TONER

Abstract

A toner includes toner particles containing a resin component. The toner particles contain, as the resin component, a crystalline vinyl resin having a unit (a) represented by the formula (1). The resin component contains the unit (a) in an amount of 15.0 mass % or more and 40.0 mass % or less based on the mass of the resin component. The content of the unit (a) in a component separated by gradient LC analysis of an acetonitrile / chloroform-eluted component of the chloroform-soluble material W of the toner particles and the storage elastic modulus at 100°C have specific relationships.

Description

BACKGROUNDTechnical FieldThe present disclosure relates to a toner. Description of Related ArtIn the field of electrophotographic apparatuses, energy saving has been considered a great technical challenge, and a significant reduction in the amount of heat associated with a fixing device has been studied. In the toners, there is an increasing demand for so-called "low-temperature fixability" which enables low-energy fixation.As a method for enabling low-temperature fixation, International Publication No. 2013 / 047296 discloses a toner to which a plasticizer has been added. The plasticizer increases the softening rate of a binder resin while maintaining the glass transition temperature (Tg) of the toner, and can improve the low-temperature fixability. However, since the toner is softened by a process in which the binder resin is plasticized after the plasticizer melts, there is a limit to how fast the toner can melt, and therefore, further improvement in low-temperature fixability is desired.Accordingly, methods have been studied in which a crystalline resin is used as a binder resin. Amorphous resins which are usually used as binder resins for toners do not have unique endothermic peaks in differential scanning calorimetry (DSC), but when a toner contains a crystalline resin component, an endothermic peak (melting point) appears in DSC.Crystalline resins in which molecular chains are regularly arranged have the property of hardly softening at temperatures below their melting point. On the other hand, the crystals melt rapidly at temperatures above their melting point, which is accompanied by a rapid drop in viscosity. Crystalline resins having such excellent in-focus property are attracting attention as materials useful for improving the low-temperature fixability of toners.In some toners, a crystalline vinyl resin having long-chain alkyl groups as side chains in its molecule is used as a crystalline resin. In general, a crystalline vinyl resin has a structure in which long-chain alkyl groups as side chains are bonded to the main chain, and the crystallization of the long-chain alkyl groups as side chains causes the crystalline vinyl resin to function as a crystalline resin.Japanese Patent Publication No. 2022-162968, as a toner using a crystalline vinyl resin, discloses a toner using a crystalline vinyl resin obtained by copolymerizing a polymerizable monomer having a long-chain alkyl group and an amorphous polymerizable monomer having a different SP value.However, crystalline vinyl resins have a disadvantage that their viscosity tends to decrease at high temperatures, so that hot offset is likely to occur. To overcome this drawback, Japanese Patent Publication No. 2021-096463 discloses a toner in which a domain-matrix structure including an amorphous resin in addition to a crystalline vinyl resin is formed.However, it has been found that such a toner in which a crystalline vinyl resin and an amorphous resin are used in combination tends to decrease in gloss at the time of fixation. At the time of fixation, the crystalline vinyl resin becomes a molten state and rapidly loses viscosity. In contrast, the amorphous resin is not in a molten state or, when molten, becomes slowly less viscous, so that relatively high and low viscosity regions form within the toner. As a result, hot offset is likely to occur, and minute concavities and concavities are formed on the surface of a fixed image, resulting in decrease in gloss. It has been found that this phenomenon occurs mainly in a low-temperature fixing and high-speed printing system in which the melting states of the resins tend to be different from each other.The present disclosure aims to provide a toner excellent in low-temperature fixability and hot offset resistance.SHORT DISPLAYThe present disclosure provides a toner including toner particles containing a resin component, the resin component containing a crystalline vinyl resin having a unit (a) represented by the formula (1), wherein in the above formula (1), R represents 1 a hydrogen atom or a methyl group, and n represents an integer of 15 to 35, and the resin component contains the unit (a) in an amount of 15.0 mass % or more and 40.0 mass % or less based on a mass of the resin component, when the toner particles are subjected to Soxhlet extraction with chloroform for 18 hours to obtain chloroform-soluble material from which a component having a molecular weight of 2000 or less is removed by recycling HPLC, to obtain chloroform-soluble material W, wherein, for the chloroform-soluble material W, acetonitrile is used as a poor solvent and chloroform is used as a good solvent, while a mobile phase is linearly changed from 100 vol % acetonitrile to 100 vol % chloroform and an eluted component is subjected to gradient LC analysis, a plurality of local maximum values are present in a diagram in which a horizontal axis represents a chloroform percentage (vol %) in the mobile phase and a vertical axis represents a signal intensity (μA) of the eluted component detected with a charged particle detector when a local maximum value is determined from a local maximum value having a highest intensity and a local maximum value having a second highest intensity among the plurality of local maximum values, wherein the chloroform percentage in the mobile phase is smaller, is a local maximum value PA, and a local maximum value at which the chloroform percentage in the mobile phase is larger, is a local maximum value PB, is a local minimum value with a lowest intensity existing between the local maximum value PA and the local maximum value PB, is a local minimum value BAB, a chloroform percentage at the local minimum value BAB VAB is vol % (20.0 < VAB < 95.0), a component whose chloroform percentage in the mobile phase is 20.0 vol % or more and less than VAB vol %, a component A, and a component, whose chloroform percentage in the mobile phase is VABvol% or more and 95.0% by volume or less, a component is B, the resin component contains the component B in an amount of 40.0% by mass or more and 80.0% by mass or less based on the mass of the resin component, when a content of the unit (a) in the chloroform-soluble material is WC mass % and a content of the unit (a) in the component is WB mass %, WC and WB satisfy the formula (2), and when a storage elastic modulus of the toner particles at 100°C is G'(T) and a storage elastic modulus of the component B at 100°C is G'(B), G'(T) and G'(B) satisfy the formulas (3) and (4),Other features of the present disclosure will become apparent from the following description of exemplary embodiments.DESCRIPTION OF THE EMBODIMENTSIn the present disclosure, the terms "XX or more and YY or less" and "XX to YY" representing numerical ranges each include a numerical range including its end points, i.e., the lower limit and the upper limit, unless otherwise specified. When numerical ranges are described in stages, the upper limit of each numerical range may be combined with the lower limit of each other numerical range.The term "(meth)acrylate" refers to an acrylate and / or a methacrylate.The term "monomer unit" refers to a reacted form of a monomeric substance in a polymer. For example, in a polymer, a portion of carbon-carbon bond in a main chain formed by polymerization of a polymerizable monomer is a unit. The polymerizable monomer can be represented by, for example, formula (C) below. In the above formula (C), 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 monovalent group.The term "crystalline resin" refers to a resin that exhibits a unique endothermic peak in differential scanning calorimetry (DSC).The present inventors have found that the above-described drawback can be solved by appropriately controlling the viscoelasticity of a resin component in toner particles containing a crystalline vinyl resin in a large amount and the viscoelasticity of the toner particles (the whole toner particles).A toner according to the present disclosure is a toner including toner particles containing a resin component, the toner particles containing, as the resin component, a crystalline vinyl resin having a unit (a) represented by the following formula (1) wherein, in the above formula (1), R 1 represents a hydrogen atom or a methyl group, and n represents an integer of 15 to 35, and the resin component contains the unit (a) in an amount of 15.0 mass % or more and 40.0 mass % or less based on a mass of the resin component when the toner particles are subjected to Soxhlet extraction with chloroform for 18 hours to obtain a chloroform-soluble material, from which a component having a molecular weight of 2000 or less is removed by recycling HPLC to obtain chloroform-soluble material W, for the chloroform-soluble material W, acetonitrile is used as a poor solvent and chloroform is used as a good solvent, while a mobile phase is linearly changed from 100 vol % acetonitrile to 100 vol % chloroform and an eluted component is subjected to gradient LC analysis, a plurality of local maximum values are present in a diagram in which a horizontal axis represents a chloroform percentage (vol %) in the mobile phase and a vertical axis represents a signal intensity (μA) of the eluted component detected with a charged particle detector, and when, of a local maximum value having a highest intensity and a local maximum value having a second highest intensity among the plurality of local maximum values, a local maximum value at which the chloroform percentage in the mobile phase is smaller is a local maximum value PA, and a local maximum value at which the chloroform percentage in the mobile phase is larger is a local maximum value PB, a local minimum value having a lowest intensity existing between the local maximum value PA and the local maximum value PB is a local minimum value BAB, a chloroform percentage at the local minimum value BAB VAB is vol % (20.0< V<95.0), a component, whose chloroform percentage in the mobile phase is 20.0% by volume or more and less than VAB% by volume, a component A, and a component whose chloroform percentage in the mobile phase is VAB% by volume or more and 95.0% by volume or less is a component B, the resin component contains the component B in an amount of 40.0% by