JP2019008234A - toner - Google Patents

Abstract

To provide a toner that is excellent in heat-resistant storage property, low-temperature fixability, and high-temperature fixability.SOLUTION: A toner particle contains an amorphous polyester resin, a first crystalline polyester resin, and a second crystalline polyester resin. The difference between the SP value of the amorphous polyester resin and the SP value of the first crystalline polyester resin is 0.3(cal/cm)or more and 0.7(cal/cm)or less in absolute value. The difference between the SP value of the amorphous polyester resin and the SP value of the second crystalline polyester resin is 0.8(cal/cm)or more and 1.2(cal/cm)or less in absolute value. The amorphous polyester resin contains bisphenol A in a ratio of 20 mol% or more and 40 mol% or less based on the total alcohol component.SELECTED DRAWING: None

Description

  The present invention relates to a toner, and more particularly to a toner for developing an electrostatic latent image.

  Patent Document 1 discloses that the SP values of an amorphous resin, a crystalline resin, and a release agent contained in a toner are defined. However, the technique disclosed in Patent Document 1 is a technique related to polymerized toner.

JP 2014-206665 A

  However, it is difficult to provide a toner excellent in heat-resistant storage stability, low-temperature fixability, and high-temperature fixability only by the technique disclosed in Patent Document 1. The technique disclosed in Patent Document 1 is a technique related to a polymerized toner, and sufficient examination has not been made on the pulverizability of the toner.

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a toner excellent in heat-resistant storage stability, low-temperature fixability, and high-temperature fixability.

The toner according to the present invention includes a plurality of toner particles containing an amorphous polyester resin. The toner particles further contain a first crystalline polyester resin and a second crystalline polyester resin. The difference between the SP value of the non-crystalline polyester resin and the SP value of the first crystalline polyester resin is 0.3 (cal / cm ³ ) ^1/2 or more and 0.7 (cal / cm ³ ) in absolute value. ^1/2 or less. The difference between the SP value of the non-crystalline polyester resin and the SP value of the second crystalline polyester resin is 0.8 (cal / cm ³ ) ^1/2 or more and 1.2 (cal / cm ³ ) in absolute value. ^1/2 or less. The non-crystalline polyester resin contains bisphenol A in a proportion of 20 mol% or more and 40 mol% or less with respect to all alcohol components.

  According to the present invention, it is possible to provide a toner excellent in heat-resistant storage stability, low-temperature fixability, and high-temperature fixability.

  An embodiment of the present invention will be described. Note that evaluation results (values indicating shape, physical properties, etc.) relating to powder (more specifically, toner base particles, external additives, toner, etc.) are included in the powder unless otherwise specified. It is the number average of the values measured for a considerable number of particles.

Unless otherwise specified, the number average particle diameter of the powder is the number average of the equivalent-circle diameters of primary particles (Haywood diameter: the diameter of a circle having the same area as the projected area of the particles) measured using a microscope. Value. Moreover, the measured value of the volume median diameter (D ₅₀ ) of the powder is measured using a laser diffraction / scattering particle size distribution measuring device (“LA-750” manufactured by Horiba, Ltd.) unless otherwise specified. It is the value. Moreover, each measured value of an acid value and a hydroxyl value is a value measured according to "JIS (Japanese Industrial Standard) K0070-1992" unless otherwise specified. Moreover, each measured value of a number average molecular weight (Mn) and a mass average molecular weight (Mw) is the value measured using the gel permeation chromatography, if not prescribed | regulated at all.

  The glass transition point (Tg) is a value measured according to “JIS (Japanese Industrial Standard) K7121-2012” using a differential scanning calorimeter (“DSC-6220” manufactured by Seiko Instruments Inc.) unless otherwise specified. It is. In the endothermic curve (vertical axis: heat flow (DSC signal), horizontal axis: temperature) at the second temperature rise measured with a differential scanning calorimeter, an inflection point (baseline extrapolation line and standing) The temperature (onset temperature) at the intersection of the descending line and the extrapolated line corresponds to Tg (glass transition point). Moreover, the softening point (Tm) is a value measured using a Koka type flow tester (“CFT-500D” manufactured by Shimadzu Corporation) unless otherwise specified. In the S curve (horizontal axis: temperature, vertical axis: stroke) measured with the Koka type flow tester, the temperature that becomes "(baseline stroke value + maximum stroke value) / 2" is Tm (softening point). Equivalent to. Moreover, the measured value of the melting point (Mp) is an endothermic curve (vertical axis: heat flow (DSC) measured using a differential scanning calorimeter (“DSC-6220” manufactured by Seiko Instruments Inc.), unless otherwise specified). Signal), horizontal axis: temperature) of the endothermic peak (that is, the temperature at which the endothermic amount is maximized).

  The chargeability means the chargeability in frictional charging unless otherwise specified. The strength of positive chargeability (or strength of negative chargeability) in frictional charging can be confirmed by a known charge train or the like.

The SP value (solubility parameter) is calculated according to the Fedors calculation method (R. F. Fedors, “Polymer Engineering and Science”, 1974, Vol. 14, No. 2, p 147-154) unless otherwise specified. Value (unit: (cal / cm ³ ) ^1/2 , temperature: 25 ° C.). The SP value is represented by the formula “SP value = (E / V) ^1/2 ” (E: molecular cohesive energy [cal / mol], V: molecular volume [cm ³ / mol]).

  Hereinafter, a compound and its derivatives may be generically named by adding “system” after the compound name. When the name of a polymer is expressed by adding “system” after the compound name, it means that the repeating unit of the polymer is derived from the compound or a derivative thereof.

  The toner according to the exemplary embodiment can be suitably used for developing an electrostatic latent image, for example, as a positively chargeable toner. The toner of the present exemplary embodiment is a powder that includes a plurality of toner particles (each having a configuration described later). The toner may be used as a one-component developer. Alternatively, a two-component developer may be prepared by mixing toner and carrier using a mixing device (for example, a ball mill). In order to form a high-quality image, it is preferable to use a ferrite carrier (specifically, a powder of ferrite particles) as a carrier. In order to form a high-quality image over a long period of time, it is preferable to use magnetic carrier particles including a carrier core and a resin layer covering the carrier core. In order to impart magnetism to the carrier particles, the carrier core may be formed of a magnetic material (for example, a ferromagnetic substance such as ferrite), or the carrier core may be formed of a resin in which magnetic particles are dispersed. Good. Further, magnetic particles may be dispersed in the resin layer covering the carrier core. In order to form a high-quality image, the amount of toner in the two-component developer is preferably 5 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the carrier. The positively chargeable toner contained in the two-component developer is positively charged by friction with the carrier.

