass

[0287] The aforementioned raw materials were loaded into an autoclave, and the system was purged with nitrogen. The temperature was then increased and maintained at 180 °C with stirring. A total of 50 parts by mass of a 2 wt% solution of di-tert-butyl peroxide in xylene was continuously added dropwise to the system over a period of 5 hours. After cooling, the solvent was separated and removed to obtain the graft polymer resin C1, which had a structure in which a vinyl resin component and a hydrocarbon compound were bonded.

[0288] Graft polymer resin C1 exhibited a softening point (Tm) of 110 °C and a glass transition temperature (Tg) of 64 °C. The molecular weight of the THF-soluble fraction, as measured by GPC, was a weight-mean molecular weight (Mw) of 7400. No peaks corresponding to the polyethylene of the raw material were confirmed. wax

[0289] The following waxes were used. [Table 4] wax type Melting point Tw / °C Wmax Wax 1 Fischer-Tropsch wax 90 42 Wax 2 Fischer-Tropsch wax 77 36 Wax 3 Ester wax (behenyl behenate) 81 44

[0290] 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 weight - Dye 1: 5 parts by mass

[0291] (Cyan pigment, Pigment Blue 15:3, manufactured by Dainichiseika Color & Chem. MFG Co., Ltd.)

[0292] The above materials were processed using a Henschel mixer (FM-75, manufactured by Nippon Coke and Engineering Co., Ltd.) at a speed of 25 s -1 The mixture was blended for 5 minutes and then kneaded in a double-speed kneader (PCM-30, Ikegai Corporation) set to 120 °C, with a screw speed of 250 rpm and an outlet temperature of 130 °C.

[0293] The resulting 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 resulting coarsely pulverized product was then finely pulverized using a mechanical pulverizer (T-250, manufactured by Freund Turbo Corporation).

[0294] Further classification was performed using a Faculty F-300 (manufactured by Hosokawa Micron Corporation), resulting in toner particles 1 with a weight-mean particle diameter (D4) of 6.0 µm, an average roundness of 0.965, and a domain-number-mean diameter of 0.20 µm. Operating conditions included a classification rotor speed of 130 s⁻¹. -1 and a dispersion rotor speed of 120 s -1 . Production examples of toner particles 2 to 26

[0295] Toner particles 2 to 26 were produced in the same manner as in the production example of toner particles 1, except that the type and mass fractions added of the crystalline resin, the type and mass fractions added of the amorphous resins A and B, and the type of wax were changed as shown in Table 5. [Table 5] Toner No. Toner particle no. Toner particle-forming raw materials External Additive toner Crystalline resin Amorphous resin A Amorphous resin B graft polymer resin C1 wax Dye 1 Silicon dioxide particles 1 Nr. parts Nr. parts Nr. parts parts type parts parts parts Complete parts 1 1 1 9 A1 52 B1 23 5 Wax 1 5 5 1 100 2 2 2 9 A1 52 B1 23 5 Wax 1 5 5 1 100 3 3 3 9 A1 52 B1 23 5 Wax 1 5 5 1 100 4 4 1 9 A2 52 B1 23 5 Wax 2 5 5 1 100 5 5 1 9 A2 52 B1 23 5 Wax 1 5 5 1 100 6 6 1 9 A3 52 B1 23 5 Wax 1 5 5 1 100 7 7 1 9 A4 52 B1 23 5 Wax 1 5 5 1 100 8 8 1 9 A5 52 B1 23 5 Wax 1 5 5 1 100 9 9 1 9 A6 52 B1 23 5 Wax 1 5 5 1 100 10 10 1 3 A6 36 B1 45 5 Wax 1 5 5 1 100 11 11 1 3 A6 56 B1 25 5 Wax 3 5 5 1 100 12 12 1 3 A6 56 B1 25 5 Wax 1 5 5 1 100 13 13 1 6 A6 56 B1 22 5 Wax 1 5 5 1 100 14 14 1 15 A6 48 B1 21 5 Wax 1 5 5 1 100 15 15 1 18 A6 46 B1 20 5 Wax 1 5 5 1 100 16 16 1 18 A6 56 B1 10 5 Wax 1 5 5 1 100 17 17 1 9 A7 52 B1 23 5 Wax 1 5 5 1 100 18 18 1 9 A8 52 B1 23 5 Wax 1 5 5 1 100 19 19 4 9 A8 52 B1 23 5 Wax 1 5 5 1 100 20 20 5 9 A8 52 B1 23 5 Wax 1 5 5 1 100 21 21 6 9 A8 52 B1 23 5 Wax 1 5 5 1 100 22 22 - 0 A9 80 B1 4 5 Wax 1 5 5 1 100 23 23 - 0 A8 18 B1 66 5 Wax 1 5 5 1 100 24 24 7 3 A8 56 B1 25 5 Wax 1 5 5 1 100 25 25 8 3 A10 56 B1 25 5 Wax 1 5 5 1 100 26 26 9 3 A11 56 B1 25 5 Wax 2 5 5 1 100