mass or more and 80.0% by mass or less based on the mass of the resin component, when a content of the unit (a) in the chloroform-soluble material W is WC% by mass and a content of the unit (a) in the component B is WB% by mass, WC and WB satisfy the following formula (2), WB / WC ≥ 0.70 (2), and when a storage elastic modulus of the toner particles at 100°C is G'(T) and a storage elastic modulus of the component B at 100°C is G'(B), G'(T) and G'(B) satisfy the following formulae (3) and (4),The toner according to the present disclosure is a toner including toner particles containing a resin component. The toner particles contain, as the resin component, a crystalline vinyl resin having a unit (a) represented by the following formula (1) In the above formula (1), R 1 represents a hydrogen atom or a methyl group, and n is an integer of 15 to 35.The unit (a) represents a unit having a long-chain alkyl group. Due to the presence of the unit (a), the resin component acts as a crystalline vinyl resin. When n in the above formula (1) is 15 to 35, the crystallinity of the crystalline vinyl resin is easy to represent. n is preferably an integer of 17 to 29.The resin component according to the present disclosure contains the unit (a) in an amount of 15.0 mass % or more and 40.0 mass % or less based on the mass of the resin component. When the amount of the unit (a) is in this range, the amount of the crystals in the toner is appropriate, and good low-temperature fixability is provided. When the amount of the unit (a) is less than 15.0 mass %, the amount of the crystals in the toner is small, resulting in low-temperature fixability. When the amount of the unit (a) is more than 40.0 mass %, the amount of crystals in the toner (toner particles) is excessively large, and the melt viscosity of the toner at the time of fixation is excessively low, resulting in low hot offset resistance. A preferable range of the unit (a) in the resin component is 20.0 mass % or more and 35.0 mass % or less.Gradient LC analysis is described. The gradient LC analysis is performed as follows unless otherwise indicated.The toner particles are subjected to soxhlet extraction with a chloroform solvent for 18 hours to obtain soluble material, from which a component having a molecular weight of 2000 or less is removed by recycling HPLC to obtain chloroform soluble material W which is used as a sample. For the chloroform-soluble material extracted from the toner particles, acetonitrile is used as a poor solvent and chloroform is used as a good solvent, the mobile phase being linearly changed from 100 vol% of acetonitrile to 100 vol% of chloroform.The eluted component thereby obtained is subjected to gradient LC analysis.As a result, a graph is obtained in which the horizontal axis represents the chloroform percentage (vol %) in the mobile phase and the vertical axis represents the signal intensity (μA) of the eluted component detected with a charged particle detector. Acetonitrile is a high polarity solvent and high polarity components are eluted first. As the chloroform percentage increases, components of low polarity are gradually eluted. Therefore, in this analysis, separation according to the polarity in the chloroform-soluble material W can be performed. The toner according to the present disclosure has a plurality of local maximum values in this analysis. Of a local maximum value having a highest intensity and a local maximum value having a second highest intensity among the plurality of local maximum values, a local maximum value at which the chloroform percentage in the mobile phase is smaller, that is, a local maximum value at which the polarity is relatively high, is a local maximum value PA. A local maximum value at which the chloroform percentage in the mobile phase is larger, i.e., a local maximum value at which the polarity is relatively low, is a local maximum value PB. A local minimum value with the lowest intensity existing between the local maximum value PA and the local maximum value PB is a local minimum value BAB, and the chloroform percentage at the local minimum value BAB is VAB vol % (20.0<VAB<95.0). A component whose chloroform percentage in the mobile phase is 20.0 vol % or more and less than VAB vol % is a component A, and a component whose chloroform percentage in the mobile phase is VAB vol % or more and 95.0 vol % or less is a component B.The resin component according to the present disclosure contains the component B in an amount of 40.0 mass % or more and 80.0 mass % or less based on the mass of the resin component. When a content of the unit (a) in the chloroform-soluble material W is WC mass % and a content of the unit (a) in the component B is WB mass %, WC and WB satisfy Formula (2) below.The unit (a) has a relatively low polarity because it has a long-chain alkyl group. Thus, satisfying the above formula (2) means that the component A and the component B are clearly separated from each other, and most of the unit (a) having crystallinity, i.e., the crystalline vinyl resin, is present in the component B.When component B is contained in an amount of 40.0 mass % or more and 80.0 mass % or less based on the mass of the resin components, it means that a component having crystallinity is present in an appropriate amount, thereby providing good low-temperature fixability. When the amount of the component B is less than 40.0 mass %, the amount of the component having crystallinity is too small, resulting in poor low-temperature fixability. When the amount of the component B is more than 80.0 mass %, the amount of the component having crystallinity is too large, resulting in low hot offset resistance. A preferable range of the component B in the resin component is 50.0% by mass or more and 75.0% by mass or less, more preferably 55.0% by mass or more and 70.0% by mass or less. The content of the component B in the resin component can be controlled by the content of the crystalline vinyl resin in the resin component, the content of the unit (a) in the crystalline vinyl resin, etc.In the toner according to the present disclosure, when the storage elastic modulus of the toner particles at 100° C. is G'(T), G'(T) satisfies Formula (3) below.The storage elastic modulus at 100°C indicates the viscosity of the toner particles after melting, and when G'(T) is in the above range, penetration of the toner particles into the paper and separation from a fixing film can be effectively achieved, and good low-temperature fixability is provided. When G'(T) is less than 5.0×10 3 Pa, the viscosity of the toner particles after melting is too low, so that migration of the toner to a fixing member (e.g., a fixing film) at the time of fixing is likely to result in low hot offset resistance. When G'(T) is more than 1.0×10 5 Pa, the viscosity of the toner particles after melting is too high, so that penetration of the toner particles into the paper at the time of fixation is less likely, resulting in poor low-temperature fixability. A preferable range for G'(T) is 8.0×10 3 Pa or more and 8.0×10 4 Pa or less, more preferably 9.0×10 3 Pa or more and 5.0×10 4 Pa or less. G'(T) can be controlled by the content of the unit (a) in the resin component in the toner particles, the molecular weight of the resin component, the content of the component B, etc.In the toner particles according to the present disclosure, when the storage elastic modulus of the component B at 100° C. is G'(B), the following formula (4) is satisfied.As described above, most of the unit (a) having crystallinity is present in the resin component in the component B. Therefore, the storage elastic modulus of the component B at 100° C. is relatively low compared to that of the toner particles. On the other hand, when components whose storage elastic moduli at 100° C. are greatly deviated from each other are present in the toner particles, regions having relatively high viscosity and low viscosity are formed within the toner particles at the time of fixation, so that minute concavities and convexities are formed on the surface of a fixed image, resulting in decrease in gloss. This phenomenon occurs especially in a low-temperature fixing and high-speed printing system in which the melting states of the resins tend to be different from each other.When the above formula (4) is satisfied, the relative difference of the storage elastic modulus is in an appropriate range, so that high gloss can be obtained even in low-temperature fixing at high speed.When G'(T)-G'(B) is less than 2.0×10 3 Pa, penetration into the paper at the time of fixation is less likely, resulting in a fixed image having low abrasion resistance. When G'(T)-G'(B) is more than 6.0×10 3 Pa, the gloss at the time of low-temperature fixing at high speed is low.G'(T)-G'(B) can be controlled by the content of the crystalline vinyl resin constituting most of the component B, the ratio of the unit (a) in the crystalline vinyl resin, the molecular weight of the crystalline vinyl resin, and so on.Component B according to the present disclosure will be described.In the component B, most of the crystalline vinyl resin is contained as described above.The component B may contain the unit (a) in an amount of 25.0 mass % or more and 50.0 mass % or less based on the mass of the component B. Within this range, the content of the unit (a) in the toner particles tends to be in an appropriate range, and the low-temperature fixability and the hot offset resistance tend to be well balanced. The amount of the unit (a) is preferably 30.0% by mass or more and 45.0% by mass or less.In the component B, the weight average molecular weight (Mw) of the tetrahydrofuran (THF)-soluble material determined by gel permeation chromatography (GPC) is preferably 30000 or more and 200000 or less. When the Mw is in this range, G'(T)-G'(B) tends to be in an appropriate range. A preferable range for the Mw is 40000 or more and 180000 or less, more preferably 60000 or more and 150000 or less.The crystalline vinyl resin according to the present disclosure will be described.The crystalline vinyl resin is a component contained mostly in the above-described component B.The crystalline vinyl resin contains the unit (a), and an example of a method for introducing the unit (a) is polymerization of a (meth)acrylate as listed below. Examples include stearyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, henicosanyl (meth)acrylate, behenyl (meth)acrylate, lignoceryl (meth)acrylate, ceryl (meth)acrylate, octacosyl (meth)acrylate, myrcyl (meth)acrylate, dotriacontyl (meth)acrylate and 2-decyltetradecyl (meth)acrylate.The unit (a) contained in the crystalline vinyl resin may be a single kind or two or more kinds.The content percentage of the unit (a) in the crystalline vinyl resin is preferably 40.0% by mass or more and 90.0% by mass or less, more preferably 