TONER

Abstract

A toner with a toner particle containing a binder resin and a release agent is provided, wherein the binder resin comprises a crystalline resin and an amorphous resin, wherein, during differential scanning calorimetry of the toner, a temperature is increased to obtain differential scanning calorimetry curve A, and then the temperature is decreased to obtain differential scanning calorimetry curve B, differential scanning calorimetry curve A exhibits endothermic peaks originating from the crystalline resin and the release agent, differential scanning calorimetry curve B exhibits exothermic peaks originating from the crystalline resin and the release agent, and these endothermic and exothermic peaks satisfy specific relationships, and a storage elasticity modulus G' (TmB) of the toner at the endothermic peak temperature of the crystalline resin is 1.0 × 10⁵ Pa to 1.0 × 108Pa.

Description

BACKGROUND OF THE INVENTIONField of the InventionThe present disclosure relates to a toner for use in electrophotography and electrostatic recording.Description of the Prior ArtEnergy saving is also regarded as an important technical issue in electrophotographic apparatuses, and research is being conducted for a marked reduction in energy required for fixing apparatuses. For toners, techniques are being studied which improve so-called low-temperature fixability enabling fixation with less energy.As a method enabling fixation at low temperatures, a technique using a crystalline resin as a binder resin for toners is being studied. Crystalline resins have excellent heat-resistant storage stability because the molecular chains are regularly arranged therein, thereby preventing softening at temperatures below the melting point very effectively. On the other hand, if the melting point is exceeded, the crystals suddenly melt, which is accompanied by a rapid drop in viscosity. For this reason, crystalline resins have attracted attention as materials having excellent in the sharp melting property and the low-temperature fixability.Normally, crystalline vinyl resins have long-chain alkyl groups as side chains and exhibit crystallinity because the long-chain alkyl groups on the side chains are aligned with each other. As a toner using a crystalline vinyl resin, Japanese Patent Application Publication No. 2020-173414 discloses a toner using a crystalline vinyl resin obtained by copolymerizing a polymerizable monomer having a long-chain alkyl group with an amorphous polymerizable monomer having an SP value different from that of the polymerizable monomer having a long-chain alkyl group.Further, Japanese Patent Application Publication No. 2018-151619 discloses a toner in which a polymerizable crosslinking agent is added or its amount is increased and the amount of a gel component having high elasticity is increased to suppress the deterioration of hot offset resistance and heat-resistant storage stability caused by the addition of a crystalline resin aimed at improving low-temperature fixability.SUMMARY OF THE INVENTIONAs mentioned above, when the melting point of a crystalline resin is exceeded, a sudden drop in viscosity occurs when the resin melts. This is a very good property from the viewpoint of low temperature fixability. On the other hand, they have a high crystallization rate, so that the viscosity of the crystalline resins rapidly increases upon cooling from the molten state. A problem resulting from a high crystallization rate is associated with color reproducibility, and this problem occurs because the viscosity increase begins before the colors are fully mixed. Another problem is associated with gloss uniformity of a fixed image, which is affected by a different volumetric shrinkage rate depending on the toner application level.The present disclosure relates to a toner which is excellent in low-temperature fixability and heat-resistant storage stability and also exhibits favorable color reproducibility and gloss uniformity of a fixed image.The present disclosure relates to a toner having a toner particle comprising a binder resin and a releasing agent, the binder resin having a crystalline resin and an amorphous resin, wherein when in the differential scanning calorimetry of the toner, a temperature is increased from 20° C. to 180° C. at a temperature increase rate of 10° C. / min to obtain a differential scanning calorimetry curve A, then the temperature is maintained at 180° C. for 10 min, and then the temperature is decreased from 180° C. to 10° C. at a temperature decrease rate of 10° C. / min to obtain a differential scanning calorimetry curve B, the differential scanning calorimetry curve A has an endothermic peak m(B) derived from the crystalline resin, and an endothermic peak m(W) derived from the release agent, the differential scanning calorimetry curve B has an exothermic peak c(B) derived from the crystalline resin and an exothermic peak c(W) derived from the release agent, and wherein, when a peak temperature (° C.) of the endothermic peak m(B) is denoted by Tm(B), a peak temperature (° C.) of the endothermic peak m(W) is denoted by Tm(W), and a peak temperature (° C.) of the exothermic peak c(B) is denoted by Tc(B), and a peak temperature (° C.) of the exothermic peak c(W) is denoted by Tc(W), the Tm(B), the Tc(B), the Tm(W) and the Tc(W) satisfy a storage elastic modulus G' (TmB) of the toner at Tm(B) [° C.] is 1.0×10 5 Pa to 1.0×10 8 Pa.The present disclosure can provide a toner excellent in low-temperature fixability and heat-resistant storage stability, and also advantageous in color reproducibility and gloss uniformity of a fixed image.Further features of the present invention will become apparent from the following description of exemplary embodiments with reference to the accompanying drawings.BRIEF DESCRIPTION OF THE DRAWINGSThe figure shows an example of mounting a sample for measurement of viscoelasticity.DESCRIPTION OF THE EMBODIMENTSIn the present disclosure, unless otherwise stated, the terms "from XX to YY" and "XX to YY" representing a numerical range include a numerical range including the lower and upper limits representing the end points. When numerical ranges are described in stages, the upper and lower limits of each numerical range may be combined in any manner. (Meth)acrylic esters means acrylic esters and / or methacrylic esters.Moreover, in the present disclosure, a description such as "at least one selected from the group consisting of XX, YY, and ZZ" means one of XX, YY, ZZ, a combination of XX and YY, a combination of XX and ZZ, a combination of YY and ZZ, and a combination of XX, YY, and ZZ. "monomer unit" refers to the reacted form of a monomer substance in a polymer. For example, a portion of the carbon-carbon bond in the main chain of a polymer in which a vinyl monomer is polymerized is considered to be a unit. A vinyl monomer can be expressed by the following formula (6).In formula (6), R A represents a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group), and R B represents a freely selected substituent.Moreover, the term "crystalline resin" in the present invention refers to a resin having a marked endothermic peak in differential scanning calorimetry (DSC).The present inventors have conducted research to solve the above-mentioned problems. From the viewpoint of low-temperature fixability, it is necessary to speed up the decrease in melt viscosity of the toner before fixation. From the viewpoint of color mixing property and gloss uniformity, a certain decrease in the rate of rise of melt viscosity is required for toners during fixation. In general, crystalline resins have a high melt rate and also a high crystallization rate, and this property has been utilized to improve low-temperature fixability. Therefore, it is in the nature of crystalline resins that the viscosity of the toner rapidly increases during fixing, and no attempt has been made to intentionally slow the increase in melt viscosity.In order to solve the above problems, the inventors have studied in detail whether it is possible to appropriately control only the viscosity increase rate of the toner during the fixing without changing the viscosity decrease rate of the toner before the fixing. In the fixing process, it is possible to soften and mix a plurality of resin components in the toner by applying heat and pressure. Therefore, the inventors have considered that this can be utilized to control the crystallization rate of the toner during the fixing, thereby solving the above-mentioned problems. An embodiment for achieving this object will be explained below.The present inventors have found that the following toner has excellent low-temperature fixability and heat-resistant storage stability, and further has excellent color reproducibility and image gloss uniformity.The present disclosure relates to a toner having a toner particle comprising a binder resin and a releasing agent, the binder resin having a crystalline resin and an amorphous resin, wherein when in the differential scanning calorimetry of the toner, a temperature is increased from 20° C. to 180° C. at a temperature increase rate of 10° C. / min to obtain a differential scanning calorimetry curve A, then the temperature is maintained at 180° C. for 10 min, and then the temperature is decreased from 180° C. to 10° C. at a temperature decrease rate of 10° C. / min to obtain a differential scanning calorimetry curve B, the differential scanning calorimetry curve A has an endothermic peak m(B) derived from the crystalline resin, and an endothermic peak m(W) derived from the release agent, the differential scanning calorimetry curve B has an exothermic peak c(B) derived from the crystalline resin and an exothermic peak c(W) derived from the release agent, and wherein, when a peak temperature (° C.) of the endothermic peak m(B) is denoted by Tm(B), a peak temperature (° C.) of the endothermic peak m(W) is denoted by Tm(W), and a peak temperature (° C.) of the exothermic peak c(B) is denoted by Tc(B), and a peak temperature (° C.) of the exothermic peak c(W) is denoted by Tc(W), the Tm(B), the Tc(B), the Tm(W) and the Tc(W) satisfy a storage elastic modulus G' (TmB) of the toner at Tm(B) [° C.] is 1.0×10 5 Pa to 1.0×10 8 Pa.The toner of the present disclosure will be described below. The toner has a toner particle including a binder resin and a release agent. The binder resin includes a crystalline resin and an amorphous resin. By the binder resin including a crystalline resin, it is possible to secure a heat-resistant storage stability of the toner while exhibiting a low-temperature fixability. As described above, it is required that the toner has a high storage elastic modulus up to a temperature required for heat-resistant