[0296] Production example of toner 1 - Toner particles 1: 99.0 parts by mass - Silicon dioxide particles 1 (silicone oil-treated pyrogenic silicon dioxide with a number-average diameter of 30 nm): 1.0 part by mass

[0297] The above materials were mixed in a Henschel FM-10C mixer (manufactured by Mitsui Miike Chemical Engineering Co., Ltd.) at a speed of 30 s -1 Mixed for 5 minutes to obtain toner 1.

[0298] The viscoelasticity of the resulting toner was measured using the method described above and is described in Table 6. [Table 6] Toner No. G'1(100) G'3(50) G'3(70) G'3(70) / G'2(70) T2 d(logG'2(T2)) / dT Wmax- Aend Cend- Aend Cend- (Cal+Cca) Mwa / Mwc Toner 1 7,0E+03 1,2E+08 7,5E+06 60,0 65,0 -0,8 24 4 8 0,30 Toner 2 8,0E+03 1,5E+08 8,0E+06 40,0 64,0 -0,6 24 4 8 0,33 Toner 3 3,0E+03 1,1E+08 7,2E+06 70,0 66,0 -1,1 24 4 10 0,25 Toner 4 1,0E+03 7,6E+07 3,0E+06 18,0 57,0 -0,3 12 -2 8 0,23 Toner 5 1,8E+04 1,0E+08 5,5E+06 41,0 68,0 -0,6 18 -2 8 0,23 Toner 6 1,2E+04 1,1E+08 8,2E+06 50,0 65,0 -0,6 20 0 8 0,32 Toner 7 7,0E+03 9,5E+07 7,5E+06 32,0 62,0 -0,6 26 6 8 0,25 Toner 8 3,6E+04 8,6E+07 5,5E+06 18,0 62,0 -0,5 28 8 8 0,45 Toner 9 1,3E+04 8,6E+07 8,8E+06 26,0 62,0 -0,6 28 8 8 0,45 Toner 10 4,7E+04 5,0E+08 2,4E+07 24,0 62,0 -0,4 28 8 8 0,45 Toner 11 4,0E+04 1,1E+08 6,0E+06 18,0 62,0 -0,6 30 8 8 0,45 Toner 12 3,8E+04 3,0E+08 1,6E+07 24,0 62,0 -0,6 28 8 8 0,45 Toner 13 2,1E+04 2,0E+08 9,5E+06 24,0 62,0 -0,6 28 8 8 0,45 Toner 14 2,2E+03 8,2E+07 6,0E+06 24,0 62,0 -0,6 28 8 8 0,45 Toner 15 1,2E+03 7,5E+07 3,0E+06 24,0 62,0 -0,6 28 8 8 0,45 Toner 16 3,0E+02 7,2E+07 2,3E+06 24,0 62,0 -0,9 28 8 8 0,45 Toner 17 2,0E+03 8,5E+07 1,2E+07 21,0 61,0 -0,4 36 16 8 0,55 Toner 18 2,4E+03 8,5E+07 2,1E+07 22,0 59,0 -0,4 42 22 8 0,59 Toner 19 2,5E+03 4,5E+07 3,7E+06 18,0 59,0 -0,4 42 18 8 0,62 Toner 20 2,5E+03 8,3E+07 2,5E+06 15,0 59,0 -0,3 42 16 4 0,57 Toner 21 2,5E+03 8,0E+07 2,4E+06 12,0 59,0 -0,3 42 14 0 0,57 Toner 22 8,0E+02 6,6E+07 1,7E+06 1,1 45,0 -0,2 - - - - Toner 23 6,0E+04 6,0E+08 5,6E+07 0,9 72,0 -0,3 - - - - Toner 24 1,6E+04 2,4E+08 1,2E+06 1,1 52,0 -0,3 - - - 0,81 Toner 25 7,0E+03 1,2E+08 8,0E+05 2,0 54,0 -0,3 - - - 0,61 Toner 26 8,0E+03 9,5E+07 6,0E+05 6,0 50,0 -0,3 28 -14 -8 1,00