  The toner according to the exemplary embodiment can be used for image formation in, for example, an electrophotographic apparatus (image forming apparatus). Hereinafter, an example of an image forming method using an electrophotographic apparatus will be described.

  First, an image forming unit (charging device and exposure device) of an electrophotographic apparatus forms an electrostatic latent image on a photosensitive member (for example, a surface layer portion of a photosensitive drum) based on image data. Subsequently, a developing device of the electrophotographic apparatus (specifically, a developing device in which a developer containing toner is set) supplies the toner to the photoconductor to develop the electrostatic latent image formed on the photoconductor. The toner is charged by friction with the carrier, the developing sleeve, or the blade in the developing device before being supplied to the photoreceptor. For example, a positively chargeable toner is positively charged. In the developing process, toner (specifically, charged toner) on a developing sleeve (for example, a surface layer portion of a developing roller in the developing device) disposed in the vicinity of the photosensitive member is supplied to the photosensitive member, and the supplied toner is By attaching to the electrostatic latent image on the photoconductor, a toner image is formed on the photoconductor. The consumed toner is replenished to the developing device from a toner container containing replenishment toner.

  In the subsequent transfer process, after the transfer device of the electrophotographic apparatus transfers the toner image on the photosensitive member to an intermediate transfer member (for example, a transfer belt), the toner image on the intermediate transfer member is further transferred to a recording medium (for example, paper). Transcript to. Thereafter, a fixing device (fixing method: nip fixing with a heating roller and a pressure roller) of the electrophotographic apparatus heats and pressurizes the toner to fix the toner on the recording medium. As a result, an image is formed on the recording medium. For example, a full color image can be formed by superposing four color toner images of black, yellow, magenta, and cyan. After the transfer step, the toner remaining on the photoreceptor is removed by a cleaning member (for example, a cleaning blade). The transfer method may be a direct transfer method in which the toner image on the photosensitive member is directly transferred to the recording medium without using the intermediate transfer member. The fixing method may be a belt fixing method.

  The toner according to this embodiment includes a plurality of toner particles. The toner particles may include an external additive. When the toner particles include an external additive, the toner particles include a toner base particle and an external additive. The external additive adheres to the surface of the toner base particles. The toner base particles contain a binder resin. The toner base particles may contain an internal additive (for example, at least one of a release agent, a colorant, a charge control agent, and a magnetic powder) in addition to the binder resin, if necessary. If not necessary, the external additive may be omitted. When omitting the external additive, the toner base particles correspond to the toner particles.

  The toner particles contained in the toner according to the present embodiment may be toner particles not having a shell layer (hereinafter referred to as non-capsule toner particles), or toner particles having a shell layer (hereinafter referred to as capsule toner particles). May be described). In the capsule toner particles, the toner base particles include a toner core and a shell layer formed on the surface of the toner core. The shell layer is substantially composed of a resin. For example, by covering a toner core that melts at a low temperature with a shell layer having excellent heat resistance, it is possible to achieve both heat-resistant storage stability and low-temperature fixability of the toner. Additives may be dispersed in the resin constituting the shell layer. The shell layer may cover the entire surface of the toner core or may partially cover the surface of the toner core. The shell layer may be substantially composed of a thermosetting resin, may be substantially composed of a thermoplastic resin, or may contain both a thermoplastic resin and a thermosetting resin. .

  Non-capsule toner particles can be produced by a pulverization method. In the pulverization method, the internal additive is easily dispersed well in the binder resin of the non-capsule toner particles. In general, toner is roughly classified into pulverized toner and polymerized toner (also called chemical toner). The toner obtained by the pulverization method belongs to the pulverized toner.

  In an example of the pulverization method, first, a binder resin, a colorant, a charge control agent, and a release agent are mixed. Subsequently, the obtained mixture is melt-kneaded using a melt-kneading apparatus (for example, a single-screw or twin-screw extruder). Subsequently, the obtained melt-kneaded product is cooled and then pulverized. Subsequently, the obtained pulverized product is classified. Thereby, toner mother particles are obtained. When the pulverization method is used, the toner base particles can often be produced more easily than when the aggregation method is used.

  When producing the capsule toner particles, the method for forming the shell layer is arbitrary. For example, the shell layer may be formed using any one of an in-situ polymerization method, a submerged cured coating method, and a coacervation method.

  The toner according to the exemplary embodiment is an electrostatic latent image developing toner having the following configuration (hereinafter referred to as a basic configuration).

(Basic toner configuration)
The toner includes a plurality of toner particles containing an amorphous polyester resin, a first crystalline polyester resin, and a second crystalline polyester resin. The difference between the SP value of the amorphous polyester resin and the SP value of the first crystalline polyester resin is 0.3 (cal / cm ³ ) ^1/2 or more and 0.7 (cal / cm ³ ) ^{1 / in} absolute value. ² or less. The difference between the SP value of the non-crystalline polyester resin and the SP value of the second crystalline polyester resin is 0.8 (cal / cm ³ ) ^1/2 or more and 1.2 (cal / cm ³ ) ^{1 / in} absolute value. ² or less. The amorphous polyester resin contains bisphenol A at a ratio of 20 mol% or more and 40 mol% or less with respect to the total alcohol component. Bisphenol A may be bisphenol A having an adduct (more specifically, bisphenol A ethylene oxide adduct or bisphenol A propylene oxide adduct, etc.).

Hereinafter, the absolute value of the difference between the SP value of the amorphous polyester resin and the SP value of the first crystalline polyester resin may be referred to as “ΔSP ₁ ”. In addition, the absolute value of the difference between the SP value of the non-crystalline polyester resin and the SP value of the second crystalline polyester resin may be described as “ΔSP ₂ ”. Further, the SP value of the amorphous polyester resin is “SP _A ”, the SP value of the first crystalline polyester resin is “SP _B ”, and the SP value of the second crystalline polyester resin is “SP _C ”, respectively. May be described. Further, when the SP value is shown by omitting the unit, the unit of the SP value is “(cal / cm ³ ) ^1/2 ”.