storage stability and that the storage elastic modulus drops sharply when the temperature is higher, i.e., the toner must have a sharp melting property. As mentioned above, crystalline resins are an example of materials having a sharp melting property.In addition, in the differential scanning calorimetry of the toner, the temperature is increased from 20° C. to 180° C. at a heating rate of 10° C. / min to obtain the differential scanning calorimetry curve A. The toner is then held at 180°C for 10 minutes, and the temperature is then lowered from 180°C to 10°C at a temperature lowering rate of 10°C / min to obtain the differential scanning calorimetry curve B. At this time, the differential scanning calorimetry curve A has an endothermic peak m(B) derived from the crystalline resin and an endothermic peak m(W) derived from the release agent. In addition, the differential scanning calorimetry curve B has an exothermic peak c(B) derived from the crystalline resin and an exothermic peak c(W) derived from the release agent.When the peak temperature (° C.) of the endothermic peak m(B) is denoted by Tm(B), the peak temperature (° C.) of the endothermic peak m(W) is denoted by Tm(W), the peak temperature (° C.) of the exothermic peak c(B) is denoted by Tc(B), and the peak temperature (° C.) of the exothermic peak c(W) is denoted by Tc(W), Tm(B), Tc(B), Tm(W), and Tc(W) satisfy the following formula.Tm(B) represents the melting point of the crystalline resin. When Tm(B) is 50.0° C. or higher, favorable heat-resistant storage stability can be achieved. Tm(B) is preferably 55.0° C. or higher, more preferably 58.0° C. or higher. Since Tm(B) is 80.0° C. or lower, favorable low-temperature fixability can be achieved. Tm(B) is preferably 75.0° C. or lower, more preferably 70.0° C. or lower. Tm(B) is preferably from 55.0° C. to 75.0° C., more preferably from 58.0° C. to 70.0° C. Tm(B) can be controlled by the type and molecular weight of the crystalline resin.The weight average molecular weight of the crystalline resin is, for example, preferably 20000 to 40000, more preferably 25000 to 40000.Tm(B)-Tc(B) is the difference between the temperature at which the crystalline resin is melted by heating and the temperature at which the crystalline resin crystallizes when cooled again after melting, i.e., the crystallization rate. A small Tm(B)-Tc(B) represents a fast crystallization rate, a large Tm(B)-Tc(B) represents a slow crystallization rate. This value is taken as a measure of a thermal property corresponding to the rate (rate) at which the toner melts by heating through the fixing member and the melt viscosity decreases during the electrophotographic fixing process, and then the toner cools after passing through the fixing unit and the melt viscosity increases.A fast crystallization rate is one of the properties of crystalline resins, so that it has been considered difficult to increase only the melting rate and conversely control the crystallization rate to be slow. In the toner of the present disclosure, Tm(B)-Tc(B) is 15.0° C. or more. Tm(B)-Tc(B) is preferably 17.0° C. or more. These ranges indicate that the crystallization rate is slower than conventional crystalline resins.The present inventors have found that advantageous color reproducibility can be obtained when Tm(B)-Tc(B) is in the above range. This is considered to be because the crystallization rate in the above range causes the melt viscosity to increase after the colors are thoroughly mixed during fixation in a multi-color application image. The inventors have also found that the gloss uniformity of the fixed image can be improved when Tm(B)-Tc(B) is in the above range. This is considered to be because the crystallization rate in the above range reduces the difference in volumetric shrinkage rate between high toner application level regions and low toner application level regions.Moreover, in the toner of the present disclosure, Tm(B)-Tc(B) is 25.0° C. or less. Tm(B)-Tc(B) is preferably 22.0° C. or less. The inventors have found that when Tm(B)-Tc(B) is in the above range, the gloss uniformity of the fixed image is improved. It is considered that this is because the crystallization rate is not too slow and appropriate, so that the fixed image can be prevented from being affected by the unevenness of the paper and from being given uneven gloss. Tm(B)-Tc(B) is preferably 17.0° C. to 22.0° C., and more preferably 19.0° C. to 22.0° C.In addition, Tc(B) is preferably 30.0° C. to 60.0° C., and more preferably 40.0° C. to 50.0° C.Tm(B)-Tc(B) and Tm(W)-Tc(W) can be controlled within the above ranges by including an amorphous resin in addition to the crystalline resin and controlling the structure, the ratio of the amount, the molecular chain length, etc. of the crystalline resin and the amorphous resin. This is considered to be because the amorphous resin interferes with the molecular arrangement of the crystalline resin and controls the crystallization rate when the toner melted during the fixation crystallizes. In particular, by making the structures and molecular chain lengths of the crystalline resin and the amorphous resin close to each other and setting the content of the amorphous resin to a preferred amount described herein, it is easier to control Tm(B)-Tc(B) within the above range. It is also believed that the above Tm(B)-Tc(B) control means makes it easier to control Tm(W)-Tc(W) within the above range due to the interaction between the resin and the releasing agent.From the viewpoint of low-temperature fixability, the content of the crystalline resin in the binder resin is preferably 25.0% by mass or more, and more preferably 35.0% by mass or more. The amount of the crystalline resin in the binder resin is preferably 25.0% by mass to 95.0% by mass, more preferably 35.0% by mass to 80.0% by mass, even more preferably 50.0% by mass to 75.0% by mass, and even more preferably 65.0% by mass to 75.0% by mass.In order to control Tm(B)-Tc(B) and Tm(W)-Tc(W) within the above ranges, it is preferable that the crystalline resin contains a crystalline vinyl resin, and it is preferable that the amorphous resin contains an amorphous vinyl resin. It is more preferred that the crystalline resin is a crystalline vinyl resin, and it is more preferred that the amorphous resin is an amorphous vinyl resin. The crystalline vinyl resin has long-chain alkyl groups as side chains, and the long-chain alkyl groups in the side chains are aligned with each other, thereby forming crystallinity. Thereby, the side chains of the crystalline vinyl resin and the amorphous vinyl resin can become more compatible and interact with each other, making it easier to control Tm(B)-Tc(B) within the above range. It is also believed that the above Tm(B)-Tc(B) control means makes it easier to control Tm(W)-Tc(W) within the above range due to the interaction between the resin and the releasing agent.From the viewpoint of controlling Tm(B)-Tc(B) and Tm(W)-Tc(W) within the above ranges, it is preferable that the crystalline resin contains a monomer unit represented by the following formula (1) (more preferably formula (1-1)).Further, it is more preferred that the crystalline resin contains a monomer unit having a lactam structure, and it is even more preferred that the crystalline resin contains a monomer unit having a five-membered lactam structure. It is even more preferable that the monomer unit having a lactam structure is represented by the following formula (L) (more preferably formula (L-1)). It is believed that when the crystalline resin has a lactam structure, the crystalline resin has polar sites that facilitate interaction with other materials such as polyfunctional ester wax In formula (1), R represents 1 a hydrogen atom or a methyl group, L represents 1 a single bond, an ester bond or an amide bond (preferably an ester bond), and m represents an integer of 15 to 30 (preferably 17 to 29, more preferably 19 to 23).In the formula (1-1), R 3 represents a hydrogen atom or a methyl group, and R 4 represents a linear alkyl group having 16 to 31 carbon atoms (preferably 18 to 28, more preferably 20 to 24).In the formulas (L) and (L-1), R 2 represents a hydrogen atom or a methyl group. n is an integer of 1 to 4 (preferably 1 to 3).In addition, the toner includes a releasing agent, and Tm(W)-Tc(W) represents the crystallization rate of the releasing agent. The present inventors have found that in order to obtain the above-mentioned effects, it is necessary to control not only the crystallization rate of the crystalline resin but also the crystallization rate of the releasing agent.The inventors have found that favorable color reproducibility can be achieved when Tm(W)-Tc(W) is set to 15.0° C. or higher. This is presumably because, as explained with respect to Tm(B)-Tc(B), in a multicolor application image, the melt viscosity increases after the colors are thoroughly mixed during fixation. The inventors have also found that the gloss uniformity of the fixed image can be improved when Tm(W)-Tc(W) is set to 15.0° C. or higher. This is believed to be due to the fact that, as explained with respect to Tm(B)-Tc(B), the difference in volumetric shrinkage rate between areas having a large application level and areas having a small application level can be reduced.Moreover, in the toner of the present disclosure, Tm(W)-Tc(W) is 25.0° C. or less. Tm(W)-Tc(W) is preferably 24.0° C. or less. The inventors have found that when Tm(W)-Tc(W) is in the above ranges, the gloss uniformity of the fixed image is improved. It is considered that this is because, as described above, the fixed image can be prevented from being affected by the unevenness of the paper and having uneven gloss. Tm(W)-Tc(W) is preferably 19.0°C to 24.0°C, more preferably 20.0°C to 24.0°C.Tm(W) is preferably 60.0° C. to 85.0° C., more preferably 70.0° C. to 80.0° C.Tc(W) is preferably 40.0° C. to 60.0° C., more preferably 47.0° C. to 57.0° C.Tm(B)-Tc(B) and Tm(W)-Tc(W) can be controlled within the above ranges by the structure, the mixing ratio and the molecular chain length of the crystalline resin and the releasing agent. This is considered to be because the crystalline resin and the releasing agent form a eutectic when the molten toner crystallizes, thereby making it possible to control the crystallization rate.As for the mixing ratio of the crystalline resin and the releasing agent, the appropriate amounts vary depending on the materials used, and the amounts can be freely selected. One method is to add the releasing agent in an amount that makes it easy to sufficiently control the crystallization rate. It is also preferable to use the content of releasing agents described below so that the crystallization rate does not become too slow.In order