[0299] In the table, T2 is the minimum value (°C) in a diagram with temperature T on the horizontal axis and d(logG'2(T)) / dT, which is the value obtained by differentiating logG'2(T) with respect to temperature T, on the vertical axis.

[0300] In the table, for example, a value such as 7.0E+03 represents 7.0 × 10 3 . Manufacturing examples of toners 2 to 26

[0301] Toner particles 2 to 26 were produced in the same way as in the production example for toner 1, except that the toner particles were replaced by toner particles 2 to 26. The physical properties are shown in Table 6.

[0302] Manufacturing example of a magnetic carrier 1 - Magnetite 1 with a number-mean particle diameter of 0.30 µm (magnetization strength of 65 Am) 2 / kg in a magnetic field of 1000 / 4π (kA / m) - Magnetite 2 with a number-average particle diameter of 0.50 µm (magnetization strength of 65 Am) 2 / kg in a magnetic field of 1000 / 4π (kA / m)

[0303] A total of 4.0 parts of a silane compound (3-(2-Aminoethylaminopropyl)trimethoxysilane) were added to 100 parts each of the above-mentioned materials, and high-speed mixing and stirring in containers at 100 °C or higher was carried out to process the respective fine particles. - Phenol: 10 wt% - Formaldehyde solution: 6 wt% (40 wt% formaldehyde, 10 wt% methanol, 50 wt% water) - Magnetite 1, treated with the above-mentioned silane compound: 58 wt% - Magnetite 2, treated with the above-mentioned silane compound: 26 wt%. A total of 100 parts of the above materials, 5 parts of a 28 wt% aqueous ammonia solution, and 20 parts of water were placed in a flask. The temperature was raised to 85 °C for 30 minutes and maintained with stirring and mixing, and a polymerization reaction was carried out for 3 hours to cure the resulting phenolic resin. The cured phenolic resin was then cooled to 30 °C, and water was added. The supernatant was subsequently removed, and the precipitate was washed with water and air-dried. This was then dried under reduced pressure (5 mmHg or less) at 60 °C to obtain a magnetic body-dispersed spherical magnetic carrier 1. The volume-based 50% particle diameter (D50) of the magnetic carrier 1 was 34.2 µm. Manufacturing example of two-component developer 1

[0304] A total of 8.0 parts of toner 1 were added to 92.0 parts of magnetic carrier 1, and the components were mixed in a V-mixer (V-20, manufactured by Seishin Enterprise Co., Ltd.) to obtain two-component developer 1. Manufacturing example of two-component developers 2 to 26

[0305] Toner 2 to 26 were used in the manufacturing example of two-component developer 1 to obtain two-component developers 2 to 26 each. Example 1: Low-temperature fixability

[0306] Evaluation was performed using the two-component developer 1 above.

[0307] A modified Canon imageRUNNER ADVANCE C5870 digital commercial printer was used as the image generation device, and two-component developer 1 was placed in a cyan developer unit. Modifications were made to the device to allow free adjustment of the fixing temperature, processing speed, DC voltage (VDC) applied to a developer-carrying element, charging voltage (VD) applied to an electrostatic latent image-carrying element, and laser power. Image output evaluation involved the output of a full frame (FFh) image at the desired aspect ratio and adjustment of VDC, VD, and laser power to achieve the desired toner deposition level on the FFh image on paper, thereby evaluating low-temperature fusing capability.

