JP2019053129A - toner - Google Patents

Abstract

To comparatively inexpensively provide a toner excellent in not only color reproducibility but also releasability and adhesion resistance.SOLUTION: A toner contains a plurality of toner particles. The toner particles each contain a binder resin, a coloring agent and a mold release agent. The coloring agent contains a cyan pigment and a green pigment. The cyan pigment is C.I.pigment blue 15:3. The green pigment is at least one selected from the group consisting of C.I.pigment green 7 and C.I.pigment green 36. The mold release agent contains one or more synthetic ester wax. A melting point of the mold release agent is 65°C or higher and 75°C or lower. In each of the toner particles, a mold release agent domain containing the mold release agent is dispersed into the binder resin. A dispersion diameter of the mold release agent domain is 0.5 μm or more and 1.5 μm or less. A surface adsorption force of the toner particles is 15 nN or more and 35 nN or less.SELECTED DRAWING: None

Description

  The present invention relates to a toner. Specifically, the present invention relates to a toner containing a cyan pigment and a green pigment.

  C. I. Pigment Blue 15 or 16 as well as C.I. I. A toner containing CI Pigment Green 7 or 36 has been proposed (see, for example, Patent Document 1 below).

Japanese Patent Laid-Open No. 01-159666

  As described in Patent Document 1, C.I. I. Pigment blue 15 and C.I. I. By using together with CI Pigment Green 7 or 36, we succeeded in providing a light blue toner excellent in color reproducibility at a relatively low cost. However, it was found that the toner described in Patent Document 1 is inferior in releasability. Further, when an attempt was made to improve the low-temperature fixability of the toner described in Patent Document 1 using a binder resin having a low melting point, the releasability was markedly reduced. When the release agent material and / or the release agent content is adjusted in order to improve the release property of the toner described in Patent Document 1, contamination with the toner may become remarkable. When the contamination by the toner becomes remarkable, it becomes difficult to charge the toner to a desired charge amount.

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a toner that is excellent not only in color reproducibility but also in releasability and adhesion resistance at a relatively low cost.

  The toner according to the present invention includes a plurality of toner particles. Each of the toner particles includes a binder resin, a colorant, and a release agent. The colorant contains a cyan pigment and a green pigment. The cyan pigment is C.I. I. Pigment Blue 15: 3. The green pigment is C.I. I. Pigment green 7 and C.I. I. At least one selected from the group consisting of CI Pigment Green 36. The mold release agent contains one or more synthetic ester waxes. The melting point of the release agent is 65 ° C. or higher and 75 ° C. or lower. In each of the toner particles, a release agent domain containing the release agent is dispersed in the binder resin. The dispersion diameter of the release agent domain in the cross section of the toner particles is 0.5 μm or more and 1.5 μm or less. The toner particles have a surface adsorption force of 15 nN to 35 nN.

  According to the present invention, it is possible to provide a toner that is excellent not only in color reproducibility but also in releasability and adhesion resistance at a relatively low cost.

  An embodiment of the present invention will be described. In addition, the evaluation result (a value indicating the shape or physical properties) of the powder is the number average of the values measured for a considerable number of particles unless otherwise specified. The powder includes, for example, a toner core, toner base particles, an external additive, and toner. The toner base particles mean toner particles before the external additive adheres.

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 not specified, and the “Coulter Counter Multisizer 3” manufactured by Beckman Coulter Co., Ltd. is used. ) Measured based on.

  The measured values of acid value (AV) and hydroxyl value (OHV) are values measured in accordance with “JIS (Japanese Industrial Standard) K0070-1992” unless otherwise specified. Each measured value of the number average molecular weight (Mn) and the mass average molecular weight (Mw) is a value measured using gel permeation chromatography unless otherwise specified. The glass transition point (Tg) and the melting point (Mp) are values measured using a differential scanning calorimeter (“DSC-6220” manufactured by Seiko Instruments Inc.) unless otherwise specified. The softening point (Tm) is a value measured using a Koka type flow tester (“CFT-500D” manufactured by Shimadzu Corporation) unless otherwise specified.

  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. Acrylic and methacrylic are sometimes collectively referred to as “(meth) acrylic”.

  The toner according to the exemplary embodiment is a toner for developing an electrostatic latent image that can be suitably used for developing an electrostatic latent image. The toner according to the exemplary embodiment may constitute a one-component developer or may constitute a two-component developer together with a carrier. When the toner constitutes a one-component developer, the toner is charged by friction with the blade in the developing device. When the toner constitutes a two-component developer, the toner is charged by friction with the carrier in the developing device. The toner according to the exemplary embodiment is positively or negatively charged by friction with the blade or the carrier.