  It is known that the low-temperature fixability of toner can be improved by using a crystalline polyester resin in addition to an amorphous polyester resin as a binder resin. However, it has been confirmed by experiments of the present inventor that deterioration of grindability becomes a problem when such a toner is produced by a grinding method. As described above, the pulverized toner is manufactured through a melt-kneading step and a pulverizing step. Prior to the pulverization step, the melt-kneaded product is cooled. However, the crystalline polyester resin melted in the melt-kneading process is not necessarily recrystallized by cooling after the melt-kneading process. If the crystalline polyester resin is present in the melt-kneaded product without being crystallized, the pulverizability of the melt-kneaded product tends to deteriorate. Prior to the pulverization step, it may be possible to carry out a long-time annealing (for example, a heat treatment for 20 hours to 30 hours) in order to crystallize the crystalline polyester resin. Sexuality gets worse. In addition, when a toner is produced by pulverizing a melt-kneaded product containing a crystalline polyester resin that is not crystallized, the heat-resistant storage stability of the obtained toner tends to be insufficient.

  In order to facilitate the crystallization of the crystalline polyester resin in the melt-kneaded product, the difference between the SP value of the amorphous polyester resin and the SP value of the crystalline polyester resin is increased so that the amorphous polyester resin and the crystalline polyester It is also conceivable that the resin is not compatible. However, if the amorphous polyester resin and the crystalline polyester resin are not sufficiently compatible, the effect of improving the low-temperature fixability of the toner cannot be obtained.

In order to solve the above problems, the present inventor has conducted experiments and studies and invented a toner having the above-described basic configuration. The inventor of the present application, as defined in the above-described basic configuration, includes an amorphous polyester resin (specifically, an amorphous polyester resin containing an appropriate amount of bisphenol A as an alcohol component) and two types of crystalline polyester resins (first By using the first crystalline polyester resin and the second crystalline polyester resin, the heat-resistant storage stability and the fixing property of the toner were successfully improved without impairing the toner productivity. SP _A (SP value of the non-crystalline polyester resin), SP _B (SP value of the first crystalline polyester resin), and SP _C (SP value of the second crystalline polyester resin) are represented by the following formula (M1). -(M4) is satisfied.

ΔSP ₁ = | SP _A −SP _B | (M1)
ΔSP ₂ = | SP _A −SP _C | (M2)
0.3 ≦ ΔSP ₁ ≦ 0.7 (M3)
0.8 ≦ ΔSP ₂ ≦ 1.2 (M4)

Specifically, the first crystalline polyester resin, which is more compatible with the amorphous polyester resin than the second crystalline polyester resin, imparts sharp melt properties to the toner, and is more amorphous than the first crystalline polyester resin. It is considered that the second crystalline polyester resin that is not easily compatible with the resin promotes recrystallization of the crystalline polyester resin in the melt-kneaded product. If ΔSP ₁ is too small, the heat-resistant storage stability of the toner tends to be insufficient (see toner TB-1 described later). On the other hand, if ΔSP ₁ is too small, hot offset is likely to occur (see toner TB-1 described later). If ΔSP ₁ is too large, the sharp melt property of the toner tends to be insufficient (see toner TB-2 described later). If ΔSP ₂ is too small, recrystallization of the crystalline polyester resin in the melt-kneaded product will not proceed easily, and the heat-resistant storage stability of the toner will tend to be insufficient (see toner TB-3 described later). If ΔSP ₂ is too large, the amorphous polyester resin and the crystalline polyester resin are not sufficiently compatible with each other, and it is difficult to appropriately melt and knead them (see toner TB-4 described later).

  The inventor of the present application, in a melt-kneaded product containing an amorphous polyester resin and a crystalline polyester resin, the amorphous polyester resin contains an appropriate amount of bisphenol A as an alcohol component (specifically, 20 mol% with respect to the total alcohol components). It has been found that when bisphenol A) in a proportion of 40 mol% or less is contained, the crystalline polyester resin in the melt-kneaded product is easily crystallized. In an environment where an appropriate amount of bisphenol A skeleton is present in the non-crystalline polyester resin, the crystalline polyester resin is likely to move and recrystallization of the crystalline polyester resin is promoted. If the amount of bisphenol A in the non-crystalline polyester resin is not appropriate, the heat-resistant storage stability and the fixing property of the toner are compatible even if the SP value requirements (formulas (M1) to (M4)) are satisfied. Is difficult (see toners TB-5 and TB-6 described later).

  Since the basic configuration described above is effective for improving the pulverization property, it is particularly preferable that the pulverized toner has the basic configuration described above. In addition, in order to obtain a pulverized toner excellent in heat-resistant storage stability and fixability, the glass transition point of the amorphous polyester resin is 50 ° C. or higher and 60 ° C. or lower in the basic configuration described above, and the first crystalline polyester resin It is particularly preferable that the amount and the amount of the second crystalline polyester resin are 5 parts by mass or more and 15 parts by mass or less with respect to 80 parts by mass of the amorphous polyester resin.

In order to obtain a toner that satisfies the above-mentioned SP value requirements (formulas (M1) to (M4)), in the above-described basic configuration, the non-crystalline polyester resin may have an adduct, It is a polymer of a monomer (resin raw material) containing 1,2-propanediol, aromatic dicarboxylic acid and trivalent carboxylic acid, and the first crystalline polyester resin and the second crystalline polyester resin are respectively , Α, ω-alkanediols and unsaturated dicarboxylic acid-containing monomers (resin raw materials) are particularly preferred. A suitable numerical range of the SP value of these polyester resins is 13.0 (cal / cm ³ ) ^1/2 or more and 14.0 (cal / cm ³ ) ^1/2 or less of the SP value of the amorphous polyester resin. The SP value of the first crystalline polyester resin is 12.7 (cal / cm ³ ) ^1/2 or more and 14.0 (cal / cm ³ ) ^1/2 or less, and the SP value of the second crystalline polyester resin 12.2 (cal / cm ³ ) ^1/2 or more and 14.8 (cal / cm ³ ) ^1/2 or less. Moreover, it is preferable that the quantity of 1st crystalline polyester resin is 0.2 to 5.0 times the quantity of 2nd crystalline polyester resin.