45.0% by mass or more and 85.0% by mass or less, even more preferably 50.0% by mass or more and 80.0% by mass or less. Within this range, a better balance is provided between low temperature fixability and hot offset resistance.The crystalline vinyl resin may contain another unit in addition to the unit (a). An example of a method for introducing another unit into the crystalline vinyl resin is polymerization of any of the above (meth)acrylates and another vinyl monomer.Examples of the other vinyl monomers include the following:styrene, α-methylstyrene and (meth)acrylates 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, such as monomers obtained by reacting amines having 3 to 22 carbon atoms [e.g., primary amines (e.g., n-butylamine, t-butylamine, propylamine and isopropylamine), secondary amines (e.g., di-n-ethylamine, di-n-propylamine and di-n-butylamine), aniline and cyclohexylamine] with isocyanates having an ethylenically unsaturated bond and 2 to 30 carbon atoms according to known methods;monomers having a carboxy group such as methacrylic acid, acrylic acid and 2-carboxyethyl (meth)acrylate;monomers having a hydroxy group, such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;monomers having an amide group such as acrylamide and monomers obtained by reacting amines having 1 to 30 carbon atoms with carboxylic acids having an ethylenically unsaturated bond and 2 to 30 carbon atoms (e.g., acrylic acid and methacrylic acid) according to known methods; andMonomers having a lactam structure such as N-vinyl-2-pyrolidone.Of these, monomers having a lactam structure are preferred, monomers having a five-membered lactam structure are preferred, and N-vinyl-2-pyrolidone is more preferred. The presence of a moiety having a lactam structure helps to improve the affinity between the crystalline vinyl resin and the paper to provide a fixed image having improved abrasion resistance.The content percentage of the unit having a lactam structure in the crystalline vinyl resin is preferably 2.0 mass % or more and 15.0 mass % or less.The crystalline vinyl resin can also be obtained by copolymerizing a (meth)acrylate for introducing the unit (a) with another vinyl monomer to synthesize a crystalline vinyl resin and then further adding another vinyl monomer by a hydrogen abstracting reaction. The hydrogen abstracting reaction is a reaction in which a hydrogen atom bonded to a carbon atom is abstracted to generate a radical, and another vinyl monomer may be further reacted from the generated radical. This enables the formation of a state in which the unit (a) in the crystalline vinyl resin is more gathered in one molecule, and contributes to the increase of crystallinity. It also helps satisfy the above formula (4).In the crystalline vinyl resin, the weight average molecular weight (Mw) of the tetrahydrofuran (THF)-soluble material determined by gel permeation chromatography (GPC) is preferably 30000 or more and 200000 or less. When the Mw is in this range, G'(T)-G'(B) tends to be in an appropriate range. A preferable range for the Mw is 40000 or more and 180000 or less, more preferably 60000 or more and 150000 or less.The content of the crystalline vinyl resin in the toner particles according to the present disclosure is preferably 30.0 mass % or more and 80.0 mass % or less based on the mass of the toner particles. Within this range, the component having crystallinity of the toner particles tends to be present in an appropriate amount, and low-temperature fixability and hot offset resistance tend to be simultaneously achieved. The content of the crystalline vinyl resin is more preferably 40.0 mass % or more and 75.0 mass % or less, even more preferably 50.0 mass % or more and 70.0 mass % or less.In the toner particles according to the present disclosure, the melting point derived from the crystalline vinyl resin in differential scanning calorimetry (DSC) is preferably 50° C. or higher and 80° C. or lower. When the melting point derived from the crystalline vinyl resin is in this range, the low-temperature fixability tends to be improved. A preferable range of the melting point is 55° C. or higher and 75° C. or lower, and a more preferable range is 57° C. or higher and 70° C. or lower.Component A according to the present disclosure will be described.The component A is a component more polar than the component B, and most of the crystalline vinyl resin is contained in the component B; therefore, most of the other resin components are contained in the component A. Examples of other resin components include an amorphous resin.The resin component may contain the component A in an amount of 10.0 mass % or more and 60.0 mass % or less based on the mass of the resin component. Within this range, the component having crystallinity of the toner particles tends to be present in an appropriate amount, and low-temperature fixability and hot offset resistance tend to be simultaneously achieved. The amount of component A is more preferably 15.0 mass % or more and 55.0 mass % or less, even more preferably 20.0 mass % or more and 50.0 mass % or less.In the component A, the weight average molecular weight (Mw) of the tetrahydrofuran (THF)-soluble material determined by gel permeation chromatography (GPC) is preferably 20000 or more and 200000 or less, more preferably 25000 or more and 150000 or less.The amorphous resin is, for example, a vinyl resin, a polyester resin, a polyurethane resin or an epoxy resin, and may be a vinyl resin or a polyester resin.When the amorphous resin is a vinyl resin, the vinyl monomer usable for the crystalline vinyl resin may be used. The (meth)acrylate for introducing the unit (a) may also be used as long as the amorphous resin does not have crystallinity.A so-called crosslinking agent having a plurality of vinyl groups per monomer may also be used. Examples of crosslinking agents include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 2,2'-bis(4-(acryloxydiethoxy)phenyl)propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis(4-(methacryloxydiethoxy)phenyl)propane, 2,2'-bis(4-(methacryloxypolyethoxy)phenyl)propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, divinyl ether, and 4,4'-divinylbiphenyl.When the amorphous resin is a polyester resin, a polyester resin obtainable by a reaction between a polycarboxylic acid having a valence of 2 or more and a polyhydric alcohol may be used.Examples of the polycarboxylic acids include the following: dibasic acids such as succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, malonic acid and dodecenylsuccinic acid, and anhydrides and lower alkyl esters thereof; aliphatic unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid and citraconic acid; and 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 polyhydric alcohols include the following: 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 adducts of alicyclic diols with alkylene oxides (ethylene oxide and propylene oxide). The alkyl moieties of the alkylene glycols and alkylene ether glycols may be linear or branched. Further examples include glycerol, trimethylolethane, trimethylolpropane and pentaerythritol. These may be used alone or in combination of two or more.For adjusting the acid value or the hydroxyl value, a monovalent acid such as acetic acid or benzoic acid or a monovalent alcohol such as cyclohexanol or benzyl alcohol may also be used as required.As a method for producing the polyester resin, for example, a transesterification method and a direct polycondensation method may be used alone or in combination.The resin component according to the present disclosure contains chloroform-insoluble matter, and the content of the chloroform-insoluble matter is preferably 3.0 mass % or more and 15.0 mass % or less based on the mass of the resin component. Within this range, the toner is provided with effective elasticity, and low-temperature fixability and hot offset resistance tend to be simultaneously achieved.The toner particles according to the present disclosure may have a core-shell structure including a core particle containing the resin and a shell covering the core particle. The resin constituting the shell is preferably a vinyl resin or a polyester resin, more preferably an amorphous polyester resin from the viewpoint of charge stability. The shell need not necessarily cover the entire core, and the core may be partially exposed. As the vinyl resin and the polyester resin constituting the shell, the vinyl resin and the polyester resin which can be used for the above-described component A and component B can be used.The toner particles may contain a wax. The wax is at least one selected from the group consisting of a hydrocarbon wax and an ester wax. The use of a hydrocarbon wax and / or an ester wax helps to provide effective releasability.Examples of hydrocarbon waxes include the following: aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight olefin copolymers, Fischer-Tropsch wax, and waxes obtained by oxidation or acid addition of these waxes.The ester wax is not limited as long as it has at least one ester bond in a molecule, and may be a natural ester wax or a synthetic ester wax.Examples of ester waxes include the following:esters of a monohydric alcohol and a monocarboxylic acid such as behenyl behenate, stearyl stearate and palmityl palmitate;ester of a dicarboxylic acid and a mono-alcohol such as dibehenyl sebacate;ester of a dihydric alcohol and a monocarboxylic acid such as ethylene glycol distearate and hexanediol dibehenate;esters of a trivalent alcohol and a monocarboxylic acid such as glyceryl tribehenate;esters of a tetravalent alcohol and a monocarboxylic acid such as pentaerythritol tetrastearate and pentaerythritol tetrapalmitate;esters of a hexahydric alcohol and a monocarboxylic acid such as Dipentaerythritolhexastearat dipentaerythritol hexapalmitate and Dipentaerythritolhexabehenat;esters of a polyfunctional alcohol and a monocarboxylic acid such as polyglyceryl behenate; andNatural ester waxes such as carnauba wax and rice wax.Of these, an ester wax which is an ester of an alcohol having a valence of 4 or more and 8 or less and an aliphatic monocarboxylic acid, or an ester wax which is an ester of a carboxylic acid having a valence of 4 or more and 8 or less and an aliphatic mono-alcohol is preferred. The presence of such a wax lowers the compatibility with the crystalline vinyl resin at the time of fixing, so that releasability at the time of low temperature fixing tends to be improved, resulting in higher low temperature fixability.Esters of a tetravalent alcohol and a monocarboxylic acid such as pentaerythritol tetrastearate, pentaerythritol tetrapalmitate, and pentaerythritol tetrabehenate; esters of a hexavalent alcohol and a monocarboxylic acid such as Dipentaerythritolhexastearat dipentaerythritol hexapalmitate, and