[0308] FFh is the hexadecimal representation of 256 gradations, where 00h is the first gradation (white area) of the 256 gradations and FFh is the 256th gradation (solid color area).

[0309] The evaluation was carried out based on the following evaluation procedure, and the results are shown in Table 7. - Paper: GFC-081 (81.0 g / m²) 2 ) (distributed by Canon Marketing Japan Inc.) - Toner application on paper: 0.80 mg / cm² 2 (adjusted by the DC voltage VDC at the developer-supporting element, the charging voltage VD at the electrostatic latent image-supporting element and the laser power) - Evaluation image: A 2 cm × 5 cm image was placed in the center of the A4 paper. - Test environment: Low temperature and low humidity environment: 15 °C temperature / 10 % relative humidity (hereinafter referred to as "L / L") - Fixing temperature: 140 °C - Process speed: 320 mm / sec.

[0310] The evaluation image was printed and its low-temperature fixability was assessed. The image density loss rate was used as the evaluation index for low-temperature fixability.

[0311] The image density loss rate was first measured in the center of the image using an X-Rite color reflectance densitometer (Series 500: manufactured by X-Rite, Inc.). Next, the fixed image was printed five times with Silbon paper under a pressure of 4.9 kPa (50 g / cm²). 2 The area where image density was measured was rubbed, and the image density was measured again. The rate of image density depreciation before and after rubbing was calculated using the following formula. The resulting rate of image density depreciation was evaluated according to the following criteria: Image density decrease rate = (Image density before rubbing - Image density after rubbing) / (Image density before rubbing) × 100

[0312] A rating of C or higher was considered excellent. Rating criteria A: Image density degradation rate is less than 1.0% B: Image density decrease rate is 1.0% or more, but less than 3.0% C: Image density decrease rate is 3.0% or more, but less than 8.0% D: Image density degradation rate is 8.0% or more Heat-resistant storage stability

[0313] A total of 5 g of toner was placed in a 100 ml plastic beaker and left to stand in a temperature- and humidity-controlled thermostat (50 °C, 54% RH) for 72 hours. The aggregation properties were then evaluated. This was done by shaking the resulting toner through a 150 µm sieve with a 0.5 mm amplitude for 10 seconds using a Hosokawa Micron Corporation PT-X powder tester. The residual toner remaining on the sieve was calculated as a rating index from the mass of toner on the sieve before and after shaking, and a rating of C or higher was considered excellent. Evaluation criteria A: Residual rate is less than 2.0% B: Residual rate is 2.0% or more, but less than 5.0% C: Residual rate is 5.0% or more, but less than 10.0% D: Residual rate is 10.0% or more Image errors during double-sided printing

[0314] The evaluation was performed based on the following evaluation procedure using the same imaging device that was also used to evaluate the low-temperature fixability. To more clearly illustrate the effects of the present disclosure, the evaluation was carried out in an environment with a temperature and humidity higher than those of the normal operating environment.

[0315] The results are shown in Table 7. - Paper: Mondi Color Copy (300 g / m 2 ) (distributed by Mondi plc) - Toner application level on paper: 0.80 mg / cm² 2 (adjusted by the DC voltage VDC at the developer-supporting element, the charging voltage VD at the electrostatic latent image-supporting element and the laser power) - Evaluation image: A 25 cm wide × 20 cm long FFh image was printed on both sides of the A3 paper with a 5 mm margin from the front edge in the transport direction. - Test environment: High temperature and high humidity environment: 35 °C / 80% RH - Fixing temperature: 160 °C - Process speed: 320 mm / sec. - Number of printouts: 10,000