to control Tm(B)-Tc(B) and Tm(W)-Tc(W) within the above ranges, it is also preferable that the releasing agent includes a multifunctional ester wax. It is believed that the multifunctional ester wax not only causes a single crystalline resin molecule to form a eutectic but also exists between the molecules in a bridging state, making it easier to apply the effect thereof to the entire resin.The polyfunctional ester wax refers to an ester compound of a polyhydric alcohol and a monocarboxylic acid and an ester compound of a polycarboxylic acid and a monohydric alcohol. The polyfunctional ester wax is preferably at least one ester compound selected from the group consisting of an ester compound of a tetrahydro- to octahydric alcohol and an aliphatic monocarboxylic acid, and an ester compound of a tetravalent- to octahydric carboxylic acid and an aliphatic monohydric alcohol. More preferably, the polyfunctional ester wax is at least one ester compound selected from the group consisting of an ester compound of a hexahydric to octahydric alcohol and an aliphatic monocarboxylic acid, and an ester compound of a hexahydric to eighthydric carboxylic acid and an aliphatic monohydric alcohol.In order to control Tm(B)-Tc(B) within the above range, it is further preferred to simultaneously contain a straight-chain fatty acid metal salt when using a crystalline resin having a monomer unit of formula (1). The straight-chain fatty acid metal salt refers to a salt of a straight-chain fatty acid and a metal other than sodium or potassium. Particularly, with respect to the relationship to m in formula (1) where the number of carbon atoms of the straight chain fatty acid of the straight chain fatty acid metal salt is denoted by C(b), it is preferable that C(b) satisfies m-10≤C(b)≤m+10, more preferably m-6≤C(b)≤m+6, and even more preferably m-4≤C(b)≤m+4. Moreover, it is preferable that the valence of the metal in the straight chain fatty acid metal salt is two or more. In other words, the straight-chain fatty acid metal salt is preferably a salt of a metal having a valence of two or more and a straight-chain fatty acid.When m - 10 ≤ C(b) ≤ m + 10 is satisfied, it means that the chain length of the alkyl group in formula (1) is close to the chain length of the straight chain fatty acid in the straight chain fatty acid metal salt. Generally, alkyl chains of similar chain lengths have a high affinity for each other. It is considered that by including a straight-chain fatty acid metal salt having a chain length close to the chain length of the alkyl group in formula (1) having crystallinity, it is possible to produce a eutectic-like state of the crystalline resin and the straight-chain fatty acid metal salt. Therefore, it is possible to control the crystallization rate.In addition, the fatty acid metal salts containing metals having a valence of two or more often have two or more alkyl chains and are easily compatible with the alkyl chains of other crystalline resin molecules. It is considered that as a result, when the toner melts and the molecular chains become movable in the fixing process, the fatty acid metal salt introduced into the molecular chain of the crystalline resin is also introduced into other molecular chains of the crystalline resin, thereby producing a pseudo-bridged state and making it possible to exert an effect on the whole resin.In the present disclosure, the valence of the metal in the straight-chain fatty acid metal salt that is two or more means a metal type in which a single metal ion can assume a valence of two or more. The divalent or higher metal is not particularly limited, and at least one metal selected from the group consisting of calcium and aluminum may be mentioned. Aluminum is preferred. The straight chain fatty acid metal salt may be selected from, for example, at least one selected from the group consisting of zinc octylate, magnesium distearate, aluminum distearate, calcium distearate, zinc distearate, calcium montanate, calcium laurate, barium laurate, calcium ricinoleate, barium ricinoleate, zinc ricinoleate, etc. It is more preferred that the straight chain fatty acid metal salt includes aluminum distearate.In addition, the toner satisfies Tc(W) ≤ Tm(B). Thereby, a toner excellent in color reproducibility and image gloss uniformity is obtained. Tc(W) ≤ Tm(B) means that the crystallization temperature of the releasing agent is equal to or lower than the melting point of the crystalline resin. That is, there is a temperature zone in which both the releasing agent and the crystalline resin are melted. In the toner of the present disclosure, the releasing agent and the crystalline resin interact with each other, for example, by forming a eutectic, so that a temperature zone in which both are melted is required, and it is considered that Tc(W)≤Tm(B) should be satisfied. It is also believed that the presence of a temperature zone in which both the release agent and the crystalline resin are melted improves color reproducibility and gloss uniformity because the crystalline resin and the release agent form a eutectic and the crystallization rate is controlled.The above range can be satisfied by the material selection of the crystalline resin and the releasing agent, as well as by the resin design such as the molecular weight.Tm(B)-Tc(W) is preferably 0.0° C. to 26.0° C., more preferably 5.0° C. to 25.0° C., and even more preferably 10.0° C. to 20.0° C.Further, in the differential scanning calorimetry curve of the toner, after obtaining the differential scanning calorimetry curve B, the temperature is maintained at 10° C. for 10 minutes, and then the temperature is raised from 10° C. to 180° C. at a temperature rise rate of 10° C. / min, to obtain a differential scanning calorimetry curve C. At this time, it is preferable that the differential scanning calorimetry curve C has an endothermic peak (B 2) derived from the crystalline resin. When the peak temperature (° C.) of the endothermic peak (B 2) is referred to as Tm(B2), it is preferable that Tm(B) and Tm(B 2) satisfy 1.0≤Tm(B)-Tm(B 2)≤10.0.When Tm(B)-Tm(B2) is in the above range, it means that Tm(B), i.e., the melting point corresponding to the toner before fixation, is higher than the melting point corresponding to the toner after fixation. When Tm(B)-Tm(B2) is in the above range, the balance between low-temperature fixability and heat-resistant storage stability is particularly advantageous. Tm(B)-Tm(B2) is more preferably 4.0° C. to 10.0° C.Tm(B)-Tm(B2) can be increased by promoting crystallization by heat treatment near the crystallization temperature of the crystalline resin during toner production. Tm(B)-Tm(B2) can also be lowered by heating to a temperature equal to or higher than the crystallization temperature of the crystalline resin during toner production and then cooling rapidly to suppress the crystallization.Further, the toner of the present disclosure has a storage elastic modulus G' (TmB) of 1.0×10 5 Pa to 1.0×10 8 Pa at Tm(B) [° C.]. G' (TmB) represents the storage elastic modulus of the toner near the melting point of the crystalline resin. Toners having a storage elastic modulus in this range retain some degree of elasticity near the melting point and are susceptible to the problems noted in the present disclosure. When G' (TmB) is less than 1.0×10 5 Pa, the image is easily affected by the unevenness of the paper, and the gloss uniformity is likely to decrease. When G' (TmB) is over 1.0×10 8 Pa, the low-temperature fixability is likely to be lower.G' (TmB) is preferably 1.0×10 6 Pa to 6.0×10 7 Pa, and more preferably 3.0×10 6 Pa to 1.0×10 7 Pa.G' (TmB) can be increased, for example, by reducing the amount of the crystalline resin added, by increasing the molecular weight of the binder resin, or by adding a crosslinking agent. G' (TmB) can be reduced, for example, by increasing the amount of the crystalline resin added or by decreasing the molecular weight of the binder resin.The crystalline resin will be described below. As mentioned above, a crystalline resin in this disclosure refers to a resin that exhibits a marked endothermic peak in differential scanning calorimetry (DSC).Examples of crystalline resins include vinyl resins, polyester resins, polyurethane resins, epoxy resins, etc. having crystallinity, with vinyl resins having crystallinity being preferred.The crystalline resin preferably contains 30.0% by mass or more of the monomer unit represented by the above formula (1) (hereinafter also referred to as monomer unit (a)). Formula (1) indicates that the resin has a long-chain alkyl group, and the presence of a long-chain alkyl group in the crystalline resin makes the resin more likely to have crystallinity. The crystalline resin preferably contains 30.0% by mass to 90.0% by mass, more preferably 60.0% by mass to 90.0% by mass, and even more preferably 75.0% by mass to 90.0% by mass of the monomer unit (a) represented by formula (1).In formula (1), m represents an integer of 15 to 30. When m is 15 to 30, the crystalline resin is more likely to have crystallinity, and a toner excellent in low-temperature fixability can be obtained.m is preferably 17 to 29 and more preferably 19 to 23.As a method for incorporating the monomer unit (a), there is a method for polymerizing the following (meth)acrylic esters. For example, there can be mentioned (meth)acrylic esters having a linear alkyl group having 16 to 36 carbon atoms [stearyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, Heneicosanyl(meth)acrylat behenyl (meth)acrylate, Lignoceryl(meth)acrylat ceryl (meth)acrylate, octacosyl (meth)acrylate, myristyl (meth)acrylate, Dotriacontyl(meth)acrylat etc.] and (meth)acrylic esters having a branched alkyl group having 18 to 36 carbon atoms [2-decyltetradecyl (meth)acrylate etc.].When the crystalline resin is a vinyl resin having crystallinity, it is possible to use other monomer units in addition to the monomer unit (a). One method of introducing the other monomer units is to polymerize the (meth)acrylic ester with other vinyl monomers. The other monomer units may be used alone or in combination of two or more.Examples of other vinyl monomers include the following styrene, α-methylstyrene, (meth)acrylic esters such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate.Monomers having a urea group: for example, monomers obtained by reacting an amine having 3 to 22 carbon atoms [primary amines (such as normal butylamine, t-butylamine, propylamine, and isopropylamine), secondary amines (such as di-normal ethylamine, di-normal propylamine, and di-normal butylamine), aniline, and cyclohexylamine] with an isocyanate having 2 to 30 carbon atoms and an ethylenically unsaturated bond using a known method.Monomers having a