Dipentaerythritolhexabehenat; and esters of an tetravalent alcohol and a monocarboxylic acid such as Tripentaerythritoloctastearat tripentaerythritol octapalmitate, and Tripentaerythritoloctabehenat are more preferred.The content of the wax in the toner particles is preferably 1.0 mass % or more and 30.0 mass % or less, more preferably 2.0 mass % or more and 25.0 mass % or less. When the content of the wax in the toner particles is in this range, releasability is more easily provided at the time of fixation.The melting point of the wax is preferably 60° C. or higher and 120° C. or lower. When the melting point of the wax is in this range, the wax easily melts at the time of fixation to bleed out from the surface of the toner particles, so that the wax easily evaporates. More preferably, the melting point of the wax is 70°C or higher and 100°C or lower.The toner particles may contain a colorant. Examples of the colorant include known organic pigments, organic dyes, inorganic pigments, carbon black as a black colorant, and magnetic particles. Moreover, conventional colorants may also be used in toners.Examples of yellow colorants include the following: condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Of these, C.I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 155, 168 and 180 are suitable for use.Examples of magenta colorants include the following: condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Of these, 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 are suitable for use.Examples of cyan colorants include the following: copper phthalocyanine compounds and their derivatives, anthraquinone compounds, and basic dye lake compounds. Of these, C.I. Pigment Blue 1, 7, 15, 15:1, 15:2, 15:3, 15:4, 60, 62, and 66 are suitable for use.The selection of the colorant is made in view of hue angle, color saturation, lightness, light fastness, OHP transparency and dispersibility in the toner.The content of the colorant in the toner particles is preferably 1.0 mass parts or more and 20.0 mass parts or less based on 100.0 mass parts of the toner particles. When magnetic particles are used as the coloring agent, their content is preferably 40.0 parts by mass or more and 150.0 parts by mass or less based on 100.0 parts by mass of the toner particles.The toner particles may contain a charge control agent. Alternatively, a charge control agent may be externally added to the toner particles. The use of a charge control agent stabilizes the charging properties and enables control of an optimum triboelectric charge amount according to the development system.The charge control agent may be a charge control agent that has a high charging speed and can stably maintain a constant charge amount.Examples of charge control agents that cause a negative charge of the toner include the following. Metal organic compounds and chelate compounds are effective, and examples include monoazo metal compounds, acetyl acetone metal compounds and aromatic oxycarboxylic acid-based, aromatic dicarboxylic acid-based, oxycarboxylic acid-based and dicarboxylic acid-based metal compounds.Examples of charge control agents which positively charge 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 in the toner particles is preferably 0.01 parts by mass or more and 20.0 parts by mass or less, more preferably 0.5 parts by mass or more and 10.0 parts by mass or less, based on 100.0 parts by mass of the toner particles.The toner particles can be used as the toner without any treatment or with an external additive or the like added and fixed to the surface of the toner particles as needed.Examples of the external additive include inorganic fine particles selected from the group consisting of silica fine particles, alumina fine particles and titanium oxide fine particles, and composite particles thereof. Examples of the composite particles include silica-aluminum fine particles and strontium titanate fine particles.The content of the external additive is preferably 0.01 parts by mass or more and 8.0 parts by mass or less, more preferably 0.1 parts by mass or more and 4.0 parts by mass or less, based on 100 parts by mass of the toner particles.The toner particles according to the present disclosure may be produced by a method such as a suspension polymerization method, an emulsion aggregation method, a solution suspension method, or a pulverization method, and may be produced by the suspension polymerization method.The suspension polymerization process will be described in detail.For example, a previously synthesized crystalline vinyl resin is added to a mixture of polymerizable monomers. Other materials such as a colorant, a wax and a charge control agent are added as needed and uniformly dissolved or dispersed to prepare a polymerizable monomer composition.Thereafter, the polymerizable monomer composition is dispersed in an aqueous medium using a stirrer or the like to prepare suspended particles of the polymerizable monomer composition. Thereafter, the polymerizable monomer contained in the particles is polymerized using an initiator or the like to obtain toner particles. By using a hydrogen abstracting reaction at the time of this polymerization reaction, the polymerizable monomers are reacted in certain amounts with the crystalline vinyl resin polymerized in advance, so that the crystalline vinyl resin can be easily controlled to have the desired physical properties.After completion of the polymerization, the toner particles are filtered, washed and dried, and an external additive is added as needed, whereby a toner can be obtained.Examples of polymerization initiators 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-butylperoxyoctoate, t-butylperoxyneodecanoate, methyl ethyl ketone peroxide, diisopropylperoxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide and lauroyl peroxide. Polymerization initiators which readily cause a hydrogen abstracting reaction are peroxide polymerization initiators suitable for use. Of these initiators, initiators such as t-butylperoxy-2-ethylhexanoate, t-butylperoxypivalate, t-butylperoxyisobutyrate, t-butylperoxyoctoate and t-butylperoxyneodecanoate are more suitable for use.The temperature during the polymerization reaction may be 15°C to 25°C higher than the 10-hour half-life temperature of an initiator. Within this range, the hydrogen abstracting reaction proceeds rather moderately, so that the crystalline vinyl resin can be easily adjusted to the desired physical properties.A chain transfer agent and / or a polymerization inhibitor may also be used.The aqueous medium may contain an inorganic and / or organic dispersion stabilizer.Examples of inorganic dispersion stabilizers include phosphates such as hydroxyapatite, three basic 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, carboxy methyl cellulose sodium salt, polyacrylic acid and its salts, and starch.When an inorganic compound is used as the dispersion stabilizer, a commercially available product can be directly used, or in order to obtain finer particles, the inorganic compound can be prepared and used in the aqueous medium.In the case of calcium phosphate such as hydroxyapatite or tribasic calcium phosphate, for example, an aqueous phosphate solution and an aqueous calcium salt solution can be mixed with vigorous stirring.The aqueous medium may contain a surfactant. 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 of a toner and toner materials will be described below.Separation of toner particles from tonerToner particles and an external additive are separated from each other in the following manner, and the obtained toner particles can be used for analyses.To prepare an aqueous sucrose solution, 160 g of sucrose (manufactured by Kishida Chemical Co., Ltd.) is added to 100 mL of deionized water and dissolved in a hot water bath. The sucrose aqueous solution in an amount of 31 g and 6 mL of contaminon N (a 10 mass % aqueous solution of a neutral detergent for cleaning precision measurement instruments, the solution being composed of a nonionic surfactant, an anionic surfactant and an organic builder and having a pH of 7, manufactured by FUJIFILM Wako Pure Chemical Corporation) is placed in a centrifuge tube to prepare a dispersion liquid. To this dispersion liquid, 1 g of a toner is added, and lumps of the toner are broken with a spatula or the like.The centrifuge tube is placed in a "KM Shaker" (model: V.SX) manufactured by Iwaki Industry Co., Ltd. and shaken for 20 minutes at 350 reciprocations per minute. After shaking, the solution is transferred to a glass tube (50 ml) for a swing rotor and centrifuged for 30 minutes at 3500 U / min by a centrifugation machine.In the glass tube subjected to centrifugation, toner particles are located in the uppermost layer, and external additives such as silica fine particles are located on the lower layer of the aqueous solution. The toner particles in the upper layer are collected, filtered, and washed with 2 L of running deionized water heated to 40° C., and the washed toner particles are taken out. Separation of Component A, Component B and chloroform-insoluble matter in resin from toner particles and measurement of percentage contentThe toner particles in an amount of 1.5 g are accurately weighed (W1 [g]) and placed in a previously accurately weighed extraction sleeve (trade name: No. 86R, size 28×100 mm, manufactured by Advantagec Toyo Kaisha, Ltd.), and the extraction sleeve is placed in a Soxhlet extractor. Using 200 mL chloroform as the solvent, extraction is carried out at a reflux rate for 18 hours so that one solvent extraction cycle is completed in about 5 minutes.After completion of the extraction, the extraction sleeve is removed and dried in air and then dried under vacuum at 40° C. for 8 hours. The mass of the extraction sleeve including the extraction residue is weighed and the mass of the extraction sleeve is subtracted so as to calculate the mass (W3 [g]) of the extraction residue (chloroform-insoluble material). When the chloroform-soluble material (W2 [g]) is recovered, it can be recovered by sufficiently distilling chloroform from the chloroform-soluble material with an evaporator.Then, the content (W4 [g]) of a resin component in the chloroform-insoluble material is determined by the following method.In a 30-mL magnetic crucible weighed beforehand, 2 g of the chloroform-insoluble matter of the toner particles is accurately weighed (Wa' [g]).The magnetic crucible is placed in an electric furnace, heated at about 900° C. for 3 hours, and then cooled in the electric furnace. At normal temperature, the magnetic crucible is allowed to cool in a desiccator for at least 1 hour. The mass of the crucible containing combustion residue pocket is weighed and the mass of the crucible is subtracted so as to calculate the mass (Wb' [g]) of the combustion residue pocket.The