[0316] The 9,000th to 10,000th output image was evaluated. The whiteness of the output image's white background and the whiteness of the evaluation paper were measured using a REFLECTOMETER MODEL TC-6DS (manufactured by Tokyo Denshoku Co., Ltd.). The difference between the whiteness of the evaluation paper and the whiteness of the output image's white background in the worst case was used as the fog density (%) to evaluate image defects during double-sided printing. An amber filter was used as a filter. A rating of C or higher was determined to be excellent. Evaluation criteria A: The veil density of all evaluated images is less than 1.0%. B: The veil density of all evaluated images is 1.0% or more, but less than 2.0%. C: The proportion of the evaluated images with a veil density of 2.0% or more was less than 2.0% of the evaluated images. D: The proportion of the evaluated images with a veil density of 2.0% or more was 2.0% or more of the evaluated images. Fusion with drum

[0317] The evaluation was performed based on the following evaluation procedure using the same image generation device that was also used for the low-temperature fixability evaluation.

[0318] The results are listed in Table 7. - Paper: CS-068 (68.0 g / m²) 2 ) (distributed by Canon Marketing Japan Inc.) - Toner application level on paper: 0.80 mg / cm² 2 (adjusted by the DC voltage VDC at the developer-supporting element, the charging voltage VD at the electrostatic latent image-supporting element and the laser power) - Evaluation image: An FFh image was arranged on one side of the A4 paper with an image print ratio of 40%. - Test environment: High temperature and high humidity environment: 35 °C / 80% RH - Fixing temperature: 160 °C - Process speed: 320 mm / sec. - Number of printouts: 100,000

[0319] After continuous output ceased, the surface of the electrostatic latent image-bearing element was viewed using a VQ-7000 digital high-resolution microscope (manufactured by Keyence Corporation) at 300x magnification. Areas of fused toner within the field of view were marked, and their area was calculated to determine the percentage of the surface covered with fused toner within the field of view. This was observed in 20 fields of view across the entire surface of the electrostatic latent image-bearing element, and the average value was used as the fusion occurrence rate. This evaluation was performed three times, and a rank was determined based on the average value. The evaluation was ranked as follows. The evaluation results are presented in Table 7. A rank of C or higher was determined to be excellent. Evaluation criteria A: Merger occurrence rate is less than 1.0% B: Merger occurrence rate is 1.0% or more, but less than 5.0% C: Merger occurrence rate is 5.0% or more, but less than 10.0% D: Merger occurrence rate is 10.0% or higher Charge stability

[0320] The evaluation was performed based on the following evaluation procedure using the same imaging device that was also used to evaluate low-temperature fixability.

[0321] The results are shown in Table 7. - Paper: CS-068 (68.0 g / m²) 2 ) (distributed by Canon Marketing Japan Inc.) - Toner application level on paper: 0.40 mg / cm² 2 (adjusted by the DC voltage VDC at the developer-supporting element, the charging voltage VD at the electrostatic latent image-supporting element and the laser power) - Evaluation image: an FFh image arranged on one side of A4 paper with an image print ratio of 2%. - Test environment: High temperature and high humidity environment: 30 °C / 80% RH - Fixing temperature: 160 °C - Process speed: 320 mm / sec.

[0322] A total of 3,000 sheets were printed under the conditions described above. After the printer was left idle for one day, a sheet with the same evaluation image was printed. The image density of the resulting image was measured and compared to the image density of the first printed sheet, which was printed before the printer was left idle for one day. The rate of change in image density was calculated as follows: Image density change rate (%) = |1 − (image density after one day of printer standby) / (image density of the first sheet before one day of printer standby) | × 100

[0323] The evaluation was carried out according to the following criteria. A rank of C or higher was determined to be excellent. Evaluation criteria A: Image density change rate is less than 2.0%. B: Image density change rate is 2.0% or more, but less than 5.0%. C: Image density change rate is 5.0% or more, but less than 10.0%. D: Image density change rate is 10.0% or more. Examples 2 to 21 and comparative examples 1 to 5

[0324] The evaluation was carried out in the same way as in Example 1, except that two-component developers 2 to 26 were used instead of two-component developer 1.