In order to obtain a toner suitable for image formation, it is preferable that the volume median diameter (D ₅₀ ) of the toner particles is 4 μm or more and 9 μm or less.

  Next, the configuration of the non-capsule toner particles will be described. Specifically, the toner base particles (binder resin and internal additive) and the external additive will be described in order. In the capsule toner particles, the toner base particles in the non-capsule toner particles shown below can be used as the toner core.

[Toner mother particles]
The toner base particles contain a binder resin. The toner base particles may contain an internal additive (for example, a colorant, a release agent, a charge control agent, and a magnetic powder).

(Binder resin)
In the toner base particles, generally, the binder resin occupies most of the components (for example, 85% by mass or more). For this reason, it is considered that the properties of the binder resin greatly affect the properties of the entire toner base particles. For example, when the binder resin has an ester group, a hydroxyl group, an ether group, an acid group, or a methyl group, the toner base particles tend to be anionic, and when the binder resin has an amino group, The toner base particles tend to be cationic.

  In the toner having the basic structure described above, the toner base particles contain an amorphous polyester resin, a first crystalline polyester resin, and a second crystalline polyester resin as a binder resin.

  The polyester resin is obtained by polycondensation of one or more polyhydric alcohols and one or more polyhydric carboxylic acids. As the alcohol for synthesizing the polyester resin, for example, a dihydric alcohol (more specifically, an aliphatic diol or bisphenol) or a trihydric or higher alcohol as shown below can be preferably used. As the carboxylic acid for synthesizing the polyester resin, for example, divalent carboxylic acids or trivalent or higher carboxylic acids as shown below can be suitably used.

  Suitable examples of the aliphatic diol include diethylene glycol, triethylene glycol, neopentyl glycol, 1,2-propanediol, α, ω-alkanediol (more specifically, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,12-dodecanediol, etc. ), 2-butene-1,4-diol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, or polytetramethylene glycol.

  Preferable examples of bisphenol include bisphenol A, hydrogenated bisphenol A, bisphenol A ethylene oxide adduct, or bisphenol A propylene oxide adduct.

  Preferable examples of trihydric or higher alcohols include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butane. Triol, 1,2,5-pentanetriol, glycerol, diglycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, or 1,3,5- Trihydroxymethylbenzene is mentioned.

  Preferable examples of the divalent carboxylic acid include aromatic dicarboxylic acid (more specifically, phthalic acid, terephthalic acid, or isophthalic acid), α, ω-alkanedicarboxylic acid (more specifically, malonic acid). Succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, or 1,10-decanedicarboxylic acid), unsaturated dicarboxylic acid (more specifically, maleic acid, fumaric acid, citraconic acid, itaconic acid, Or glutaconic acid or the like), or cycloalkane dicarboxylic acid (more specifically, cyclohexane dicarboxylic acid or the like).

  Preferred examples of the trivalent or higher carboxylic acid include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra (methylenecarboxyl) Examples include methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, or empole trimer acid.

  Preferable examples of the amorphous polyester resin include bisphenol A (for example, bisphenol A propylene oxide adduct) which may have an adduct, 1,2-propanediol, and aromatic dicarboxylic acid (for example, terephthalate). Acid) and a polymer of a monomer (resin raw material) containing a trivalent carboxylic acid (for example, trimellitic acid). Moreover, the monomer (resin raw material) of this example is further unsaturated dicarboxylic acid (preferably unsaturated dicarboxylic acid having 4 to 10 carbon atoms) and α, ω-alkanedicarboxylic acid (preferably having 2 carbon atoms). It is particularly preferable to contain 8 or less α, ω-alkanediol). Preferable examples of the unsaturated dicarboxylic acid include C 4 fumaric acid. Preferable examples of α, ω-alkanedicarboxylic acid include adipic acid having 6 carbon atoms.

  As the 1,2-propanediol for synthesizing the amorphous polyester resin (binder resin), plant-derived 1,2-propanediol is particularly preferable. Plant-derived 1,2-propanediol can be produced using, for example, chemical synthesis, fermentation, or a combination of these methods. In an example of a method for producing a plant-derived 1,2-propanediol, plant biomass containing a saccharide such as glucose is hydrolyzed to obtain glycerin. Subsequently, plant-derived 1,2-propanediol is obtained by reacting glycerin with hydrogen. As the plant biomass, for example, one or more vegetable oils and fats selected from the group consisting of soybean oil, palm oil, palm oil, castor oil, and cacao oil can be used. As a method for hydrolyzing plant biomass, a chemical method using an acid or a base may be employed, a biological method using an enzyme or a microorganism may be employed, or another method may be employed. Also good.

  Preferable examples of the first crystalline polyester resin include α, ω-alkanediol (preferably α, ω-alkanediol having 2 to 8 carbon atoms) and unsaturated dicarboxylic acid (preferably 4 or more carbon atoms). And a polymer of a monomer (resin raw material) containing 10 or less unsaturated dicarboxylic acids). Further, it is particularly preferable that the monomer (resin raw material) of this example further contains α, ω-alkanedicarboxylic acid (preferably α, ω-alkanediol having 8 to 12 carbon atoms). Preferable examples of α, ω-alkanediol include 1,4-butanediol having 4 carbon atoms. Preferable examples of the unsaturated dicarboxylic acid include C 4 fumaric acid. Preferable examples of the α, ω-alkanedicarboxylic acid include sebacic acid having 10 carbon atoms.

  Preferable examples of the second crystalline polyester resin include α, ω-alkanediol (preferably α, ω-alkanediol having 2 to 8 carbon atoms) and unsaturated dicarboxylic acid (preferably having 4 or more carbon atoms). And a polymer of a monomer (resin raw material) containing 10 or less unsaturated dicarboxylic acids). Further, it is particularly preferable that the monomer (resin raw material) of this example further contains α, ω-alkanedicarboxylic acid (preferably α, ω-alkanediol having 8 to 12 carbon atoms). Preferable examples of α, ω-alkanediol include 1,4-butanediol having 4 carbon atoms. Preferable examples of the unsaturated dicarboxylic acid include C 4 fumaric acid. Preferable examples of the α, ω-alkanedicarboxylic acid include sebacic acid having 10 carbon atoms.