mass (W5[g]) of the combustion residue in the sample W1[g] is calculated according to the following formula.Subsequently, the mass (W4[g]) of a resin component C which is a resin component without the combustion residue in the chloroform-insoluble material of the toner particles is calculated according to the following formula.When the toner particles contain a wax, it is necessary to separate the resin and the wax from each other.The separation of the resin and the wax is carried out by recycling HPLC, wherein a component having a molecular weight of 2000 or less is regarded as a wax. The measurement method will be described below. First, the chloroform-soluble material is separated and dissolved in chloroform by the above-described method. The resulting solution is then filtered through a solvent-resistant membrane filter "CornHori 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, measurement is performed 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 calculating the molecular weight of the sample, a molecular weight calibration curve prepared using a standard polystyrene resin (for example, trade name "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, or A-500" manufactured by Tosoh Corporation) is used.Based on the molecular weight curve thus obtained, the component having a molecular weight of 2000 or less is repeatedly recovered to separate a resin component (W) and a wax component (Wd) in the chloroform-soluble material of the toner. The content (W6[g]) of the resin component in the chloroform-soluble material (W2) in the toner particles W1[g] is then calculated according to the following formula.In the separation of a component A and a component B from the toner particles, the above-described resin component (W) in the chloroform-soluble material of the toner particles is used as a sample. The sample is adjusted with chloroform to have a sample concentration of 1.0% by mass. This solution is filtered through a 0.45 μm PTFE filter and the filter residue is subjected to measurement. The conditions for gradient polymer LC measurement are listed below.Apparatus: UlTIATE 3000 (manufactured by Thermo Fisher Scientific)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 is controlled to be linear)Flow rate: 1.0 mL / minInjection: 1.0 mass %×20 μLColumn: Tosoh TSKgel ODS (4.6 mm diameter×150 mm length×25 μm)Column temperature: 40°CDetector: Corona charged particle detector (Corona CAD) (manufactured by Thermo Fisher Scientific)For a time-signal intensity graph (μA) obtained by the measurement, the time is converted into chloroform percentage (vol %). Then, from the observed local maximum values, a local maximum value with the highest signal intensity and a local maximum value with a second highest signal intensity are selected. Of these two local maximum values, a local maximum value at which the chloroform percentage in the mobile phase is smaller is determined as PA, and a local maximum value at which the chloroform percentage in the mobile phase is larger is determined as PB. In addition, a local minimum value with the lowest intensity between PA and PB is determined as BAB and a chloroform percentage at BAB is determined as VAB (vol %).Thereafter, the above measurement is repeated 50 times. A region where the content of the mobile phase is 20.0 vol % or more and less than VAB vol % is recovered as the acetonitrile / chloroform solution of the component A, and a region where the content of the mobile phase is VAB vol % or more and 95.0% or less is recovered as the acetonitrile / chloroform solution of the component B. Acetonitrile / chloroform is sufficiently distilled off with an evaporator so as to collect the component A (We [g]) and the component B (Wf [g]).The content (W7 [g]) of the component A and the content (W8 [g]) of the component B in the chloroform-soluble material (W2) of the toner particles W1 [g] are calculated according to the following formulae.The percent content (W 9 [mass %]) of the component A, the percent content (W 10 [mass %]) of the component B, and the percent content (W 11 [mass %]) of the chloroform-insoluble material of the resin component based on the mass of the resin component in the present disclosure are calculated according to the following formulas. Method for Measuring Percentages of Unit (a) in Resin Component, Chloroform-Soluble Material W and Component BThe measurement of the percentages of the unit (a) in the resin component, the chloroform-soluble material W and the component B is carried out by 1 H-NMR under the following conditions.Measuring apparatus: FT-NMR apparatus JNM-EX400 (manufactured by JEOL Ltd.)Measurement frequency: 400 MHzPulse condition: 5.0 μsFrequency range: 10500 HzNumber of scans: 64Measurement temperature: 30° CSample: prepared in the following mannerA measurement sample in an amount of 50 mg is placed in a sample tube having an inner diameter of 5 mm, deuterochloroform (CDCl 3) is added as a solvent, and the resulting mixture is dissolved in a constant temperature bath at 40° C. to prepare a sample.The obtained 1 H-NMR chart is analyzed to identify the structures of the units. As an example, the measurement of the percentage content of the unit (a) in the component B will be described here. From the peaks assigned to the constituent elements of the unit (a) in the obtained 1 H-NMR chart, a peak independent from the peaks assigned to the constituent elements of other units is selected, and an integral value S1 of this peak is calculated. For each of the other units contained in the resin, the integral value is calculated in the same manner.When the component B is composed of the unit (a) and another unit, the content percentage of the unit (a) is determined in the following manner by using the integral value S1 and an integral value S2 of the peak of the other unit. n1 and n2 each represent the number of hydrogen atoms in a component to which the peak of interest is assigned to each unit.Even if two or more other units are present, the percentage of the unit (a) can be calculated in the same manner (using S3... Sx and n3... nx).When a monomer containing no hydrogen atoms is used as a component other than vinyl groups, measurement is performed in a single pulse mode using 13 C-NMR, wherein the nucleus to be measured is 13 C, and the content percentage can be calculated in the same manner by 1 H-NMR. The percentage (mol %) of each unit calculated by the above method is multiplied by the molecular weight of each unit to convert the percentage content of each unit into a mass %. Measurement of storage elastic modulus of toner particles and component B at 100° CThe storage elastic moduli are measured with an MCR302 (manufactured by Anton Paar GmbH). The method for measuring the storage elastic modulus of the toner particles at 100° C. will be described below.The toner particles in an amount of 120 mg are weighed and molded by a tablet machine at 20 kN for 1 minute to obtain a disk-shaped sample having a diameter of 8 mm.The sample thus obtained is placed in a measuring apparatus under the following conditions. Name of Measuring Tool: Measuring Plate PP08 / SD: 8 mm, Sandblast Setting Conditions: 80° C., 0.1 NSubsequently, viscoelasticity was measured under the following conditions.Frequency: 1 HzNormal force: 100 mNApplied elongation: changed from 0.5% to 7.0% at 0.22% / minWhile the temperature is raised from 70°C to 130°C at 2°C / min, the measurement is carried out for 30 minutes. The sampling rate is 1 point / 0.5 minutes during this time.In the measurement, the calculated storage elastic modulus (Pa) at 100° C. is determined as the storage elastic modulus G'(T) of the toner particles at 100° C. Also, the storage elastic modulus at 100° C. obtained when the component B is used as a sample is determined as the storage elastic modulus G'(B). Method for Determining Molecular Weight (Weight Average Molecular Weight Mw) of Component BThe molecular weight (weight average molecular weight Mw) of the THF-soluble material of the component B is determined by gel permeation chromatography (GPC) in the following manner.First, component B is dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. The resulting solution is filtered through a solvent-resistant membrane filter "CornHori 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 THF-soluble components is 0.8 mass %. With this sample solution, measurement is performed under the following conditions.Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)Column: Shodex KF-801, 802, 803, 804, 805, 806 and 807, seven connected columns (manufactured by Resonac Holdings Corporation)- Eluent: tetrahydrofuran (THF)Flow rate: 1.0 mL / min- Oven temperature: 40.0°C- Sample injection volume: 0.10 mLIn the calculation of the molecular weight (weight average molecular weight Mw) of the sample, a molecular weight calibration curve prepared using a standard polystyrene resin (e.g., trade name "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, or A-500" manufactured by Tosoh Corporation) is used.EXAMPLESA more detailed description is given below with reference to examples. In the following formulations, "parts" means "% by mass" unless otherwise specified.Preparation of Resin A1The following materials were placed in an autoclave equipped with a decompressing device, a water separating device, a nitrogen gas introducing device, a temperature measuring device and a stirring device. <row><cell>terephthalic acid< / cell><cell>25,3 Parts< / cell>< / row><row><cell>propylene oxide 2 mol %) adduct of bisphenol A< / cell><cell>74,7 Parts< / cell>< / row><row><cell>potassium titanium oxalate (catalyst)< / cell><cell>0,02 Parts< / cell>< / row><p xml:id="_a187b30242" n="0143">Then, the materials were allowed to react in a nitrogen atmosphere under normal pressure at 220°C for 5 hours and under reduced pressure at 220°C for 3 hours. After the temperature was lowered, the resultant was pulverized to obtain a resin A1. The resin A1 had a weight average molecular weight (Mw) of 10280.<head xml:id="_a187b30243">Preparation of Resin A2< / head><p xml:id="_a187b30244" n="0144">An autoclave was charged with 50.0 parts of xylene and purged with nitrogen, then the temperature was raised to 185°C with stirring in a hermetically sealed state. Into the autoclave, 79.0 parts of styrene, 17.0 parts of n-butyl acrylate, 3.1 parts of divinylbenzene, 0.9 part of acrylic acid and a mixed solution of 1.0 part of di-tert-butyl peroxide and 20.0 parts of xylene were continuously added dropwise for 3 hours to obtain a polymerization effect while the temperature in the autoclave was controlled to 185°C. Then, the temperature was maintained for 1 hour to complete the polymerization, and the solvent was removed to obtain a resin A2. The resin A2 had a weight average molecular weight (Mw) of 60000.