carboxy group: for example, methacrylic acid, acrylic acid and 2-carboxyethyl (meth)acrylate.Monomers having a hydroxy group: for example, 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate.Monomers having an amide group: for example, acrylamide and monomers obtained by reacting an amine having 1 to 30 carbon atoms with a carboxylic acid having 2 to 30 carbon atoms and an ethylenically unsaturated bond (such as acrylic acid and methacrylic acid) according to a known method.Monomers having a lactam structure, for example N-vinyl-2-pyrrolidone.Among these, it is preferable to use a monomer having a lactam structure, and it is even more preferable that the lactam structure has a five-membered lactam structure. Preferably, N-vinyl-2-pyrrolidone is used as a monomer having a five-membered lactam structure. Monomer units having a lactam structure are exemplified by monomer units represented by the above-mentioned formula (L) (preferably formula (L-1)). The crystalline resin preferably contains 1.0% by mass to 15.0% by mass, and more preferably 4.0% by mass to 10.0% by mass of the monomer unit represented by the formula (L) (preferably formula (L-1)).The crystalline resin may also contain a styrene-based monomer unit. The crystalline resin preferably contains 1.0% by mass to 25.0% by mass, and more preferably 7.0% by mass to 15.0% by mass of the styrene-based monomer unit.The crystalline resin may also contain a monomer unit based on (meth)acrylic acid. The crystalline resin preferably contains 0.5 mass % to 5.0 mass %, and more preferably 1.5 mass % to 4.0 mass % of the (meth)acrylic acid-based monomer unit.When the crystalline resin is a polyester resin, a resin having crystallinity and derived from a group of polyester resins obtainable by a reaction between a carboxylic acid having two or more carboxy groups and a polyhydric alcohol may be used.Examples of carboxylic acids having two or more carboxy groups include the following compounds.Dibasic acids such as succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, malonic acid and dodecenylsuccinic acid, their anhydrides and lower alkyl esters, and aliphatic unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid and citraconic acid.Examples of the carboxylic acid having two or more carboxy groups also include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, and anhydrides and lower alkyl esters thereof. These may be used alone or in combination of two or more.Examples of the polyhydric alcohol include the following compounds.Alkylene glycols (ethylene glycol, 1,2-propylene glycol and 1,3-propylene glycol); alkylene ether glycols (polyethylene glycol and polypropylene glycol); alicyclic diols (1,4-cyclohexanedimethanol); bisphenols (bisphenol A); and alkylene oxide (ethylene oxide and propylene oxide) adducts of alicyclic diols. Alkyl radicals in alkylene glycols and alkylene ether glycols can be linear or branched.Further examples of polyhydric alcohols include glycerol, trimethylolethane, trimethylolpropane and pentaerythritol. These may be used alone or in combination of two or more.It is also possible to use a monohydric acid such as acetic acid or benzoic acid or a monohydric alcohol such as cyclohexanol or benzyl alcohol for adjusting the acid number or the hydroxyl number.Although there is no particular limitation on the process for producing the polyester resin, the polyester resin may be produced either by a transesterification process or a direct polycondensation process or a combination of these processes.The binder resin contains an amorphous resin in addition to the crystalline resin. Examples of amorphous resins include vinyl resins, polyester resins, polyurethane resins and epoxy resins, but amorphous vinyl resins such as polystyrene are preferred.Examples of the vinyl monomer include styrene, α-methylstyrene, and (meth)acrylic esters such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.Monomers having a urea group: for example, monomers obtained by reacting an amine having from 3 to 22 carbon atoms [primary amines (such as normal butylamine, t-butylamine, propylamine and isopropylamine), secondary amines (such as di-normal ethylamine, di-normal propylamine and di-normal butylamine), aniline and cyclohexylamine] with an isocyanate having from 2 to 30 carbon atoms and an ethylenically unsaturated bond according to a known method.Monomers having a carboxy group: for example, methacrylic acid, acrylic acid and 2-carboxyethyl (meth)acrylate.Monomers having a hydroxy group: for example, 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate.Monomers having an amide group: for example, acrylamide and monomers obtained by reacting an amine having from 1 to 30 carbon atoms with a carboxylic acid having from 2 to 30 carbon atoms and an ethylenically unsaturated bond (such as acrylic acid and methacrylic acid) according to a known method.Among these, styrene, (meth)acrylic acid, methyl (meth)acrylate and t-butyl (meth)acrylate are preferably used. The amorphous vinyl resin preferably contains a monomer unit of styrene.The content of the amorphous resin in the binder resin is preferably 5.0% by mass to 75.0% by mass, more preferably 5.0% by mass to 50.0% by mass, even more preferably 20.0% by mass to 50.0% by mass, and even more preferably 25.0% by mass to 35.0% by mass.The binder resin may contain a crosslinking agent if necessary. Examples of crosslinking agents that may be used include, but are not limited to, the following compounds:Ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, divinylbenzene, bis(4-acryloxypolyethoxyphenyl)propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diacrylates of polyethylene glycol #200, #400, and #600, dipropylene glycol diacrylate, polypropylene glycol diacrylate, and polyester diacrylate (MANDA, manufactured by Nippon Kayaku Co., Ltd.), as well as the above-mentioned acrylates replaced with methacrylates.The content of the crosslinking agent in the binder resin is preferably 0.01 mass % to 10.00 mass %, and more preferably 0.03 mass % to 5.00 mass %.The toner contains a releasing agent. Examples of the releasing agent include hydrocarbon wax and ester wax. The release agent preferably contains a polyfunctional ester wax.The hydrocarbon wax is not particularly limited, but examples thereof are as follows. Aliphatic hydrocarbon waxes: low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight olefin copolymers, Fischer-Tropsch waxes and waxes obtained by oxidation or acid addition.The ester wax should have at least one ester bond per molecule and may be a natural ester wax or a synthetic ester wax.Ester waxes are not particularly limited, but examples thereof are the following: esters of a monohydric alcohol and a monocarboxylic acid such as behenyl behenate, stearyl stearate and palmityl palmitate; esters of a dicarboxylic acid and a mono-alcohol such as dibehenenyl sebacate; esters of a dihydric alcohol and a monocarboxylic acid such as ethylene glycol distearate and hexanedibehenate; esters of a monohydric alcohol and a monocarboxylic acid such as glycerol tribehenate; esters of a tetravalent alcohol and a monocarboxylic acid such as pentaerythritol tetrastearate and pentaerythritol tetrapalmitate; esters of a hexavalent alcohol and a monocarboxylic acid such as Dipentaerythritolhexastearat dipentaerythritol hexapalmitate and Dipentaerythritolhexabehenat; Esters of a polyfunctional alcohol and a monocarboxylic acid such as polyglycerol behenate; and natural ester waxes such as carnauba wax and rice wax.Among these, at least one selected from the group consisting of esters of hexahydronic alcohols and monocarboxylic acids such as Dipentaerythritolhexastearat dipentaerythritol hexapalmitate, and Dipentaerythritolhexabehenat is preferred. More preferably, the release agent contains Dipentaerythritolhexastearat.As the releasing agent, a hydrocarbon wax or an ester wax may be used alone or a combination of a hydrocarbon wax and an ester wax or a mixture of two or more of them.In the toner, the content of the releasing agent in the toner particle is preferably 1.0% by mass to 30.0% by mass, more preferably 2.0% by mass to 25.0% by mass, even more preferably 5.0% by mass to 15.0% by mass, and even more preferably 6.0% by mass to 13.0% by mass. When the content of the releasing agent in the toner particle is within the above range, the above eutectic effect with the crystalline resin is easily exhibited.The melting point of the release agent is preferably 60° C. to 120° C. When the melting point of the release agent is within the above range, the release agent melts during fixation and easily migrates to the surface of the toner particles, thereby exhibiting easy releasability. More preferably, the melting point of the releasing agent is 70°C to 100°C.The toner may also contain a colorant. Examples of colorants include known organic pigments, organic dyes, inorganic pigments, as well as carbon black and magnetic particles as black colorants. Other colorants commonly used in toners may also be used. Examples of yellow colorants include condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specifically, C.I. pigments yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 155, 168, and 180 may be preferably used.Examples of magenta colorants include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specifically, C.I. Pigment Red 2, 3, 5, 6, 7, 23, 48:2, 48:3, 48:4, 57:1, 81:1, 122, 144, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, and 254 may be preferably used. Examples of cyan colorants include copper phthalocyanine compounds and their derivatives, anthraquinone compounds, and basic dye lake compounds. Specifically, C.I. Pigment Blue 1, 7, 15, 15:1, 15:2, 15:3, 15:4, 60, 62, and 66 may preferably be used.The selection of the colorants is made in consideration of hue angle, chroma, lightness, weather resistance, OHP transparency and dispersibility in the toner. The content of the colorant is preferably from 1.0 to 20.0 parts by mass per 100.0 parts by mass of the binder resin. When a magnetic particle is used as the colorant, its content is preferably 40.0 to 150.0 parts by mass per 100.0 parts by mass of the binder resin.The toner particle may include a charge control agent, if desired. A charge control agent may also be added to the toner particle from the outside. By mixing a charge control agent, it is possible to stabilize the charging characteristics and control the triboelectric charge amount to a level suitable for the developing system.A known charge control agent can be used, and a charge control agent that provides a fast charging speed and keeps a uniform charge amount stable is particularly desirable.Organic metal compounds and chelate compounds are effective