(Coloring agent)
The toner base particles may contain a colorant. As the colorant, a known pigment or dye can be used according to the color of the toner. In order to obtain a toner suitable for image formation, the amount of the colorant is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin.

  The toner base particles may contain a black colorant. An example of a black colorant is carbon black. The black colorant may be a colorant that is toned to black using a yellow colorant, a magenta colorant, and a cyan colorant.

  The toner base particles may contain a color colorant such as a yellow colorant, a magenta colorant, or a cyan colorant.

  As the yellow colorant, for example, one or more compounds selected from the group consisting of condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and arylamide compounds can be used. Examples of the yellow colorant include C.I. I. Pigment Yellow (3, 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155 168, 174, 175, 176, 180, 181, 191, or 194), naphthol yellow S, Hansa yellow G, or C.I. I. Vat yellow can be preferably used.

  The magenta colorant is, for example, selected from the group consisting of condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. One or more compounds can be used. Examples of the magenta colorant include C.I. I. Pigment Red (2, 3, 5, 6, 7, 19, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 144, 146, 150, 166, 169, 177 184, 185, 202, 206, 220, 221 or 254) can be preferably used.

  As the cyan colorant, for example, one or more compounds selected from the group consisting of a copper phthalocyanine compound, an anthraquinone compound, and a basic dye lake compound can be used. Examples of cyan colorants include C.I. I. Pigment blue (1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, or 66), phthalocyanine blue, C.I. I. Bat Blue, or C.I. I. Acid blue can be preferably used.

(Release agent)
The toner base particles may contain a release agent. The release agent is used, for example, for the purpose of improving the fixing property or offset resistance of the toner. In order to improve the fixing property or offset resistance of the toner, the amount of the release agent is preferably 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the binder resin.

  Examples of the release agent include low molecular weight polyethylene, low molecular weight polypropylene, polyolefin copolymer, polyolefin wax, microcrystalline wax, paraffin wax, or aliphatic hydrocarbon wax such as Fischer-Tropsch wax; oxidized polyethylene wax or a block thereof Oxides of aliphatic hydrocarbon waxes such as copolymers; plant waxes such as candelilla wax, carnauba wax, wood wax, jojoba wax, or rice wax; animal properties such as beeswax, lanolin, or whale wax Waxes; mineral waxes such as ozokerite, ceresin, or petrolatum; waxes based on fatty acid esters such as montanate ester wax or castor wax; fats such as deoxidized carnauba wax The wax portion of the ester or the whole was deoxygenated can be suitably used. One type of release agent may be used alone, or multiple types of release agents may be used in combination.

(Charge control agent)
The toner base particles may contain a charge control agent. The charge control agent is used, for example, for the purpose of improving the charge stability or charge rising property of the toner. The charge rising characteristic of the toner is an index as to whether or not the toner can be charged to a predetermined charge level in a short time.

  By adding a negatively chargeable charge control agent (more specifically, an organometallic complex or a chelate compound) to the toner base particles, the anionicity of the toner base particles can be enhanced. Further, by adding a positively chargeable charge control agent (more specifically, pyridine, nigrosine, quaternary ammonium salt, or the like) to the toner base particles, the cationicity of the toner base particles can be increased. However, if sufficient chargeability is ensured in the toner, it is not necessary to add a charge control agent to the toner base particles.

(Magnetic powder)
The toner base particles may contain magnetic powder. Examples of magnetic powder materials include ferromagnetic metals (more specifically, iron, cobalt, nickel, or alloys containing one or more of these metals), ferromagnetic metal oxides (more specifically, Ferrite, magnetite, chromium dioxide, or the like) or a material subjected to ferromagnetization treatment (more specifically, a carbon material or the like imparted with ferromagnetism by heat treatment) can be suitably used. One type of magnetic powder may be used alone, or a plurality of types of magnetic powder may be used in combination.

[External additive]
An external additive (specifically, a powder containing a plurality of external additive particles) may be adhered to the surface of the toner base particles. Unlike the internal additive, the external additive does not exist inside the toner base particles, but selectively exists only on the surface of the toner base particles (surface layer portion of the toner particles). For example, by stirring together the toner base particles (powder) and the external additive (powder), the external additive particles can be attached to the surface of the toner base particles. The toner base particles and the external additive particles do not chemically react with each other and are physically bonded instead of chemically. The strength of the bond between the toner base particles and the external additive particles depends on the stirring conditions (more specifically, the stirring time, the rotation speed of the stirring, etc.), the particle diameter of the external additive particles, and the shape of the external additive particles. And the surface condition of the external additive particles.

  In order to fully perform the functions of the external additive while suppressing the detachment of the external additive particles from the toner particles, the amount of the external additive (if multiple types of external additive particles are used, The total amount of external additive particles) is preferably 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the toner base particles.

  The external additive particles are preferably inorganic particles such as silica particles or metal oxide particles (more specifically, alumina, titanium oxide, magnesium oxide, zinc oxide, strontium titanate, or barium titanate). Particularly preferred. In order to improve the fluidity of the toner, it is preferable to use inorganic particles (powder) having a number average primary particle diameter of 5 nm to 30 nm as external additive particles. However, particles of an organic acid compound such as a fatty acid metal salt (more specifically, zinc stearate) or resin particles may be used as the external additive particles. Moreover, you may use the composite particle which is a composite of a multiple types of material as external additive particle | grains. One type of external additive particles may be used alone, or a plurality of types of external additive particles may be used in combination.