<head xml:id="_a187b30245">Preparation of Resin B1< / head><p xml:id="_a187b30246" n="0145">A reaction vessel equipped with a reflux condenser, a stirrer, a thermometer and a nitrogen inlet tube was charged with the following materials under nitrogen atmosphere.<title desc="title" / ><row><cell>toluene< / cell><cell>100,0 Parts< / cell>< / row><row><cell>- monomer composition< / cell><cell>100,0 Parts< / cell>< / row><p xml:id="_a187b30260" n="0146">(The monomer composition is a mixture of the following monomers in the following proportion)<title desc="title" / ><row><cell>behenyl acrylate< / cell><cell>60,0 Parts< / cell>< / row><row><cell>styrene< / cell><cell>20,0 Parts< / cell>< / row><row><cell>methacrylonitrile< / cell><cell>10,0 Parts< / cell>< / row><row><cell>N-vinyl-2-pyrolidone< / cell><cell>10,0 Parts< / cell>< / row><row><cell>polymerization initiator t-butylperoxypivalate (perbutyl PV, manufactured by< / cell>< / row><row><cell>NOF Corporation),< / cell><cell>0,5 Parts by mass< / cell>< / row><p xml:id="_a187b30285" n="0147">While the above materials were stirred in a reaction vessel at 200 U / min, a polymerization reaction was carried out at an elevated temperature of 70°C for 12 hours to obtain a solution in which a polymer in the monomer composition was dissolved in toluene. Then, the solution was cooled to 25 °C and then added into 1000.0 parts of methanol with stirring to precipitate methanol-insoluble matter. The obtained methanol-insoluble matter was separated by filtration, further washed with methanol, and then dried at 40°C in vacuofor 24 hours to obtain a resin B1. Physical properties of resin B1 are shown in Table 1.<head xml:id="_a187b30286">Preparation of Resins B2 to B6< / head><p xml:id="_a187b30287" n="0148">Crystalline resins B2 to B6 were prepared in the same manner as resin B1, except that the amount of the monomer composition added was changed as shown in Table 1. The physical properties of resins B2 to B6 are shown in Table 1. Table 1<title desc="title" / ><row><cell>Resin B1< / cell><cell>Behenyl acrylate< / cell><cell>21< / cell><cell>60,0< / cell><cell>Styrene< / cell><cell>20,0< / cell><cell>Acrylonitrile< / cell><cell>10,0< / cell><cell>N-vinyl-2-pyrolidone< / cell><cell>10,0< / cell><cell>0,5< / cell><cell>30200< / cell>< / row><row><cell>Resin B2< / cell><cell>Behenyl acrylate< / cell><cell>21< / cell><cell>60,0< / cell><cell>Styrene< / cell><cell>20,0< / cell><cell>Acrylonitrile< / cell><cell>20,0< / cell><cell>-< / cell><cell>-< / cell><cell>0,5< / cell><cell>29860< / cell>< / row><row><cell>Resin B3< / cell><cell>Behenyl acrylate stearyl acrylate< / cell><cell>21 17< / cell><cell>50,0 10,0< / cell><cell>Styrene< / cell><cell>20,0< / cell><cell>Acrylonitrile< / cell><cell>10,0< / cell><cell>N-vinyl-2-pyrolidone< / cell><cell>10,0< / cell><cell>0,5< / cell><cell>32450< / cell>< / row><row><cell>Resin B4< / cell><cell>Behenyl acrylate< / cell><cell>21< / cell><cell>80,0< / cell><cell>Styrene< / cell><cell>10,0< / cell><cell>Acrylonitrile< / cell><cell>5,0< / cell><cell>N-vinyl-2-pyrolidone< / cell><cell>5,0< / cell><cell>0,5< / cell><cell>31560< / cell>< / row><row><cell>Resin B5< / cell><cell>Behenyl acrylate< / cell><cell>21< / cell><cell>50,0< / cell><cell>Styrene< / cell><cell>30,0< / cell><cell>Acrylonitrile< / cell><cell>10,0< / cell><cell>N-vinyl-2-pyrolidone< / cell><cell>10,0< / cell><cell>0,5< / cell><cell>32130< / cell>< / row><row><cell>Resin B6< / cell><cell>Behenyl acrylate< / cell><cell>21< / cell><cell>60,0< / cell><cell>Styrene< / cell><cell>27,5< / cell><cell>Acrylonitrile< / cell><cell>10,0< / cell><cell>Acrylic acid< / cell><cell>2,5< / cell><cell>0,5< / cell><cell>34000< / cell>< / row><row><cell>Polymerization initiator: t-butylperoxypivalate (perbutyl PV, manufactured by NOF Corporation)< / cell>< / row><head xml:id="_a187b30385">Example 1< / head><head xml:id="_a187b30386">Production of toner by suspension polymerization method< / head><head xml:id="_a187b30387">Production of Toner Particles 1< / head><p xml:id="_a187b30388" n="0149">A mixture of the following materials was prepared.<title desc="title" / ><row><cell>styrene< / cell><cell>45,0 Parts< / cell>< / row><row><cell>n-Butyl acrylate< / cell><cell>15,0 Parts< / cell>< / row><row><cell>Pigment Blue 15:3 (colorant)< / cell><cell>6,5 Parts< / cell>< / row><p xml:id="_a187b30405" n="0150">The mixture was placed in an attritor (manufactured by Nippon Coke & Engineering Co., Ltd.), and dispersed with zirconia beads having a diameter of 5 mm for 2 hours at 200 rpm to obtain a raw material dispersion liquid.<p xml:id="_a187b30406" n="0151">Separately, 735.0 parts of deionized water and 16.0 parts of trisodium phosphate (dodecahydrate) were placed in a vessel equipped with a high-speed stirrer, HOMO MIXER (manufactured by PRIMIX Corporation), and a thermometer, and heated to 60° C. at 12000 U / min with stirring. An aqueous calcium chloride solution in which 9.0 parts of calcium chloride (dihydrate) was dissolved in 65.0 parts of deionized water was added thereto and stirred at 12000 U / min for 30 minutes while maintaining the temperature at 60° C. To the mixture was added 10% hydrochloric acid to adjust the pH to 6.0, thereby obtaining an aqueous medium in which a hydroxyapatite-containing inorganic dispersion stabilizer was dispersed in water.<p xml:id="_a187b30407" n="0152">Subsequently, the raw material dispersion liquid was transferred to a container equipped with an apparatus for stirring and a thermometer, and heated to 60° C. at 100 U / min with stirring. The following materials were added.<title desc="title" / ><row><cell>resin A1< / cell><cell>4,0 Parts< / cell>< / row><row><cell>- Resin B< / cell><cell>135,0 Parts< / cell>< / row><row><cell>DP18 (dipentaerythritol stearate-Wac manufactured by The Nisshin OilliO Group, Ltd.)hs; melting point, 79°C< / cell><cell>9,0 Parts< / cell>< / row><row><cell>HDDA (hexanediol diacrylate)< / cell><cell>0,1 Parts< / cell>< / row><p xml:id="_a187b30427" n="0153">The mixture was stirred at 100 rpm for 30 minutes while maintaining the temperature at 60°C, and then further stirred for one minute while adding 8.0 parts of t-butylperoxypivalate (Perbutyl PV, manufactured by NOF Corporation) as a polymerization initiator. Thereafter, the resulting mixture was placed in the aqueous medium and stirred at 12000 U / min with the high-speed stirrer. While the temperature was maintained at 60° C., stirring was continued at 12000 U / min for 20 minutes with the high-speed stirring device to obtain a granulated liquid.<p xml:id="_a187b30428" n="0154">The granulated 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 76° C. under stirring at 150 U / min in a nitrogen atmosphere. While the temperature was maintained at 76° C., a polymerization reaction was carried out at 150 U / min for 6 hours to obtain a toner particle dispersion liquid.<p xml:id="_a187b30429" n="0155">The toner particle dispersion liquid thus obtained was cooled to 45°C with stirring at 150 U / min, and then heat-treated for 5 hours while maintaining the temperature at 45°C. Thereafter, diluted hydrochloric acid was added to a pH of 1.5 with constant stirring to dissolve the dispersion stabilizer. Solids were separated by filtration, washed thoroughly with deionized water, and then vacuum-dried at 30° C. for 24 hours to obtain Toner Particle 1.<head xml:id="_a187b30430">Preparation of Toner 1< / head><p xml:id="_a187b30431" n="0156">To 98.0 parts of the toner particles 1, 2.0 parts of silica fine particles (hydrophobicized with hexamethyldisilazane; number average primary particle diameter, 10 nm; BET specific surface area, 170 m <hi rend="superscript">2< / hi> / g) as an external additive were added and mixed for 15 minutes with a Henschel mixer (manufactured by Nippon Coke & Engineering Co., Ltd.) to obtain a toner 1. Physical properties, etc. of the obtained toner 1 are shown in Table 3.<head xml:id="_a187b30433">Examples 2 to 23< / head><p xml:id="_a187b30434" n="0157">Toner particles 2 to 23 were prepared in the same manner as in Example 1 except that the kind and the addition amount of the polymerizable monomers used, the addition amount of the polymerization initiator, the kind and the addition amount of the releasing agent, the other additives, the reaction temperature and the reaction time were changed as shown in Table 2.<p xml:id="_a187b30435" n="0158">In addition, the same external addition as in Example 1 was carried out to obtain toners 2 to 23. The physical properties of the toners are shown in Table 3.<head xml:id="_a187b30436">Comparative Examples 1 to 6< / head><p xml:id="_a187b30437" n="0159">Comparative toner particles 1 to 6 were obtained in the same manner as in Example 1, except that the kind and the addition amount of the polymerizable monomers used, the addition amount of the polymerization initiator, the kind and the addition amount of the releasing agent, the other additives, the reaction temperature and the reaction time were changed as shown in Table 2.<p xml:id="_a187b30438" n="0160">In addition, the same external addition as in Example 1 was carried out to obtain Comparative Toners 1 to 6. The physical properties of the toners are shown in Table 3.<head xml:id="_a187b30439">Comparative Example 7< / head><head xml:id="_a187b30440">Preparation of Comparative Toner Particles 7< / head><p xml:id="_a187b30441" n="0161">A mixture of the following materials was prepared.<title desc="title" / ><row><cell>methacrylonitrile< / cell><cell>30,0 Parts< / cell>< / row><row><cell>styrene< / cell><cell>13,0 Parts< / cell>< / row><row><cell>ethyl methacrylate< / cell><cell>7,0 Parts< / cell>< / row><row><cell>aluminum di-t-butyl salicylate< / cell><cell>1,0 Parts< / cell>< / row><row><cell>- Colorant, Pigment Blue 15:< / cell><cell>36,5 Parts< / cell>< / row><p xml:id="_a187b30464" n="0162">The mixture was placed in an attritor (manufactured by Nippon Coke & Engineering Co., Ltd.), and dispersed with zirconia beads having a diameter of 5 mm for 2 hours at 200 rpm to obtain a raw material dispersion liquid. Separately, 735.0 parts of deionized water and 16.0 parts of trisodium phosphate (dodecahydrate) were placed in a vessel equipped with a high-speed stirrer, HOMO MIXER (manufactured by PRIMIX Corporation), and a thermometer, and heated to 60° C. at 12000 U / min with stirring. An aqueous calcium chloride solution in which 9.0 parts of calcium chloride (dihydrate) was dissolved in 65.0 parts of deionized water was added thereto and stirred at 12000 U / min for 30 minutes while maintaining the temperature at 60° C. To the mixture was added 10% hydrochloric acid to adjust the pH to 6.0, thereby obtaining an aqueous medium in which a hydroxyapatite-containing inorganic dispersion stabilizer was dispersed in water.