[0325] The evaluation results are shown in Table 7. [Table 7] Toner No. Two-component developer no. Evaluation of toner properties Low-temperature fixability Heat-resistant storage stability Image errors during double-sided printing Fusion with drum Charge stability Rank Density decrease rate (%) Rank Remaining payment (%) Rank X / Y Rank Merger occurrence rate (%) Rank Density change rate (%) Example 1 1 1 A 0,6 A 0,9 A 0,6 / 0 A 0,6 A 0,8 Example 2 2 2 A 0,6 A 0,9 A 0,7 / 0 A 0,6 A 0,8 Example 3 3 3 A 0,6 A 1,2 A 0,7 / 0 A 0,6 A 0,9 Example 4 4 4 A 0,8 C 8,0 B 1,8 / 0 C 7,0 A 1,0 Example 5 5 5 A 0,7 B 4,2 B 1,6 / 0 B 3,0 A 1,0 Example 6 6 6 A 0,7 A 1,0 A 0,8 / 0 A 0,8 A 1,0 Example 7 7 7 A 0,7 A 1,5 A 0,8 / 0 A 0,8 A 1,2 Example 8 8 8 B 1,2 B 2,4 B 1,6 / 0 B 4,0 A 1,5 Example 9 9 9 A 0,8 B 3,0 B 1,3 / 0 B 4,0 A 1,5 Example 10 10 10 C 7,0 A 1,0 B 1,5 / 0 B 4,0 A 1,8 Example 11 11 11 B 2,5 B 2,2 C 3,0 / 1,2 C 8,0 A 1,8 Example 12 12 12 B 1,6 B 2,4 B 1,4 / 0 B 4,5 A 1,8 Example 13 13 13 A 0,8 B 2,6 B 1,2 / 0 B 4,5 A 1,6 Example 14 14 14 A 0,8 B 2,8 B 1,3 / 0 B 4,5 A 1,7 Example 15 15 15 A 0,8 C 7,0 C 2,4 / 1,5 C 7,5 B 3,2 Example 16 16 16 A 0,8 C 8,0 C 3,0 / 1,9 C 7,9 B 4,0 Example 17 17 17 A 0,8 C 9,0 B 1,7 / 0 C 8,6 C 6,4 Example 18 18 18 A 0,8 C 8,0 B 1,8 / 0 C 9,2 C 7,3 Example 19 19 19 A 0,8 C 8,5 C 3,2 / 1,7 C 8,2 C 6,9 Example 20 20 20 A 0,8 C 8,5 C 2,9 / 1,6 C 8,0 C 7,1 Example 21 21 21 A 0,8 C 8,5 C 3,3 / 1,8 C 9,2 C 8,0 Comparative example 1 22 22 A 0,8 D 14,0 D 4,5 / 5 D 15,0 C 8,1 Comparative example 2 23 23 D 15,0 B 4,0 B 1,5 / 0 C 7,0 B 4,0 Comparative example 3 24 24 A 0,8 C 9,5 D 6,0 / 4 D 17,0 C 8,2 Comparative example 4 25 25 A 0,9 C 9,0 D 4,1 / 3,5 D 13,0 C 9,6 Comparative example 5 26 26 A 0,9 C 9,0 D 4,0 / 4,5 D 12,0 C 7,9

[0326] In the table, “X” denotes the maximum veil density and “Y” denotes the percentage of evaluation images with a veil density of 2.0% or more.

[0327] While the present disclosure has been described with reference to embodiments, it is to be understood that the present disclosure is not limited to the disclosed embodiments. The scope of the following claims is to be interpreted in the broadest possible way to include all such modifications and equivalent structures and functions. QUOTES INCLUDED IN THE DESCRIPTION

[0000] This list of documents cited by the applicant was automatically generated and is included solely for the reader's convenience. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions. Cited patent literature

[0000] JP 2019

[0005] JP 194682

[0005] JP 2019-056767

[0006]