  The external additive particles may be surface-treated. For example, when silica particles are used as the external additive particles, hydrophobicity and / or positive chargeability may be imparted to the surface of the silica particles by the surface treatment agent. Examples of the surface treatment agent include a coupling agent (more specifically, a silane coupling agent, a titanate coupling agent, or an aluminate coupling agent), a silazane compound (for example, a chain silazane compound or a cyclic silazane compound). ) Or silicone oil (more specifically, dimethyl silicone oil or the like) can be preferably used. As the surface treatment agent, a silane coupling agent or a silazane compound is particularly preferable. Preferable examples of the silane coupling agent include silane compounds (more specifically, methyltrimethoxysilane or aminosilane). A preferred example of the silazane compound is HMDS (hexamethyldisilazane). When the surface of the silica substrate (untreated silica particles) is treated with the surface treatment agent, a large number of hydroxyl groups (—OH) present on the surface of the silica substrate are partially or entirely derived from the surface treatment agent. Substituted with a functional group. As a result, silica particles having a functional group derived from the surface treating agent (specifically, a functional group that is more hydrophobic and / or positively charged than the hydroxyl group) on the surface can be obtained.

  Examples of the present invention will be described. Table 1 shows toners TA-1 to TA-10 and TB-1 to TB-8 (respectively positively chargeable toners) according to examples or comparative examples. Tables 2 and 3 show binder resins A to C used for the production of the toners shown in Table 1.

In Table 1, regarding the binder resin A, “APES-1” to “APES-5” mean the non-crystalline polyester resins APES-1 to APES-5 shown in Table 2, respectively.
In Table 1, regarding binder resins B and C, “CPES-1” to “CPES-8” mean crystalline polyester resins CPES-1 to CPES-8 shown in Table 3, respectively.
The unit of “amount” in Table 1 is parts by mass. Each “amount” of the binder resins B and C (respectively crystalline polyester resins) indicates a relative amount with respect to 80 parts by mass of the binder resin A (non-crystalline polyester resin).
In Table 1, ΔSP ₁ (specifically, the absolute value of the difference between the SP value of the binder resin A and the SP value of the binder resin B) and ΔSP ₂ (specifically, the SP value of the binder resin A and the binder resin) The unit of each of (the absolute value of the difference between the C SP value) is “(cal / cm ³ ) ^1/2 ”.

In Table 2, “BPA-PO” means a bisphenol A propylene oxide adduct, and “C3 diol” means 1,2-propanediol.
Among the monomers shown in Table 2, BPA-PO and C3 diol correspond to the alcohol component, and fumaric acid, terephthalic acid, adipic acid, and trimellitic acid correspond to the acid component. In Table 2, the numerical value in parentheses indicating the amount indicates the molar ratio (unit: mol%) of each component (alcohol component or acid component).

In Table 3, “C2 diol” means ethylene glycol, “C4 diol” means 1,4-butanediol, and “C6 diol” means 1,6-hexanediol.
Among the monomers shown in Table 3, C2 diol, C4 diol, and C6 diol correspond to the alcohol component, and fumaric acid and sebacic acid correspond to the acid component. In Table 3, the numerical value in parentheses indicating the amount indicates the molar ratio (unit: mol%) of each component (alcohol component or acid component).

  Hereinafter, a manufacturing method, an evaluation method, and an evaluation result of toners TA-1 to TA-10 and TB-1 to TB-8 will be described in order. In the evaluation in which an error occurs, a considerable number of measurement values with sufficiently small errors are obtained, and the arithmetic average of the obtained measurement values is used as the evaluation value.

[Preparation of materials]
(Preparation method of non-crystalline polyester resin)
In a 5 L four-necked flask equipped with a thermometer (thermocouple), dehydration tube, nitrogen introduction tube, and stirrer, the types and amounts of monomers (resin raw materials) shown in Table 2 and dibutyltin oxide 4 g was added. For example, in the preparation of the amorphous polyester resin APES-1, 1020 g of bisphenol A propylene oxide adduct (30 mol% of all alcohol components), 4500 g of 1,2-propanediol (70 mol% of all alcohol components), 1800 g of fumaric acid (40 mol% of the acid component), 3050 g of terephthalic acid (40 mol% of the acid component), 1000 g of adipic acid (15 mol% of the acid component), and 200 g of trimellitic acid (5 mol% of the acid component) ) And 4 g of dibutyltin oxide were added (see Table 2).

Subsequently, the contents of the flask were reacted at a temperature of 220 ° C. for 9 hours. Subsequently, the pressure in the flask was reduced, and the reaction product (resin) had a Tm (softening point) shown in Table 2 under a reduced pressure atmosphere (pressure 8 kPa) and a temperature of 220 ° C. (in the case of non-crystalline polyester resin APES-1). The contents of the flask were reacted until the temperature reached 95 ° C. As a result, amorphous polyester resins APES-1 to APES-5 having physical properties shown in Table 2 were obtained. Regarding the amorphous polyester resin APES-1, Tm (softening point) is 95 ° C., Tg (glass transition point) is 55 ° C., acid value is 15 mgKOH / g, hydroxyl value is 30 mgKOH / g, Mw (mass average molecular weight). Was 45000, Mn (number average molecular weight) was 2500, and SP value was 13.5 (cal / cm ³ ) ^1/2 .

(Preparation method of crystalline polyester resin)
In a 5 L four-necked flask equipped with a thermometer (thermocouple), dehydration tube, nitrogen introduction tube, and stirrer, the types and amounts of monomers (resin raw materials) shown in Table 3 and 1, 4 -Add 2.5 g of benzenediol. For example, in the preparation of the crystalline polyester resin CPES-1, 1560 g of 1,4-butanediol (100 mol% of all alcohol components), 800 g of fumaric acid (60 mol% of acid components), and 550 g of sebacic acid (acid components) 40 mol%) and 2.5 g of 1,4-benzenediol were added (see Table 3).

  Subsequently, the temperature of the flask contents was raised to 170 ° C. in a normal pressure atmosphere, and the flask contents were reacted for 5 hours in a normal pressure atmosphere and a temperature of 170 ° C. Subsequently, the temperature of the flask contents was raised to 210 ° C. in a normal pressure atmosphere, and the flask contents were reacted for 1.5 hours in a normal pressure atmosphere and a temperature of 210 ° C.

Subsequently, the pressure inside the flask was reduced, and the reaction product (resin) had a Tm (softening point) shown in Table 3 at a reduced pressure atmosphere (pressure 8 kPa) and a temperature of 210 ° C. (in crystalline polyester resin CPES-1, The flask contents were reacted until the temperature reached 89 ° C. As a result, crystalline polyester resins CPES-1 to CPES-8 having physical properties shown in Table 3 were obtained. Regarding crystalline polyester resin CPES-1, Tm (softening point) is 89 ° C., Mp (melting point) is 79 ° C., acid value is 3.0 mgKOH / g, hydroxyl value is 7.0 mgKOH / g, Mw (mass average molecular weight) ) Was 54000, Mn (number average molecular weight) was 3600, and SP value was 13.0 (cal / cm ³ ) ^1/2 .