<p xml:id="_a187b30465" n="0163">Subsequently, the raw material dispersion liquid was transferred to a container equipped with an apparatus for stirring and a thermometer, and heated to 60° C. at 100 U / min with stirring. The following materials were added.<title desc="title" / ><row><cell>behenyl acrylate< / cell><cell>50,0 Parts< / cell>< / row><row><cell>- DP18< / cell><cell>10,0 Parts< / cell>< / row><p xml:id="_a187b30479" n="0164">The mixture was stirred at 100 U / min for 30 minutes while the temperature was maintained at 60°C. Thereafter, the resulting mixture was further stirred for 1 minute, to which 7.0 parts of t-butylperoxypivalate (Perbutyl PV, manufactured by NOF Corporation) and 1.0 parts of t-butylperoxyisobutyrate (L80, manufactured by ARKEMA Yoshitomi, Ltd.) as polymerization initiators were added. Thereafter, the resulting mixture was placed in the aqueous medium and stirred at 12000 U / min with the high-speed stirrer. While the temperature was maintained at 60° C., stirring was continued at 12000 U / min for 20 minutes with the high-speed stirring device to obtain a granulated liquid.<p xml:id="_a187b30480" n="0165">The granulated 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 stirring at 150 U / min in a nitrogen atmosphere, where a first stage of the polymerization reaction was carried out at 150 U / min for 5 hours. Thereafter, the temperature was raised to 90°C, and a second stage of the polymerization reaction was carried out for 5 hours while the temperature was maintained at 90°C, to obtain a toner particle dispersion liquid.<p xml:id="_a187b30481" n="0166">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 to a pH of 1.5 with constant stirring to dissolve the dispersion stabilizer. Solids were separated by filtration, washed thoroughly with deionized water, and then vacuum-dried at 30°C for 24 hours to obtain comparative toner particles 7. In addition, the same external addition as in Example 1 was carried out to obtain a comparative toner 7. The physical properties of the obtained comparative toner 7 are shown in Table 3.<head xml:id="_a187b30482">Comparative Example 8< / head><head xml:id="_a187b30483">Production Example of Comparative Toner Particles 8< / head><p xml:id="_a187b30484" n="0167">The following materials were mixed.<title desc="title" / ><row><cell>Resin A2< / cell><cell>40 Parts< / cell>< / row><row><cell>-Resin B6< / cell><cell>60 Parts< / cell>< / row><p xml:id="_a187b30498" n="0168">The mixture was fed to a twin-screw kneader (manufactured by Kurimoto, Ltd., S5KR kneader) at 1 kg / hr, and simultaneously 4.0 parts of t-butylperoxyisopropyl monocarbonate as a radical reaction initiator at 0.1 kg / hr was fed. The kneading extrusion was carried out at 160° C. for 5 minutes at 100 U / min to effect the reaction. Further, nitrogen was supplied through a vent and mixing was performed while removing the organic solvent. A kneaded product obtained by kneading was cooled to obtain a comparative resin 8. Measurement by gel permeation chromatography (GPC) revealed that the resin A2 and the resin B6 were partially reacted, resulting in an increase in the weight-average molecular weight. The content of the reacted resins in the comparative resin 8 was 5 mass %.<p xml:id="_a187b30499" n="0169">The following materials were mixed with a Henschel mixer (model FM-75, manufactured by Nippon Coke & Engineering Co., Ltd.) at a rotation speed of 20 s <hi rend="superscript">-1< / hi> and a rotation time of 5 minutes.<title desc="title" / ><row><cell>Comparative resin 8< / cell><cell>100 Parts< / cell>< / row><row><cell>hydrocarbon wax< / cell><cell>5,0 Parts< / cell>< / row>(Fischer-Tropsch wax: peak temperature of maximum endothermic peak of DSC, 90°C)<title desc="title" / ><row><cell>C. I. Pigment Blue 15:< / cell><cell>36,5 Parts< / cell>< / row><p xml:id="_a187b30524" n="0170">Thereafter, the mixture was kneaded with a twin screw kneader (Model PCM-30 manufactured by Ikegai Corporation) at a screw speed of 250 U / min and an outlet temperature of 130° C. The resultant kneaded product was cooled and roughly pulverized to 1 mm or less with a hammer mill to obtain a pulverized product. The obtained pulverized product was finely pulverized by a mechanical pulverizer (T-250 manufactured by FREUND-TURBO CORPORATION).<p xml:id="_a187b30525" n="0171">Further, classification was carried out with a Faculty F-300 (manufactured by Hosokawa Micron Corporation) to obtain comparative toner particles 8 having a weight average particle diameter of about 6.0 μm. The operating conditions were as follows:<list xml:id="_a187b30526" type="bulleted"><item>Classifying Rotor Rotational Speed, 130 s <hi rend="superscript">-1< / hi>;< / item><item>Dispersive rotor rotational speed, 120 s <hi rend="superscript">-1< / hi>.< / item>< / list><p xml:id="_a187b30531" n="0172">The following materials were mixed with a Henschel mixer FM-10C (manufactured by Chemical Machinery Division of Nippon Coke & Engineering Co., Ltd.) at a rotation speed of 30 seconds <hi rend="superscript">-1< / hi> and a rotation time of 10 minutes to obtain a comparative toner 8.<title desc="title" / ><row><cell>- Comparative toner particles 8< / cell><cell>100 Parts< / cell>< / row><row><cell>hydrophobic silica fine primary particle diameters of 15 nm particles having a number average< / cell><cell>0,5 Parts< / cell>< / row><row><cell>hydrophobic silica fine particles having a number average primary particle diameter of 80 nm< / cell><cell>1,0 Parts< / cell>< / row><p xml:id="_a187b30549" n="0173">The physical properties of the obtained comparative toner 8 are shown in Table 3. Table 2-1<title desc="title">Table 2-1Example 11Suspension PolymerizationResin B140,0Styrene45,0n-Butyl acrylate15,0HDDA0,1Resin A14,0Example 22Suspension PolymerizationResin B135,0Styrene48,8n-Butyl acrylate16,3HDDA0,1Resin A14,0Example 33Suspension PolymerizationResin B125,0Styrene56,3n-Butyl acrylate18,8HDDA0,2Resin A14,0Example 44Suspension PolymerizationResin B153,0Styrene35,3n-Butyl acrylate11,8HDDA0,1Resin A14,0Example 55Suspension PolymerizationResin B160,0Styrene30,0n-Butyl acrylate10,0HDDA0,1Resin A14,0Example 66Suspension PolymerizationResin B125,0Styrene56,3n-Butyl acrylate18,8HDDA0,1Resin A14,0Example 77Suspension PolymerizationResin B160,0Styrene30,0n-Butyl acrylate10,0HDDA0,1Resin A14,0Example 88Suspension PolymerizationResin B140,0Styrene45,0n-Butyl acrylate15,0HDDA0,1Resin A14,0Example 99Suspension PolymerizationResin B125,0Styrene56,3n-Butyl acrylate18,8HDDA0,5Resin A14,0Example 1010Suspension PolymerizationResin B140,0Styrene45,0n-Butyl acrylate15,0HDDA0,1Resin A14,0Example 1111Suspension PolymerizationResin B140,0Styrene45,0n-Butyl acrylate15,0HDDA0,1Resin A14,0Example 1212Suspension PolymerizationResin B140,0Styrene45,0n-Butyl acrylate15,0HDDA0,1Resin A14,0Example 1313Suspension PolymerizationResin B140,0Styrene45,0n-Butyl acrylate15,0HDDA0,1Resin A14,0Example 1414Suspension PolymerizationResin B140,0Styrene45,0n-Butyl acrylate15,0HDDA0,1Resin A14,0Example 1515Suspension PolymerizationResin B140,0Styrene45,0n-Butyl acrylate15,0HDDA1,0Resin A14,0Example 1616Suspension PolymerizationResin B140,0Styrene45,0n-Butyl acrylate15,0HDDA1,3Resin A14,0Example 1717Suspension PolymerizationResin B140,0Styrene45,0n-Butyl acrylate15,0HDDA0,1Resin A14,0Example 1818Suspension PolymerizationResin B140,0Styrene45,0n-Butyl acrylate15,0HDDA0,1Resin A14,0Example 1919Suspension PolymerizationResin B160,0Styrene30,0n-Butyl acrylate10,0HDDA0,1--Example 2020Suspension PolymerizationResin B240,0Styrene45,0n-Butyl acrylate15,0HDDA0,1Resin A14,0Example 2121Suspension PolymerizationResin B340,0Styrene45,0n-Butyl acrylate15,0HDDA0,1Resin A14,0Example 2222Suspension PolymerizationResin B430,0Styrene52,5n-Butyl acrylate17,5HDDA0,1Resin A14,0Example 2323Suspension PolymerizationResin B550,0Styrene37,5n-Butyl acrylate12,5HDDA0,1Resin A14,0Comparative Example 1Comparison 1Suspension PolymerizationResin B122,0Styrene58,5n-Butyl acrylate19,5HDDA0,2Resin A14,0Comparative Example 2Comparison 2Suspension PolymerizationResin B165,0Styrene26,3n-Butyl acrylate8,8HDDA0,1Resin A14,0Comparative Example 3Comparison 3Suspension PolymerizationResin B122,0Styrene58,5n-Butyl acrylate19,5HDDA0,1Resin A14,0Comparative Example 4Comparison 4Suspension PolymerizationResin B170,0Styrene22,5n-Butyl acrylate7,5HDDA0,1Resin A14,0Comparative Example 5Comparison 5Suspension PolymerizationResin B140,0Styrene45,0n-Butyl acrylate15,0HDDA0,1Resin A14,0Comparative Example 6Comparison 6Suspension PolymerizationResin B140,0Styrene45,0n-Butyl acrylate15,0HDDA0,1Resin A14,0Table 2-2Table 2-2Example 11-8,0Dipentaerythritol stearate wax9,076,06,0Example 22-9,0Dipentaerythritol stearate wax9,076,06,0Example 33-10,0Dipentaerythritol stearate wax9,076,06,0Example 44-8,0Dipentaerythritol stearate wax9,076,06,0Example 55-8,0Dipentaerythritol stearate wax9,076,06,0Example 66-10,0Dipentaerythritol stearate wax9,077,06,0Example 77-7,0Dipentaerythritol stearate wax9,076,06,0Example 88-8,0Dipentaerythritol stearate wax9,074,06,0Example 99-13,0Dipentaerythritol stearate wax9,077,06,0Example 1010-6,0Dipentaerythritol stearate wax9,074,06,0Example 1111-4,0Dipentaerythritol stearate wax9,073,06,0Example 1212-9,0Dipentaerythritol stearate wax9,076,06,0Example 1313-9,5Dipentaerythritol stearate wax9,076,06,0Example 1414-8,0Dipentaerythritol stearate wax9,076,06,0Example 1515-8,0Dipentaerythritol stearate wax9,076,06,0Example 1616-8,0Dipentaerythritol stearate wax9,076,06,0Example 1717-8,0Pentaerythritol stearate wax9,076,06,0Example 1818-8,0Paraffin wax (HNP51)9,076,06,0Example 19190,58,0Dipentaerythritol stearate wax9,076,06,0Example 2020-8,0Dipentaerythritol stearate wax9,076,06,0Example 2121-8,0Dipentaerythritol stearate wax9,076,06,0Example 2222-8,5Dipentaerythritol stearate wax9,076,06,0Example 2323-6,0Dipentaerythritol stearate wax9,076,06,0Comparative Example 1Comparison 1-10,0Dipentaerythritol stearate wax9,076,06,0Comparative Example 2Comparison 2-8,0Dipentaerythritol stearate wax9,076,06,0Comparative Example 3Comparison 3-12,0Dipentaerythritol stearate wax9,077,06,0Comparative Example 4Comparison 4-8,0Dipentaerythritol stearate wax9,074,06,0Comparative Example 5Comparison 5-4,0Dipentaerythritol stearate wax9,072,06,0Comparative Example 6Comparison 6-10,5Dipentaerythritol stearate wax9,076,06,0Polymerization initiator: t-butylperoxypivalate (perbutyl PV, manufactured by NOF Corporation), half-life 10 hours (58°C)Table 3-1Table 3-1Example 1126,665,50,97102003350Example 2221,652,00,97484003040Example 3315,442,00,98869003980Example 4433,472,00,9569703500Example 5537,978,00,9253403590Example 6615,464,30,98875104030Example 7736,863,40,9053903520Example 8825,844,50,97124003620Example 9915,476,00,97867803540Example 101025,364,50,91115004890Example 111125,365,80,91101505890Example 121225,368,90,91115002810Example 131325,369,70,91124002120Example 141424,465,50,9791803400Example 