Claims

Toner comprising a toner particle comprising a binder resin and a wax, wherein the binder resin comprises a crystalline resin; when measuring the viscoelasticity of the toner, Step (i): The temperature is increased from 30 °C to 100 °C at a rate of 2 °C / min to obtain a curve G'1(T) of the storage elasticity modulus G' [Pa] versus temperature T [°C], Step (ii): After step (i), the temperature is decreased from 100 °C to 30 °C at a rate of 2 °C / min to obtain a curve G'2(T) of the storage elasticity modulus G' [Pa] versus temperature T [°C], Step (iii): After step (ii), the temperature is increased from 30 °C to 100 °C at a rate of 2 °C / min to obtain a curve G'3(T) of the storage elasticity modulus G' [Pa] versus temperature T [°C] to obtain;where the storage elastic modulus G' at 100 °C on curve G'1(T) is denoted by G'1(100) [Pa], the storage elastic modulus G' at 70 °C on curve G2(T) is denoted by G'2(70) [Pa], the storage elastic modulus G' at 50 °C on curve G'3(T) is denoted by G'3(50) [Pa], and the storage elastic modulus G' at 70 °C on curve G'3(T) is denoted by G'3(70) [Pa], 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 × 10⁴ Pa; G' 3 ( 50 ) ≤ 7.0 × 10 7 Pa G' 3 (70) ≤ 2.0 × 10 6 Pa G' 3 (70) / G' 2 (70) ≥ 10 Toner according to claim 1, wherein in a diagram of the curve G'2(T), in which a horizontal axis represents the temperature T and a vertical axis represents a value d(logG'2(T)) / dT obtained by differentiating logG'2(T) with respect to the temperature T, a minimum value is in a range of 55.0 to 70.0 °C, and wherein a temperature at which the minimum value is observed is denoted by T2 (°C), d ( logG' 2 ( T2 ) ) / dT is − 2.0 to − 0.

3. Toner according to claim 1 or 2, wherein the binder resin further comprises an amorphous polyester resin A, wherein the amorphous polyester resin A has a molecular chain end condensed with at least one linear alkyl compound A selected from the group consisting of aliphatic linear monocarboxylic acids and aliphatic linear monoalcohols, and wherein a number of carbon atoms in the linear alkyl compound A is designated Aend and a number of carbon atoms corresponding to a peak detected as the maximum peak when the wax is analyzed by GC / MS is designated Wmax, wherein Aend and Wmax satisfy the following relationships: Aend ≥ 16 16 ≤ Wmax − Aend ≤ 30 . Toner according to claim 1 or 2, wherein the crystalline resin comprises a crystalline polyester resin and 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 to a molecular chain end. Toner according to claim 4, wherein the binder resin further comprises an amorphous polyester resin A and the amorphous polyester resin A has a molecular chain end condensed with at least one linear alkyl compound A selected from the group consisting of aliphatic linear monocarboxylic acids and aliphatic linear monoalcohols. Toner according to claim 5, wherein a number of carbon atoms in the linear alkyl compound A is designated by Aend and a number of carbon atoms in the linear alkyl compound C is designated by Cend, the Aend and the Cend satisfying the following relationships: Cend ≥ 16 − 4 ≤ ​​Cend − Aend ≤ 6 . Toner according to any one of claims 4 to 6, wherein the crystalline polyester resin comprises a condensation polymer of a monomer composition comprising an aliphatic diol and an aliphatic dicarboxylic acid, and wherein a number of carbon atoms in the aliphatic diol in the crystalline polyester resin is designated by Cal, a number of carbon atoms in the aliphatic dicarboxylic acid is designated by Cca, and a number of carbon atoms in the linear alkyl compound C is designated by Cend, the Cal, the Cca, and the Cend satisfy the following relationship: Cend − (Cal + Cca) ≥ 8. Toner according to claim 5 or 6, wherein the linear alkyl compound A comprises an aliphatic linear monocarboxylic acid. Toner according to claim 5, 6 or 8, wherein a weight-averaged molecular weight of a THF-soluble fraction of the amorphous polyester resin A is designated as Mwa and a weight-averaged molecular weight of a THF-soluble fraction of the crystalline polyester resin is designated as Mwc, Mwa and Mwc satisfy the condition Mwa / Mwc ≤ 0.50.