[Toner Production Method]
(Preparation of toner base particles)
Using an FM mixer (“FM-20B” manufactured by Nippon Coke Kogyo Co., Ltd.), the types and amounts of binder resins A to C shown in Table 1 (however, in the production of each of toner TB-7 and TB-8, Binder resins A and B only), 5 parts by mass of ester wax (“Nissan Electol (registered trademark) WEP-3” manufactured by NOF Corporation) and carbon black (“MA-100” manufactured by Mitsubishi Chemical Corporation) 4 parts by mass and 1 part by mass of a quaternary ammonium salt (“BONTRON (registered trademark) P-51” manufactured by Orient Chemical Co., Ltd.) were mixed. For example, in the production of toner TA-1, 80 parts by mass of amorphous polyester resin APES-1, 5 parts by mass of crystalline polyester resin CPES-1, 5 parts by mass of crystalline polyester resin CPES-2, 5 parts by mass of ester wax (Nissan Electol WEP-3), 4 parts by mass of carbon black (MA-100), and 1 part by mass of a quaternary ammonium salt (BONTRON P-51) were mixed.

  Subsequently, the obtained mixture was mixed at a material supply speed of 6 kg / hour, a shaft rotation speed of 160 rpm, and a melt kneading temperature (cylinder temperature) of 120 ° C. using a twin screw extruder (“PCM-30” manufactured by Ikegai Co., Ltd.) It was melt-kneaded under the conditions. Thereafter, the obtained kneaded material was cooled. Subsequently, the cooled kneaded material was coarsely pulverized using a pulverizer (“Rotoplex 16/8” manufactured by Toa Machinery Co., Ltd.). Subsequently, the obtained coarsely pulverized product was finely pulverized using a pulverizer (“Turbo Mill RS Model” manufactured by Freund Turbo Co., Ltd.). Subsequently, the obtained finely pulverized product was classified using a classifier (“Elbow Jet EJ-LABO type” manufactured by Nippon Steel Mining Co., Ltd.). As a result, toner mother particles having a volume median diameter of 7 μm were obtained.

(External addition process)
Using an FM mixer (“FM-10B” manufactured by Nippon Coke Kogyo Co., Ltd.) under the conditions of a rotational speed of 3000 rpm and a jacket temperature of 20 ° C., 100 parts by mass of toner base particles and hydrophobic silica particles (manufactured by Nippon Aerosil Co., Ltd. “ AEROSIL (registered trademark) RA-200H ", content: dry silica particles surface-modified with trimethylsilyl group and amino group, number average primary particle size: about 12 nm), 1.5 parts by mass of conductive titanium oxide fine particles (titanium) “EC-100” manufactured by Kogyo Co., Ltd., substrate: TiO ₂ particles, coating layer: Sb-doped SnO ₂ layer, volume median diameter: about 0.35 μm) and 0.8 part by mass were mixed for 2 minutes. As a result, external additives (silica particles and titanium oxide particles) adhered to the surface of the toner base particles. Then, sieving was performed using a 300 mesh sieve (aperture 48 μm). As a result, toners (toners TA-1 to TA-10 and TB-1 to TB-8) containing a large number of toner particles were obtained.

[Evaluation method]
The evaluation method of each sample (toners TA-1 to TA-10 and TB-1 to TB-8) is as follows.

(Heat resistant storage stability)
2 g of toner (evaluation target: any one of toners TA-1 to TA-10 and TB-1 to TB-8) is put in a 20 mL polyethylene container, and the container is set in a thermostatic chamber set at a temperature of 55 ° C. It was allowed to stand for 3 hours. Thereafter, the toner taken out from the thermostat was cooled to room temperature (about 25 ° C.) to obtain an evaluation toner.

Subsequently, the obtained toner for evaluation was placed on a sieve having a known mass of 200 mesh (aperture 75 μm). Then, the mass of the sieve containing the evaluation toner was measured, and the mass of the toner on the sieve (the mass of the toner before sieving) was determined. Subsequently, the above sieve is set in a powder property evaluation apparatus (“Powder Tester (registered trademark)” manufactured by Hosokawa Micron Corporation), and according to the manual of the powder tester, the sieve is vibrated for 30 seconds under the conditions of the rheostat scale 5 for evaluation. The toner was sieved. After sieving, the mass of toner remaining on the sieve without passing through the sieve (the mass of toner after sieving) was measured. Based on the mass of the toner before sieving and the mass of the toner after sieving, the degree of toner aggregation (unit: mass%) was determined according to the following formula.
Toner aggregation degree = 100 × mass of toner after sieving / mass of toner before sieving

  When the toner aggregation degree was 20% by mass or less, it was evaluated as good (good), and when the toner aggregation degree was higher than 20% by mass, it was evaluated as x (not good).

(Fixing conditions)
Using a ball mill, 100 parts by mass of developer carrier (FS-C5250DN carrier) and 5 parts by mass of toner (evaluation target: toners TA-1 to TA-10 and TB-1 to TB-8) are used. Were mixed for 30 minutes to prepare a two-component developer.

  As an evaluation machine, a printer having a Roller-Roller type heating and pressing type fixing device (an evaluation machine in which “FS-C5250DN” manufactured by Kyocera Document Solutions Co., Ltd. was modified to change the fixing temperature) was used. The two-component developer prepared as described above is put into a developing device of an evaluation machine, and a replenishing toner (evaluation object: any one of toners TA-1 to TA-10 and TB-1 to TB-8) is evaluated. Into the toner container of the machine.

Using the above-mentioned evaluation machine in an environment of a temperature of 23 ° C. and a humidity of 50% RH, an evaluation paper (“ColorCopy (registered trademark)” manufactured by Mondi, A4 size, basis weight 90 g / m ² ) is applied to a linear speed of 200 mm / second. Then, a solid image (specifically, an unfixed toner image) having a size of 25 mm × 25 mm was formed under the condition of an applied toner amount of 1.0 mg / cm ² . Subsequently, the paper on which the image was formed was passed through the fixing device of the evaluation machine.