151530,264,50,96489003010Example 161632,662,20,96878403880Example 171726,665,50,94112803900Example 181826,665,50,92106403700Example 191927,962,80,9799503100Example 202026,365,50,97115803730Example 212126,563,80,9898603280Example 222226,664,80,9494803700Example 232327,766,80,9494803700Comparative Example 1Comparison 113,938,70,98968003350Comparative Example 2Comparison 241,183,10,9152803640Comparative Example 3Comparison 313,964,50,981053103730Comparative Example 4Comparison 442,963,40,9046203810Comparative Example 5Comparison 525,164,80,91101506750Comparative Example 6Comparison 625,370,50,91124001720Comparative Example 7Comparison 748,11001,0054800Comparative Example 8Comparison 833,665,00,9786807840Table 3-2Table 3-2Example 1139,49750027,57,0Example 2240,318750044,53,5Example 3336,021250054,53,5Example 4444,16570023,54,5Example 5544,64158017,54,5Example 6623,510891032,23,5Example 7752,27824033,53,1Example 8856,28987050,05,5Example 9919,67986020,53,5Example 101035,74986030,94,6Example 111135,02990029,64,6Example 121233,412890026,54,6Example 131333,013780025,74,6Example 141436,19750031,72,8Example 151545,018907022,712,8Example 161650,321580022,015,8Example 171738,29750027,57,0Example 181837,49750027,57,0Example 191943,19730030,27,0Example 202039,08985028,06,5Example 212140,79298029,46,8Example 222238,69948028,27,0Example 232339,09180026,27,0Comparative Example 1Comparison 135,122150056,84,5Comparative Example 2Comparison 245,03980012,34,6Comparative Example 3Comparison 321,112540030,94,6Comparative Example 4Comparison 460,97824033,53,1Comparative Example 5Comparison 535,22480031,04,2Comparative Example 6Comparison 632,615980024,94,6Comparative Example 7Comparison 748,1880000,00,0Comparative Example 8Comparison 850,24280035,00,0Method for Toner EvaluationThe toners of Examples 1 to 23 and Comparative Examples 1 to 8 were each subjected to the following evaluations.<1> Low-temperature fixabilityA process cartridge filled with toner (a process cartridge for a laser beam printer (LBP-712Ci, manufactured by CANON KABUSHIKI KAISHA)) was allowed to stand at 25° C. and 40% relative humidity for 48 hours. With a modified laser beam printer-based apparatus (LBP-712Ci manufactured by CANON KABUSHIKI KAISHA) modified to operate without a fixing unit, an unfixed image of an image pattern in which 10 mm×10 mm square images were uniformly arranged at 9 dots pitch throughout the recording paper was outputted. The toner amount on the recording paper was set to 0.80 mg / cm 2 and the fixing start temperature was evaluated. As the recording paper, A4 paper (Plover Bond paper: 105 g / m 2, manufactured by Fox River Paper Company) was used.As the fixing unit, an external fixing unit was used which was prepared by taking out the fixing unit of the laser beam printer (LBP-712Ci manufactured by CANON KABUSHIKI KAISHA) and modifying the fixing unit so as to function also outside the laser beam printer. While the fixing temperature of the external fixing unit was increased from 90° C. in 5° C. steps, fixing was effected at a process speed of 360 mm / s.The fixed image was visually observed, and evaluation of low-temperature fixability was made from the lowest temperature at which no cold offset occurred as a fixing start temperature. The evaluation results are shown in Table 4.<2> Adhesiveness to paper (fixed image abrasion resistance)A fixed image was printed in the same manner as in the evaluation of <1> above. The fixing temperature was set to a temperature 5°C above the fixing start temperature. Soft thin paper (Dusper manufactured by Ozu Corporation) was put on an image portion of the obtained fixed image, and the image portion was rubbed back and forth five times while applying a load of 4.9 kPa from above to the thin paper. The image densities before and after the rubbing were measured, and the rate of decrease ΔD (%) of the image density was calculated according to the following formula. ΔD (%) was used as an index of abrasion resistance.The image density was measured with a color reflection densitometer (X-Rite 404A manufactured by X-Rite Inc.). The evaluation results are shown in Table 4.<3> Hot offset resistanceThe highest temperature at which no hot offset was observed under the same conditions as in the evaluation of <1> above was determined as the highest fixing temperature, and a difference between the highest fixing temperature and the lowest fixing temperature was determined as the fixable range. The evaluation results are shown in Table 4.<4> Evaluation of GlossThe fixed image at the fixing start temperature was used in the evaluation of <1> above. The gloss value was measured with a Handy PG-1 gloss meter (manufactured by Nippon Denshoku Industries Co., Ltd.). Under the measurement conditions in which the light emission angle and the light reception angle were each set to 75°, all the image patterns in which the images were arranged at a pitch of 9 points were measured, and their average value was evaluated. The evaluation results are shown in Table 4. In the table, C.O. denotes the cold offset and H.O. denotes the hot offset. Table 4 Table 4Example 111001,85528,2Example 221152,25527,6Example 331252,45526,2Example 441001,92527,2Example 55952,01526,9Example 661202,26025,2Example 77952,22026,5Example 881102,95526,2Example 991202,22026,1Example 10101002,25520,3Example 11111002,85015,2Example 12121004,94526,9Example 13131006,84027,2Example 1414951,83020,2Example 15151102,35524,2Example 16161152,95522,9Example 17171002,25028,1Example 18181101,95024,2Example 19191001,93526,9Example 20201003,94526,2Example 21211002,24526,2Example 22221001,95527,4Example 23231002,35526,4Comparative Example 1Comparison 11402,25526,2Comparative Example 2Comparison 2952,9526,5Comparative Example 3Comparison 31352,46024,8Comparative Example 4Comparison 4952,0527,1Comparative Example 5Comparison 51002,25513,8Comparative Example 6Comparison 610010,84026,9Comparative Example 7Comparison 71002,21027,8Comparative Example 8Comparison 81104,24513,2Although the present disclosure has been described with reference to exemplary embodiments, 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 embrace 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 citedWO 2013 / 047296

[0003] JP 2022-162968

[0007] JP 2021-096463

[0008]

Claims

A toner comprising: toner particles containing a resin component, wherein the resin component contains a crystalline vinyl resin having a unit (a) represented by the formula (1), the resin component contains the unit (a) in an amount of 15.0 mass% or more and 40.0 mass% or less based on a mass of the resin component, in the formula (1), R l represents a hydrogen atom or a methyl group, and n represents an integer of 15 to 35 when the toner particles are subjected to Soxhlet extraction with chloroform for 18 hours to obtain chloroform-soluble material from which a component having a molecular weight of 2000 or less is removed by recycling HPLC, to obtain chloroform-soluble material W, wherein, for the chloroform-soluble material W, acetonitrile is used as a poor solvent and chloroform is used as a good solvent, while a mobile phase is linearly changed from 100 vol % acetonitrile to 100 vol % chloroform and an eluted component is subjected to gradient LC analysis, a plurality of local maximum values are present in a diagram in which a horizontal axis represents a chloroform percentage (vol %) in the mobile phase and a vertical axis represents a signal intensity (μA) of the eluted component detected with a charged particle detector when a local maximum value is determined from a local maximum value having a highest intensity and a local maximum value having a second highest intensity among the plurality of local maximum values, wherein the chloroform percentage in the mobile phase is smaller, is a local maximum value PA, and a local maximum value at which the chloroform percentage in the mobile phase is larger, is a local maximum value PB, is a local minimum value with a lowest intensity existing between the local maximum value PA and the local maximum value PB, is a local minimum value BAB, a chloroform percentage at the local minimum value BAB VAB is vol % (20.0 < VAB < 95.0), a component whose chloroform percentage in the mobile phase is 20.0 vol % or more and less than VAB vol %, a component A, and a component, whose chloroform percentage in the mobile phase is VABvol% or more and 95.0% by volume or less, a component is B, the resin component contains the component B in an amount of 40.0% by mass or more and 80.0% by mass or less based on the mass of the resin component, when a content of the unit (a) in the chloroform-soluble material is WC mass % and a content of the unit (a) in the component is WB mass %, WC and WB satisfy the formula (2), WB / WC ≥ 0.70 and when a storage elastic modulus of the toner particles at 100°C is G'(T) and a storage elastic modulus of the component B at 100°C is G'(B), G'(T) and G'(B) satisfy the formulae (3) and (4), 5.0 × 10 3 Pa ≤ G'(T) ≤ 1.0 × 10 5 Pa 2,0 × 10 3 Pa ≤ G'(T)-G'(B) ≤ 6.0 × 10 5 Pa The toner according to claim 1, wherein the component B contains the unit (a) in an amount of 25.0 mass% or more and 50.0 mass% or less based on a mass of the component B.The toner according to claim 1 or 2, wherein the component B has a weight average molecular weight (Mw) of 30000 or more and 200000 or less.The toner according to any one of claims 1 to 3, wherein the resin component contains the component A in an amount of 10.0 mass% or more and 60.0 mass% or less based on the mass of the resin component.The toner according to any one of claims 1 to 4, wherein the resin component contains chloroform-insoluble matter in an amount of 3.0 mass% or more and 15.0 mass% or less based on the mass of the resin component.The toner according to any one of claims 1 to 5, wherein the toner particles contain a wax, and the wax is at least one selected from the group consisting of an ester of an alcohol having a valence of 4 or more and 8 or less and an aliphatic monocarboxylic acid, and an ester wax of a carboxylic acid having a valence of 4 or more and 8 or less and an aliphatic mono-alcohol.The toner according to any one of claims 1 to 6, wherein the toner particles have a core-shell structure including a core containing the crystalline vinyl resin and a shell containing an amorphous resin.The toner according to any one of claims 1 to 7, wherein the component B has a lactam structure.The toner according to claim 8, wherein the lactam structure contains a unit having a five-membered ring lactam structure.The toner according to any one of claims 1 to 9, wherein the crystalline vinyl resin contains a crystalline vinyl resin obtained by polymerizing a vinyl monomer containing a (meth)acrylate for introducing the unit (a) and then further reacting another vinyl monomer by hydrogen abstracting reaction.