as charge control agents for giving a negative charge to the toner, and examples include monoazo metal compounds, acetyl acetone metal compounds and metal compounds using aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids and dicarboxylic acids.Examples of charge control agents which impart a positive charge to the toner include nigrosine, quaternary ammonium salts, higher fatty acid metal salts, diorganotin borates, guanidine compounds and imidazole compounds.The content of the charge control agent is preferably 0.01 to 20.0 parts by mass, more preferably 0.5 to 10.0 parts by mass, per 100.0 parts by mass of the toner particle.The toner particle as such may be used as a toner, but a toner may be optionally formed by mixing an external additive or the like to attach the external additive to the surface of the toner particle.Examples of external additives include inorganic fine particles selected from the group consisting of silica fine particles, alumina fine particles and titania fine particles, and composite oxides thereof. Examples of the composite particles include silica-aluminum fine particles and strontium titanate fine particles.The content of the external additive is preferably from 0.01 parts by mass to 8.0 parts by mass, and more preferably from 0.1 parts by mass to 4.0 parts by mass, based on 100 parts by mass of the toner particle.The toner particles can be prepared by any conventional method such as suspension polymerization, emulsion aggregation, solution suspension or pulverization in the present case. However, it is preferred to produce the toner particles by suspension polymerization.The method of suspension polymerization will be described in detail below.For example, a polymerizable monomer composition is prepared by mixing a crystalline resin synthesized beforehand, polymerizable monomers to form an amorphous resin, a releasing agent, and other materials such as a colorant and a charge control agent, and uniformly dissolving or dispersing the mixture.Then, the polymerizable monomer composition is dispersed in an aqueous medium by means of a stirrer or the like to prepare suspended particles of the polymerizable monomer composition. The polymerizable monomers contained in the particles are then polymerized by an initiator or the like to obtain toner particles.After polymerization, the toner particles are filtered, washed and dried according to known methods, and an external additive is added as needed to obtain the toner.A known polymerization initiator may be used.Examples of the polymerization initiator include: azo or diazo polymerization initiators such as 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile and azobisisobutyronitrile; and peroxide polymerization initiators such as benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, t-butylperoxypivalate, t-butylperoxyisobutyrate, t-butylperoxyneodecanoate, methyl ethyl ketone peroxide, diisopropylperoxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide and lauroyl peroxide.For adjusting the molecular weight, a known chain transfer agent and a known polymerization inhibitor may also be used.The aqueous medium may contain an inorganic or organic dispersion stabilizer. A known dispersion stabilizer may be used.Examples of inorganic dispersion stabilizers include: phosphates such as hydroxyapatite, tribasic calcium phosphate, dibasic calcium phosphate, magnesium phosphate, aluminum phosphate and zinc phosphate; carbonates such as calcium carbonate and magnesium carbonate; metal hydroxides such as calcium hydroxide, magnesium hydroxide and aluminum hydroxide; sulfates such as calcium sulfate and barium sulfate; calcium metasilicate; bentonite; silica and alumina.Examples of organic dispersion stabilizers include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salts of carboxymethyl cellulose, polyacrylic acid and its salts, and starch.When an inorganic compound is used as the dispersion stabilizer, a commercially available inorganic compound may be used as such, or the inorganic compound may be produced in an aqueous medium to obtain a finer particle.In the case of calcium phosphate such as hydroxyapatite or tribasic calcium phosphate, for example, an aqueous solution of the phosphate and an aqueous solution of a calcium salt can be mixed under high-speed stirring.The aqueous medium may contain a surfactant. A known surfactant may be used. Examples of the surfactant include: anionic surfactants such as sodium dodecyl benzene sulfate and sodium oleate; cationic surfactants; amphoteric surfactants; and nonionic surfactants.Methods for calculating and measuring various physical properties will be described below.Measurement Method for Differential Scanning Calorimetry (DSC)The endothermic peak temperature and exothermic peak temperature (Tm(B), Tm(W), Tc(B), Tc(W) and Tm(B2)) of the crystalline resin and the releasing agent are measured according to ASTM D3418-82 with a differential scanning calorimeter "Q1000" (manufactured by TA Instruments). The melting points of indium and zinc are used to correct the temperature of the device, and the heat of fusion of indium is used to correct the amount of heat.Toner measurements are made by first weighing 10 mg of toner and placing it in an aluminum dish with a blank aluminum dish as a reference. In the first temperature increase process, the temperature of the sample is increased from 20° C. to 180° C. during the measurements at 10° C. / min, and the differential scanning calorimetry curve A is prepared. Thereafter, the temperature is maintained at 180° C. for 10 minutes, then the cooling process is performed by lowering the temperature from 180° C. to 10° C. at 10° C. / min while the measurements are performed, and the differential scanning calorimetry curve B is obtained. Subsequently, the temperature is maintained at 10° C. for 10 minutes and then increased again from 10° C. to 180° C. in the second temperature increase process at 10° C. / min while measurements are performed, and the differential scanning calorimetry curve C is obtained. The peak peak temperatures of the peaks appearing in the obtained differential scanning calorimetry curves are determined and used as peak temperatures.By separating the crystalline resin and the releasing agent from the toner using the method described below and performing a separate DSC measurement of the crystalline resin or the releasing agent, it is possible to confirm whether the obtained peak is derived from the crystalline resin or the releasing agent.Method for Measuring Storage Elastic Modulus G' (TmB)The storage elastic modulus G' (TmB) is measured with a viscoelasticity measuring apparatus (rheometer) ARES (manufactured by Rheometrics Scientific).The procedure of the measurement is described in ARES Handbooks 902-30004 (August 1997 edition) and 902-00153 (July 1993 edition) edited by Rheometrics Scientific, and is as follows- Measuring tool: torsion rectangular.Measurement sample: For the toner, a rectangular sample having a width of 12 mm, a height of 20 mm and a thickness of 2.5 mm is prepared by a compression molding machine (25 kN is maintained at room temperature for 30 minutes). The printing machine used is a 100 kN press NT-100H manufactured by NPa System Co. Ltd.A device and the sample are allowed to stand at room temperature (23° C.) for 1 hour, then the sample is attached to the device. See the figure. As shown in the figure, the two are fixed so that the measurement part has a width of 12.0 mm, a thickness of 2.5 mm and a height of 10.0 mm. After the temperature is set to the measurement start temperature of 30° C. for 10 minutes, measurement is performed with the following settings.- Measurement frequency: 6.28 rad / s.Setting of measurement elongation: The initial value is set to 0.1%, and measurement is performed in the automatic measurement mode.correction of the sample elongation: is set in the automatic measurement mode.Measurement temperature: The temperature is increased from 30°C to 150°C at a rate of 2°C per minute.Measurement interval: viscoelastic data are measured every 30 seconds, i.e., every 1° C.The data is transferred via an interface to the RSI Orchestrator (control, data acquisition and analysis software) (manufactured by Rheometrics Scientific) running under Microsoft Windows 2000.From the measurement data, the storage elastic modulus G' at Tm(B)°C obtained by the above-described DSC measurement is read, and G' (TmB) is calculated.Method for Separating Toner Particles from TonerIn the analysis of toner particles, when the surface of the toner particles has been treated with an external additive, the external additive is separated by the following method to obtain toner particles.To prepare a concentrated sucrose solution, 160 g of sucrose (manufactured by Kishida Chemical Co., Ltd.) in total is added to 100 ml of ion-exchanged water and dissolved in a hot water bath. A total of 31 g of the concentrated sucrose solution and 6 ml of contaminon N (a 10% aqueous solution of a neutral detergent having a pH of 7 for cleaning precision measurement instruments, which is composed of a nonionic surfactant, an anionic surfactant and an organic builder and manufactured by Wako Pure Chemical Industries, Ltd.) are placed in a centrifuge tube to prepare a dispersion.To this dispersion liquid, 1.0 g of toner in total is added and lumps of toner are crushed with a spatula or the like. The centrifuge tube is shaken for 20 minutes with a shaker at 350 strokes per minute. After shaking, the solution is transferred to a glass tube (50 mL) for a swing rotor, and separation is performed in a centrifuge at 3500 U / min for 30 minutes. In this process, the toner particles are separated from the detached external additives.The sufficient separation of toner and aqueous solution is visually checked, and the toner having settled in the uppermost layer is separated with a spatula or the like. The collected toner is filtered with a vacuum filter and then dried in a dryer for at least 1 hour to obtain toner particles. This operation is carried out several times to obtain the desired amount.Method for Measuring Molecular WeightThe molecular weight such as the weight average molecular weight Mw is measured by gel permeation chromatography (GPC) as follows.First, the sample is dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. The resulting solution is filtered through a solvent-resistant membrane filter (Cornhori Disk, Tosoh Corp.) having a pore diameter of 0.2 μm to obtain a sample solution. The concentration of the THF-soluble components in the sample solution is adjusted to about 0.8 mass %. The measurement is carried out under the following conditions with this sample solution.Device: HLC8120 GPC (detector: RI) (Tosoh