(Fixability: low temperature)
In the evaluation of the minimum fixing temperature, the measuring range of the fixing temperature was 100 ° C. or higher and 200 ° C. or lower. The fixing conditions were as described above. Specifically, the fixing temperature of the fixing device was increased from 100 ° C. by 5 ° C., and whether or not fixing was possible was determined for each fixing temperature, and the lowest temperature (minimum fixing temperature) at which a solid image (toner image) can be fixed on paper was measured. Whether or not the toner could be fixed was confirmed by a rubbing test as shown below. Specifically, the evaluation paper passed through the fixing device was folded in half so that the surface on which the image was formed was on the inside, and the image on the crease was rubbed 5 times with a 1 kg brass weight coated with a cloth. . Subsequently, the paper was spread and the bent portion of the paper (the portion where the solid image was formed) was observed. Then, the length (peeling length) of toner peeling at the bent portion was measured. The lowest temperature among the fixing temperatures at which the peeling length was 1 mm or less was defined as the lowest fixing temperature. When the minimum fixing temperature was 140 ° C. or lower, it was evaluated as “good”, and when the minimum fixing temperature exceeded 140 ° C., it was evaluated as “poor” (not good).

(Fixability: high temperature)
In the evaluation of the maximum fixing temperature, the measuring range of the fixing temperature was 150 ° C. or higher and 230 ° C. or lower. The fixing conditions were as described above. Specifically, the fixing temperature of the fixing device was increased from 150 ° C. by 5 ° C., and the maximum temperature at which no offset occurred (maximum fixing temperature) was measured. The evaluation sheet passed through the fixing device was visually checked to determine whether or not an offset occurred. Specifically, it was determined that an offset had occurred if there was dirt on the evaluation paper due to toner adhering to the fixing roller. When the maximum fixing temperature was 190 ° C. or higher, it was evaluated as “good”, and when the maximum fixing temperature was lower than 190 ° C., it was evaluated as “poor” (not good).

[Evaluation results]
Table 4 shows the evaluation results for each sample (toners TA-1 to TA-10 and TB-1 to TB-8). The evaluation results shown in Table 4 are the minimum fixing temperature for low temperature fixability, the maximum fixing temperature for high temperature fixability, and the toner aggregation degree for heat resistant storage stability.

Toners TA-1 to TA-10 (toners according to Examples 1 to 10) each had the above-described basic configuration. Specifically, in the toners TA-1 to TA-10, the toner particles are non-crystalline polyester resin (binder resin A), first crystalline polyester resin (binder resin B), and second crystalline polyester resin ( Binder resin C) (see Table 1). The absolute value (ΔSP ₁ ) of the difference between the SP value of the non-crystalline polyester resin and the SP value of the first crystalline polyester resin is 0.3 (cal / cm ³ ) ^1/2 or more and 0.7 (cal / cm ³ ) ^1/2 or less (see Tables 1 to 3). The absolute value (ΔSP ₂ ) of the difference between the SP value of the non-crystalline polyester resin and the SP value of the second crystalline polyester resin is 0.8 (cal / cm ³ ) ^1/2 or more and 1.2 (cal / cm ³ ) ^1/2 or less (see Tables 1 to 3). The amorphous polyester resin contained bisphenol A in a proportion of 20 mol% or more and 40 mol% or less with respect to all alcohol components (see Tables 1 and 2).

  As shown in Table 4, the toners TA-1 to TA-10 were excellent in heat-resistant storage stability, low-temperature fixability, and high-temperature fixability.

  In the production of the toner TB-4, the amorphous polyester resin and the crystalline polyester resin were not sufficiently compatible with each other, and could not be appropriately melt-kneaded.

  The toner according to the present invention can be used to form an image in, for example, a copying machine, a printer, or a multifunction machine.

Claims (6)

A toner comprising a plurality of toner particles containing an amorphous polyester resin,
The toner particles further contain a first crystalline polyester resin and a second crystalline polyester resin,
The difference between the SP value of the non-crystalline polyester resin and the SP value of the first crystalline polyester resin is 0.3 (cal / cm ³ ) ^1/2 or more and 0.7 (cal / cm ³ ) in absolute value. ^1/2 or less,
The difference between the SP value of the amorphous polyester resin SP value and the second crystalline polyester resin is an absolute value 0.8 (cal / cm ^{3) 1/2} or more 1.2 (cal / cm ^{3) 1/2} or less,
The non-crystalline polyester resin is a toner containing bisphenol A at a ratio of 20 mol% or more and 40 mol% or less with respect to all alcohol components. The toner is a pulverized toner;
The glass transition point of the non-crystalline polyester resin is 50 ° C. or more and 60 ° C. or less,
The amount of the first crystalline polyester resin and the amount of the second crystalline polyester resin are respectively 5 parts by mass or more and 15 parts by mass or less with respect to 80 parts by mass of the amorphous polyester resin. The toner described. The non-crystalline polyester resin is a polymer of monomers including bisphenol A which may have an adduct, 1,2-propanediol, aromatic dicarboxylic acid and trivalent carboxylic acid,
The said 1st crystalline polyester resin and the said 2nd crystalline polyester resin are polymers of the monomer containing (alpha), omega-alkanediol and unsaturated dicarboxylic acid, respectively. toner. The SP value of the non-crystalline polyester resin is 13.0 (cal / cm ³ ) ^1/2 or more and 14.0 (cal / cm ³ ) ^1/2 or less,
The SP value of the first crystalline polyester resin is 12.7 (cal / cm ³ ) ^1/2 or more and 14.0 (cal / cm ³ ) ^1/2 or less,
The toner according to claim 3, wherein the SP value of the second crystalline polyester resin is 12.2 (cal / cm ³ ) ^1/2 or more and 14.8 (cal / cm ³ ) ^1/2 or less.   5. The toner according to claim 3, wherein the amount of the first crystalline polyester resin is 0.2 to 5.0 times the amount of the second crystalline polyester resin.   The toner according to any one of claims 1 to 5, which is a positively chargeable toner.