Corp.)Columns: Shotex KF-801, 802, 803, 804, 805, 806, 807 (a total of 7) (Showa Denko)- Eluent: tetrahydrofuran (THF)Flow rate: 1.0 mL / min- Oven temperature: 40.0°C- Sample injection volume: 0.10 mLA molecular weight calibration curve prepared using standard polystyrene resin (such as TSK standard polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500, Tosoh Corp.) is used to calculate the molecular weights of the samples.Method for Separating Crystalline Resin from Toner ParticleThe crystalline resin can be separated from the toner by known methods, an example of which is shown below.Gradient polymer LC is used as a method for separating resin components from toner. In this analysis, the separation can be carried out according to the polarity of the resin in the binder resin irrespective of the molecular weight.First, the toner is dissolved in chloroform. The sample is adjusted to a sample concentration of 0.1 mass % in chloroform, and the solution filtered by a 0.45 μm PTFE filter is used for measurement.The measurement conditions for the gradient polymer LC are listed below.Apparatus: Ultimate 3000 (manufactured by Thermo Fisher Scientific Inc.) Mobile phase: A chloroform (HPLC), B acetonitrile (HPLC)Gradient: 2 min (A / B=0 / 100)→25 min (A / B=100 / 0) (The gradient of the change of the mobile phase was designed linearly.)Flow rate: 1.0 mL / minInjection: 0.1 mass %×20 μLColumn: Tosoh TSKgel ODS (4.6 mmφ×150 mm×25 μm) Column temperature: 40° CDetector: Corona charged aerosol detector (corona CAD) (manufactured by Thermo Fisher Scientific Inc.)The resin components can be separated into two peaks according to their polarity in the time-intensity diagram obtained by the measurement. Thereafter, the above measurement is again performed, and the separation into two kinds of resins may be performed by fractionation at the time when the valleys of the respective peaks are reached.The separated resins are subjected to DSC measurement, whereby the resin having a melting point peak is regarded as a crystalline resin and that having no such peak is regarded as an amorphous resin.As for the releasing agent in the toner, components having a molecular weight of 3000 or less are separated as the releasing agent by HPLC recycling. The measurement method is illustrated below.First, a chloroform solution of the toner is prepared according to the above-described method. The resulting solution is then filtered through a solvent-resistant membrane filter "Myshori Disc" (manufactured by Tosoh Corporation) having a pore size of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the chloroform-soluble components is 1.0% by mass. With this sample solution, measurements are made under the following conditions.Apparatus: LC-Sakura NEXT (manufactured by Japan Analytical Industry Co., Ltd.)Column: JAIGEL 2H, 4H (manufactured by Japan Analytical Industry Co., Ltd.)- Eluent: chloroformFlow rate: 10.0 mL / min- Oven temperature: 40.0°C- Sample injection volume: 1.0 mLFor the calculation of the molecular weight of the sample, a molecular weight calibration curve prepared using standard polystyrene resins (e.g., product names "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500", Tosoh Corporation) is used.From the molecular weight curve thus obtained, the components having a molecular weight of 3000 or less are repeatedly fractionated and the release agent is removed from the toner. The molecular weight to be fractionated may be changed in consideration of the molecular weight of the separating agent.A method for measuring the ratio of the content of various monomer units such as monomer unit (a) in the resin and the number of carbon atoms in the alkyl groupThe ratio of the content of monomer units (a) and the like in the resin and the number of carbon atoms in the alkyl group are measured by 1 H-NMR under the following conditions. The crystalline resin fractionated by the above method can be used as a measurement sample.Measuring apparatus: FT-NMR apparatus JNM-EX400 (manufactured by JEOL Ltd.)Measurement frequency: 400 MHzPulse condition: 5.0 μsFrequency range: 10500 HzNumber of Accumulation: 64Measurement temperature: 30° CSample: To prepare the sample, 50 mg of the measurement sample is placed in a sample tube having an inner diameter of 5 mm, deuterated chloroform (CDCl 3) is added as a solvent, and dissolved in a thermostatic bath at 40° C.The obtained 1 H-NMR chart is analyzed to identify the structure of the individual monomer units. Here, for example, measurement of the ratio of the content of the monomer unit (a) in the crystalline resin and the number of carbon atoms in the alkyl group will be described.In the obtained 1 H-NMR chart, a peak independent of the peaks to be attributed to the constituents of monomer unit (a) is selected from the peaks to be attributed to the constituents of other monomer units, and the integral value S1 of this peak is calculated. The integral values of the other monomer units contained in the crystalline resin are also calculated in the same manner.When the monomer units constituting the crystalline resin are the monomer unit (a) and another monomer unit, the ratio of the content of the monomer unit (a) is calculated in the following manner by using the integral value S1 and the integral value S2 of the peak of the other monomer unit. Here, n1and n2are the number of hydrogen atoms in the constitutional elements to which the peak of interest belongs for each segment.Although there are two or more kinds of other monomer units, the ratio of the content of the monomer unit (a) can be calculated in the same manner (using S3... Sx, n3... nx).Also, the number of carbon atoms in the alkyl group can be calculated from the integral ratio of proton peaks in the 1 H-NMR chart.When a polymerizable monomer containing no hydrogen atoms in constitutional elements other than the vinyl group is used, the measurement atomic nucleus is set to 13 C using 13 C-NMR, measurement is performed in a single pulse mode, and calculation is performed in the same manner as in 1 H-NMR. Moreover, if necessary, measurement results of infrared absorption spectrum (IR) and gas chromatography-mass spectrometry (GC-MS) can be used.Measurement of crystalline resin content ratio in tonerIn the above-mentioned method for separating the crystalline resin from toner particles, the ratio of the content of the crystalline resin in the toner is calculated on the basis of the mass of the toner before dissolving in chloroform and the mass of the crystalline resin separated from the toner particles.Method for Separating Fatty Acid Metal Salt from Toner ParticlesA total of 10.0 g of toner particles from which external additives have been separated are weighed and the toner particles are placed in a cylindrical filter paper (Toyo Roshi No. 84) and placed in a Soxhlet extractor. A total of 200 mL of tetrahydrofuran (THF) as a solvent is added, extraction is carried out for 20 hours, and the THF-insoluble matter remaining on the cylindrical filter paper is dried and solidified. The obtained THF-insoluble matter is again filled in the cylindrical filter paper and put in the Soxhlet extractor. A total of 200 mL of chloroform is added as a solvent, and extraction is carried out for 8 hours. The fatty acid metal salt is separated from the toner particles by concentrating and drying the extract. The procedure is repeated as required to obtain the required amount of fatty acid metal salt.Measurement of the number of carbon atoms in the straight chain fatty acid in the straight chain fatty acid metal saltAfter extraction of the fatty acid metal salt by the method described above, the number of carbon atoms is measured by the same method as used for measurement of the number of carbon atoms in the alkyl group described above.Identification of Metal Valence in Straight Chain Fatty Acid Metal SaltsAfter extraction of the fatty acid metal salt by the above-described method, the kind of the metal contained in the straight-chain fatty acid metal salt is analyzed by an inductively coupled plasma atomic emission spectrometer (ICP-AES (manufactured by Seiko Instruments Inc.)).As a pretreatment, 8.00 ml of 60% nitric acid (manufactured by Kanto Chemical Co., for atomic absorption spectrometry) is added to 100.0 mg of the fatty acid metal salt to perform acid decomposition. During the acid decomposition, the treatment is carried out in a sealed vessel at an internal temperature of 220°C for 1 hr using a microwave high performance sample pre-treatment apparatus ETHOS1600 (manufactured by Milestone General Co., Ltd.) to prepare a polyvalent metal element-containing solution sample. Thereafter, high purity water is added to obtain 50.00 g in total for preparing the measurement sample. A calibration curve is prepared for each metal element, the type of metal contained in the fatty acid metal salt is determined, and the valence of the metal is determined based on the type. In the present disclosure, the valence of the metal in the straight-chain fatty acid metal salt of two or more means a metal type in which a single metal ion can assume a valence of two or more.EXAMPLESThe present disclosure will be explained in more detail below with reference to examples, which however do not serve to restrict the present disclosure in any way. In the following formulations, parts are by weight unless otherwise indicated.Preparation of crystalline resin 1The following materials were placed under a nitrogen atmosphere in a reaction vessel equipped with a reflux condenser, stirrer, thermometer and nitrogen inlet tube. <row><cell>-< / cell><cell>Toluene< / cell><cell>100,0 Parts< / cell>< / row><row><cell>-< / cell><cell>Monomer Composition< / cell><cell>100,0 Parts< / cell>< / row>(The monomer composition is a mixture of the following monomers in the ratio indicated below)<title desc="title" / ><row><cell / ><cell>(Docosyl acrylate (monomer (a))< / cell><cell>80,0 Parts)< / cell>< / row><row><cell / ><cell>(Styrene< / cell><cell>10,0 Parts)< / cell>< / row><row><cell / ><cell>(N-Vinyl-2-pyrrolidone< / cell><cell>7,0 Parts)< / cell>< / row><row><cell / ><cell>(Methacrylic acid< / cell><cell>3,0 Parts)< / cell>< / row><row><cell>-< / cell><cell>Polymerization initiator: t-butylperoxypivalate (Perbutyl PV, manufactured by NOF Corp.)< / cell><cell>0,5 Parts< / cell>< / row><row><cell / >< / row><p xml:id="_6c04ed0302" n="0169">The inside of the reaction vessel was heated to 70°C with stirring at 200 U / min, and the polymerization reaction was carried out for 12 hours to obtain a solution in which the polymer of the monomer composition was dissolved in toluene. The temperature of the solution was then lowered to 25°C, and the solution was poured into 1000.0 parts of methanol with stirring to precipitate the methanol-insoluble matter. The resulting methanol-insoluble matter was filtered off, washed with methanol, and then dried at 40°C in vacuofor 24 hours to obtain crystalline resin 1.<head xml:id="_6c04ed0303">Preparation of crystalline resins 2 to 7< / head><p xml:id="_6c04ed0304" n="0170">Crystalline resins 2 to 7 were prepared in the same manner as crystalline resin 1 except that the kinds and amounts of the monomer composition and the polymerization initiator added were changed as shown in Table 1. [Table 1] Table 1]<title desc="title">[Table 1] Table 1]Crystalline Resin 1Docosyl acrylate80,0Styrene10,0N-vinyl-2-pyrrolidone7,0Methacrylic acid3,00,534800Crystalline Resin 2Docosyl acrylate80,0Styrene10,0N-vinyl-2-pyrrolidone7,0Methacrylic acid3,01,028700Crystalline Resin 3Docosyl acrylate80,0Styrene10,0N-vinyl-2-pyrrolidone7,0Methacrylic acid3,00,339100Crystalline Resin 4Hentriacontyl acrylate86,0Styrene10,0N-vinyl-2-pyrrolidone2,0Methacrylic acid2,00,535400Crystalline Resin 5Docosyl acrylate80,0Styrene17,0N-vinyl-2-pyrrolidone0,0Methacrylic acid3,00,533600Crystalline Resin 6Docosyl acrylate80,0Styrene10,0N-vinyl-2-pyrrolidone7,0Methacrylic acid3,02,019400Crystalline Resin 7Docosyl acrylate80,0Styrene10,0N-vinyl-2-pyrrolidone7,0Methacrylic acid3,00,140900Mw denotes the weight average molecular weight.Preparation of crystalline resin 8A total of 281 parts of decanedioic acid and 283 parts of 1,6-hexanediol were placed in a reaction vessel equipped with a stirrer, a thermometer, a cooling tube and a nitrogen gas inlet tube. After the inside of the reaction vessel was replaced with dry nitrogen gas, 0.1 part of Ti(OBu) 4 was added, and the reaction was carried out under a nitrogen gas stream at about 180°C for 8 hours with stirring. Further, 0.2 part of Ti(OBu) 4 was added, the temperature was raised to about 220°C, and the reaction was carried out for 6 hours with stirring. Thereafter, the pressure in the reaction vessel was reduced to 1333.2 Pa and the reaction was carried out under reduced pressure to obtain crystalline resin 8 of crystalline polyester resins. The number average molecular weight (Mn) of the crystalline resin 8 was 5500; the weight average molecular weight (Mw) was 18000; and the melting point was 67° C.Example 1Production of toner by suspension polymerization methodProduction of Toner Particles 1<row><cell>-< / cell><cell>Styrene< / cell><cell>30,0 Parts< / cell>< / row><row><cell>-< / cell><cell>Colorant: copper phthalocyanine (C.I. PigmentBlue 15:3 manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.)< / cell><cell>6,5 Parts< / cell>< / row><row><cell / >< / row><p xml:id="_6c04ed0432" n="0173">A mixture of the above materials was prepared. The mixture was placed in an attritor (Nippon Cooke Corporation), and dispersed for 2 hours at 200 U / min by means of zirconia beads having a diameter of 5 mm to obtain a raw material dispersion liquid.<p xml:id="_6c04ed0433" n="0174">Meanwhile, 735.0 parts of ion-exchanged water and 16.0 parts of trisodium phosphate (12 hydrate) were placed in a vessel equipped with a high-speed stirrer Homomixer (Primix Corporation) and a thermometer, and the temperature was raised to 60° C. at 12000 U / min with stirring. An aqueous calcium chloride solution prepared by dissolving 9.0 parts of calcium chloride (dihydrate) in 65.0 parts of ion-exchanged water was added, and the mixture was stirred at 12000 U / min for 30 minutes while maintaining the temperature at 60° C. Subsequently, 10% hydrochloric acid was added to adjust the pH to 6.0 to obtain an aqueous medium in which an inorganic dispersion stabilizer containing hydroxyapatite was dispersed in water.<p xml:id="_6c04ed0434" n="0175">The raw material dispersion liquid was then transferred to a vessel equipped with a stirrer and a thermometer, and the temperature was raised to 60° C. under stirring at 100 U / min.<title desc="title" / ><row><cell>-< / cell><cell>Crystalline Resin 1< / cell><cell>70,0 Parts< / cell>< / row><row><cell>-< / cell><cell>Release Agent< / cell><cell>9,0 Parts< / cell>< / row><row><cell>(Release agent: DP18 (Dipentaerythritolhexastearat), melting point 79°C, manufactured by Nippon Seiro Co., Ltd.)< / cell>< / row><row><cell>-< / cell><cell>Fatty acid metal salt (aluminum distearate)< / cell><cell>0,5 Parts< / cell>< / row><p xml:id="_6c04ed0457" n="0176">The above materials were added and stirred at 100 rpm for 30 minutes while maintaining the temperature at 60°C. Thereafter, 9.0 parts of t-butylperoxypivalate (Perbutyl PV, manufactured by NOF Corp.) was added as a polymerization initiator and stirred for another minute. The mixture was then poured into the aqueous medium and stirred in the high speed stirring apparatus at 12000 U / min. Stirring was continued for 20 minutes at 12000 rpm in the apparatus while the temperature was maintained at 60°C to obtain a granulation liquid.<p xml:id="_6c04ed0458" n="0177">The granulation liquid was transferred to a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer and a nitrogen inlet tube, and the temperature was raised to 70° C. under nitrogen atmosphere at 150 U / min with stirring. The polymerization reaction was carried out at 150 U / min and a temperature of 70° C. for 12 hours, and a toner particle dispersion liquid was obtained.<p xml:id="_6c04ed0459" n="0178">The toner particle dispersion liquid thus obtained was cooled to 45°C with stirring at 150 U / min, and then heat-treated at 45°C for 5 hours. Thereafter, diluted hydrochloric acid was added with stirring until the pH reached 1.5 to dissolve the dispersion stabilizer. The solid content was filtered off, washed thoroughly with ion-exchanged water, and then vacuum-dried at 30°C for 24 hours to obtain toner particles 1.<head xml:id="_6c04ed0460">Preparation of Toner 1< / head><p xml:id="_6c04ed0461" n="0179">To 98.0 parts of Toner Particle 1, 2.0 parts of silica fine particles (hydrophobicized with hexamethyldisilazane, number-average particle size of primary particles: 10 nm, BET specific surface area: 170 m <hi rend="superscript">2< / hi> / g) as an external additive was added. This was mixed for 15 minutes at 3000 U / min with a Henschel mixer (manufactured by Nippon Cook Corporation) to obtain Toner 1.<p xml:id="_6c04ed0463" n="0180">The physical properties of the obtained toner 1 are shown in Table 2. Table 3 also shows the results of evaluation by the toner evaluation methods described below. [Table 2]<title desc="title">[Table 2]165,044,021,075,052,023,05×10^65,013,0252,031,021,075,052,023,05×10^65,00,0378,057,021,075,052,023,05×10^65,026,0465,049,016,075,052,023,05×10^65,013,0565,041,024,075,052,023,05×10^65,013,0665,044,021,075,059,016,05×10^65,06,0765,044,021,075,050,025,05×10^65,015,0865,044,021,075,052,023,03×10^55,013,0965,044,021,075,052,023,05×10^75,013,01065,044,021,075,052,023,08×10^75,013,01165,049,016,073,050,023,05×10^65,015,01265,044,021,075,052,023,05×10^60,013,01365,044,021,075,052,023,05×10^61,513,01465,044,021,075,052,023,05×10^68,513,01565,044,021,075,052,023,05×10^612,013,01667,052,015,075,052,023,05×10^65,015,01765,049,016,075,052,023,05×10^65,013,01865,048,017,075,052,023,05×10^65,013,01965,047,018,075,052,023,05×10^65,013,02065,047,018,081,058,023,05×10^65,07,02165,047,018,075,052,023,05×10^65,013,0C. 148,027,021,075,052,023,05×10^65,0-4,0C. 282,061,021,075,052,023,05×10^65,030,0C. 365,052,013,075,052,023,05×10^65,013,0C. 465,038,027,075,052,023,05×10^65,013,0C. 552,034,018,081,058,023,05×10^65,0-6,0C. 665,044,021,075,062,013,05×10^65,03,0C. 765,044,021,075,048,027,05×10^65,017,0C. 865,044,021,075,052,023,08×10^45,013,0C. 965,044,021,075,052,023,05×10^85,013,0In the table, for example, a description such as 5×10^6represents 5×10 6. "C." means "comparison.". [Table 3] [Table 3]1100A. AA. A83A. A0,8A. A295A. AC. C83A. A0,8A. A3115C. CA. A83A. A0,8A. A4100A. AA. A74C. C2,2C. C5100A. AA. A86A. A2,5C. C6100A. AA. A76B. B1,8B. B7100A. AA. A83A. A1,3B. B8100A. AA. A82A. A2,2C. C9110B. BA. A82A. A0,8A. A10120C. CA. A82A. A0,8A. A11100A. AA. A73C. C2,1C. C12100A. AC. C83A. A0,8A. A13100A. AB. B83A. A0,8A. A14105B. BA. A83A. A0,8A. A15110B. BA. A82A. A0,8A. A16110B. BA. A73C. C2,7C. C17100A. AA. A74C. C2,1C. C18100A. AA. A76B. B1,9B. B19100A. AA. A77B. B1,2B. B20100A. AA. A74C. C2,1C. C21100A. AA. A74C. C2,1C. CC. 195A. AD. D82A. A0,8A. AC. 2130D. DA. A83A. A0,8A. AC. 3100A. AA. A67D. D3,4D. DC. 4100A. AA. A82A. A3,6D. DC. 595A. AB. B67D. D3,4D. DC. 6100A. AA. A67D. D3,4D. DC. 7100A. AA. A82A. A3,6D. DC. 895A. AA. A82A. A3,6D. DC. 9135D. DA. A83A. A0,8A. AIn the table, "C." means "comparison.".Toner Evaluation Method<1> Low-temperature fixabilityThe process cartridges filled with the toners 1 to 21 and the comparative toners 1 to 9 were stored at a temperature of 25° C. and an atmospheric humidity of 40% RH for 48 hours. With the LBP-712Ci (Canon Inc.) modified to function even with the fixing unit removed, an unfixed image was output with an image pattern in which nine square images of 10 mm×10 mm were uniformly arranged on the entire transfer paper. The toner application level on the transfer paper was set to 0.80 mg / cm 2 and the fixing start temperature was evaluated. The transfer paper used was A4 paper ("Prover Bond Paper": 105 g / m 2, manufactured by Fox River Co.).The fixing unit of the LBP-712Ci was removed to the outside, and an external fixing unit configured to operate outside the laser beam printer was used. The fixing temperature in the external fixing unit could be raised from 90°C in 5°C steps, and fixing was performed at a process speed of 260 mm / sec.The fixed image was visually checked, the lowest temperature at which no cold offset occurred was defined as the fixing start temperature, and the low-temperature fixability was evaluated according to the following criteria. The evaluation results are shown in Table 3.Evaluation CriteriaA: Fixing start temperature is 100° C. or lessB: Fixing start temperature is from 105°C to 110°CC: Fixing start temperature is from 115° C. to 120° CD: Fixing start temperature exceeds 120°C<2> Evaluation of heat-resistant storage stability / blocking resistanceA total of 10 g of toner was placed in a 100 mL resin beaker and stored for 7 days in an environment having a temperature of 45° C. and a relative humidity of 95%. Then, the degree of occurrence of agglomerates was visually confirmed and the heat-resistant storage stability was evaluated according to the following criteria. Evaluation results are shown in Table 3.Evaluation CriteriaA: Agglomerates are not observed.B: Agglomerates are visible, but they break down easily.C: Agglomerates are visible, but they break down on shaking.D: Agglomerates are graspable and do not easily crumb.<3> Evaluation of color reproducibilityFor evaluation of color reproducibility, the width of the color gamut was evaluated by the Japan Color Inclusion Rate. As the image forming apparatus, LBP-712Ci was used, and the images were formed and evaluated with the ink cartridges provided in the supply scope of the apparatus except for the cyan cartridge. The printing environment was normal temperature and normal humidity (temperature 23° C., relative humidity 50%).For the images of the evaluation of the color scale, the certification and proofing apparatus / operation certification tables used in the Japan Colour Certification System were used. Printing was performed according to "ISO-compliant Japan Color for Sheet-fed Printing 2011: Japan Color 2011 for Sheet-fed Offset based on ISO12647-2 Manual". The pressure conditions are as follows.Pressure ConditionsPrinting paper: OKtop Coat 128 (Oji Paper Co., Ltd.)Print density: Yellow 1.35, Magenta 1.53, Cyan 1.55, Black 1.70 (measurement conditions: after drying, Status E, black support, absolute density (including paper white)). The toner application level was adjusted for each color so as to attain the above printing density.Color Scale Evaluation Methods and Criteria for Image SamplesThe evaluation of the image sample for evaluation was performed with X-Rite eXact (X-Rite Co., Ltd.). Color measurement was performed according to "ISO-compliant Japan Color for Sheet-fed Printing 2011: Japan Color 2011 for Sheet-fed Offset based on ISO12647-2 Manual". The measurement conditions are as follows.Measurement ConditionsSupport: white supportUV blocking filters: noneIncidence / reflection method: 45 / 0Light source for observation: D50Observation conditions: 2 degrees of observation angleLighting standard: MOWith the above-mentioned apparatus, chromaticity (L*, a*, b*) in the L*a*b* color system was measured for each of the colors red, green and blue. Chroma (C*) was calculated from the measured color characteristics according to the following formula.The evaluation was made by calculating, as a percentage ratio, the color scale obtained for each image for color scale evaluation included the color scale of Japan Color.Evaluation criteria for Japan Color Inclusion RateA: 80% or moreB: 75% or more and less than 80%C: 70% or more and less than 75%D: less than 70%<4> Evaluation of Gloss UniformityThe fixed image having color reproducibility in the evaluation of <3> above was used. The gloss value was measured with a handy gloss meter PG-1 (manufactured by Nippon Denshoku Industries Co., Ltd.). As for the measurement conditions, both the projection angle and the reception angle were set to 75°, and all the image patterns in which the plot level was changed were measured. The standard deviation of these measurements was used to evaluate gloss uniformity. The evaluation results are shown in Table 3.Evaluation Criteria of Gloss UniformityA: Standard deviation of gloss is 1.0 or lessB: Standard deviation of gloss is more than 1.0 and 2.0 or lessC: Standard deviation of gloss is more than 2.0 and 3.0 or lessD: Standard deviation of gloss is more than 3,0Examples 2 to 21, Comparative Examples 1 to 9Toner particles 2 to 21 and Comparative Toner particles 1 to 9 were obtained in the same manner as in Example 1 except that the materials used and the amounts added were changed as shown in Table 4. Further, external addition was carried out in the same manner as in Example 1 to obtain Toners 2 to 21 and Comparative Toners 1 to 9. Table 2 shows the physical properties of the toners. Table 3 shows the results of evaluation by the toner evaluation methods described above. From the above analysis, it is understood that in the toners 1 and 2 to 21 and the comparative toners 1 to 9, each monomer unit constituting the crystalline resin was contained in the same content ratio as in the formulation described in Table 1. [Table 4] [Table 4]1170,030,0DP189,0Al distearate0,52270,030,0DP189,0Al distearate0,53370,030,0DP189,0Al distearate0,54173,027,0DP187,0Al distearate0,55167,033,0DP1811,0Al distearate0,56170,030,0DP187,0Al distearate0,57170,030,0DP1811,0Al distearate0,58185,015,0DP189,0Al distearate0,59135,065,0DP189,0Al distearate0,510125,075,0DP189,0Al distearate0,511170,030,0HNP99,0Al distearate0,512170,030,0DP189,0Al distearate0,513170,030,0DP189,0Al distearate0,514170,030,0DP189,0Al distearate0,515170,030,0DP189,0Al distearate0,516870,030,0DP189,0Al distearate0,517470,030,0DP189,0Al distearate0,518170,030,0DP189,0-019170,030,0DP189,0Calcium laurate0,520170,030,0WEP-59,0Al distearate0,521570,030,0DP189,0Al distearate0,5C. 1670,030,0DP189,0Al distearate0,5C. 2770,030,0DP189,0Al distearate0,5C. 3180,020,0DP185,0Al distearate0,5C. 4160,040,0DP1813,0Al distearate0,5C. 5270,030,0WEP-59,0Al distearate0,5C. 6170,030,0DP185,0Al distearate0,5C. 7170,030,0DP1813,0Al distearate0,5C. 8195,05,0DP189,0Al distearate0,5C. 9123,077,0DP189,0Al distearate0,5In the table, "C." means "comparison", and the number of parts indicates the number of mass parts. The release agents are as follows.HNP9 is a paraffin having a melting point of 75°C manufactured by Nippon Seiro Co., Ltd.WEP-5 is a monofunctional ester wax manufactured by NOF Corporation, Nissan Electric WEP-5, having a melting point of 85°C.As is apparent from Table 3, Examples 1 to 21 are superior in low temperature fixability and heat-resistant storage stability to Comparative Examples 1 to 9, and are also superior in color reproducibility and image gloss uniformity.While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. The scope of the following claims is to be construed as broadly as possible to include all such modifications and equivalent structures and functions.References included in the specificationThis list of documents cited by the applicant has been produced in an automated manner and is only included for the better information of the reader. The list is not part of the German patent application or utility model application. The DPMA does not take any adhesion for any faults or omissions.Patent Literature citedJP 2020-173414

[0004] JP 2018-151619

[0005] Cited Non-Patent LiteratureRheometrics Scientific published ARES Handbooks 902-30004 (August 1997 edition) and 902-00153 (July 1993 edition

[0133] ISO12647-2

[0188] ISO-compliant Japan Color for Sheet-fed Printing 2011: Japan Color 2011 for Sheet-fed Offset based on ISO12647-2 Manual

[0189]

Claims

A toner comprising a toner particle containing a binder resin and a releasing agent, wherein the binder resin comprises a crystalline resin and an amorphous resin, wherein when in the differential scanning calorimetry of the toner a temperature is raised from 20°C to 180°C at a temperature rise rate of 10°C / min to obtain a differential scanning calorimetry curve A, then the temperature is maintained at 180°C for 10 min and subsequently the temperature is lowered from 180°C to 10°C at a temperature lowering rate of 10°C / min to obtain a differential scanning calorimetry curve B, the differential scanning calorimetry curve A comprises an endothermic peak m(B) derived from the crystalline resin and an endothermic peak m(W) derived from the releasing agent, According to the present invention, the differential scanning calorimetry curve B includes an exothermic peak c(B) derived from the crystalline resin and an exothermic peak c(W) derived from the releasing agent, and wherein, when a peak temperature (° C.) of the endothermic peak m(B) is referred to as Tm(B), a peak temperature (° C.) of the endothermic peak m(W) is referred to as Tm(W), and a peak temperature (° C.) of the exothermic peak c(B) is referred to as Tc(B), and a peak temperature (° C.) of the exothermic peak c(W) is referred to as Tc(W), the Tm(B) is referred to as Tc(B), the Tm(W) and the Tc(W) satisfy 50.0 ≤ Tm(B) ≤ 80.0, 15,0 ≤ Tm(B)-Tc(B) ≤ 25.0, Tc(W) ≤ Tm(B), and 15,0 ≤ Tm(W)-Tc(W) ≤ 25.0, and a storage elastic modulus G' (TmB) of the toner at Tm(B) [°C] is 1.0×10 5 Pa to 1.0×10 8 Pa.The toner according to claim 1, wherein the releasing agent comprises a polyfunctional ester wax.The toner according to claim 1 or 2, wherein when in the differential scanning calorimetry of the toner after obtaining the differential scanning calorimetry curve B, the temperature is maintained at 10°C for 10 minutes and then the temperature is raised from 10°C to 180°C at a temperature rise rate of 10°C / min to obtain a differential scanning calorimetry curve C, the differential scanning calorimetry curve C has an endothermic peak (B2) derived from the crystalline resin, and wherein when the peak temperature (°C) of the endothermic peak (B2) is denoted as Tm(B2), Tm(B) and Tm(B2) satisfy 1.0 ≤ Tm(B) - Tm(B2) ≤ 10.0.The toner according to any one of claims 1 to 3, wherein a content of the crystalline resin in the binder resin is at least 25.0 mass%.The toner according to any one of claims 1 to 4, wherein the crystalline resin comprises a crystalline vinyl resin.The toner according to claim 5, wherein the crystalline resin includes a monomer unit represented by the following formula (1): in the formula (1), R 1 represents a hydrogen atom or a methyl group, L 1 represents a single bond, an ester bond or an amide bond, and m represents an integer of 15 to 30.The toner according to claim 6, wherein the toner particle has a straight-chain fatty acid metal salt, wherein when the number of carbon atoms of the straight-chain fatty acid in the straight-chain fatty acid metal salt is denoted by C(b), the C(b) and m in formula (1) satisfy m - 10 ≤ C(b) ≤ m + 10, and the valence of the metal in the straight-chain fatty acid metal salt is 2 or more.The toner according to any one of claims 1 to 7, wherein the releasing agent comprises a polyfunctional ester wax, and the polyfunctional ester wax is at least one ester compound selected from the group consisting of an ester compound of a tetrahydro to octahydric alcohol with an aliphatic monocarboxylic acid and an ester compound of a tetravalent to tetravalent carboxylic acid with an aliphatic monohydric alcohol.The toner according to claim 8, wherein the polyfunctional ester wax is at least one ester compound selected from the group consisting of an ester compound of a hexahydric to octahydric alcohol with an aliphatic monocarboxylic acid and an ester compound of a hexahydric to eighthydric carboxylic acid with an aliphatic monohydric alcohol.The toner according to any one of claims 1 to 9, wherein the crystalline resin has a monomer unit having a lactam structure.The toner according to claim 10, wherein the lactam structure is a 5-membered lactam structure.The toner according to any one of claims 1 to 11, wherein the amorphous resin comprises an amorphous vinyl resin.

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