  The toner according to the exemplary embodiment can be used for forming an image 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 electrostatic latent image is formed on the photoconductor based on the image data. Next, the formed electrostatic latent image is developed using toner. In the developing step, 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 attached to the electrostatic latent image to form a toner image on the photosensitive member. In the subsequent transfer process, the toner image on the photoreceptor is transferred to a recording medium (for example, paper). Thereafter, the toner is heated to fix the toner on the recording medium. As a result, an image is formed on the recording medium.

[Basic toner configuration]
The toner according to the exemplary embodiment has the following configuration (hereinafter, sometimes referred to as “basic configuration”). Specifically, the toner according to the exemplary embodiment includes a plurality of toner particles. Each toner particle includes a binder resin, a colorant, and a release agent. The colorant contains a cyan pigment and a green pigment. The cyan pigment is C.I. I. Pigment Blue 15: 3. The green pigment is C.I. I. Pigment green 7 and C.I. I. At least one selected from the group consisting of CI Pigment Green 36. The release agent contains one or more synthetic ester waxes. The melting point of the release agent is 65 ° C. or higher and 75 ° C. or lower. In each of the toner particles, a release agent domain containing a release agent is dispersed in the binder resin. The dispersion diameter of the release agent domain in the cross section of the toner particle is 0.5 μm or more and 1.5 μm or less. The surface adsorption force of the toner particles is 15 nN or more and 35 nN or less. Hereinafter, “CI Pigment Blue 15: 3” is referred to as “Cyan Pigment X”. “At least one pigment selected from the group consisting of CI Pigment Green 7 and CI Pigment Green 36” is referred to as “Green Pigment Y”. The “dispersion diameter of the release agent domain in the cross section of the toner particle” is simply referred to as “dispersion diameter of the release agent domain”.

  The inventor has succeeded in providing a light blue toner excellent in color reproducibility at a relatively low cost by using the cyan pigment X and the green pigment Y in combination. However, it has been found that the toner containing the cyan pigment X and the green pigment Y (first prototype toner) is inferior in releasability compared with the toner not containing the green pigment Y. In particular, when the green pigment Y having a small particle diameter is used in order to improve the color developability, the releasability is markedly lowered. Even when an attempt was made to improve the low-temperature fixability of the first prototype toner using a binder resin having a low melting point, the releasability was significantly reduced.

  Generally, the toner releasability is enhanced by adding a release agent to the toner. Therefore, the present inventor adjusts the material of the release agent and / or the content of the release agent in the first trial toner, and not only the color reproducibility but also the excellent release property (second trial toner). I thought we could provide However, when an image was formed using the second prototype toner, contamination with the toner occurred. In particular, when an image was formed using the second prototype toner in a high temperature and high humidity environment, the toner was significantly contaminated.

  The inventor has intensively studied the reason why the second prototype toner has poor adhesion resistance. It has been found that the toner having the above-described basic configuration is excellent not only in color reproducibility but also in releasability and adhesion resistance. Further, it has been found that the toner having the above-described basic configuration is excellent in low-temperature fixability, heat resistance, and charging stability.

  Specifically, in the toner according to the present embodiment, the toner particles contain a cyan pigment X and a green pigment Y. Thereby, the light blue toner excellent in color reproducibility can be provided relatively inexpensively.

  In the toner according to the exemplary embodiment, the releasing agent has a melting point of 65 ° C. or higher and 75 ° C. or lower. The release agent contains one or more synthetic ester waxes. The dispersion diameter of the release agent domain is 0.5 μm or more and 1.5 μm or less. The surface adsorption force of the toner particles is 15 nN or more and 35 nN or less. For these reasons, the toner according to the exemplary embodiment is excellent in releasability and adhesion resistance, and is also excellent in low-temperature fixability, heat resistance, and charging stability.

  More specifically, when the melting point of the release agent is 65 ° C. or higher and 75 ° C. or lower, the melting point of the toner can be within a desired temperature range. Specifically, if the melting point of the release agent is 65 ° C. or more and 75 ° C. or less, the melting point of the toner can be prevented from becoming too low, and thus the heat resistance of the toner is easily improved. For example, even when the toner according to this embodiment is stored in a high temperature environment, aggregation of toner particles can be effectively prevented. The higher the melting point of the release agent, the higher the melting point of the toner. Further, when the melting point of the release agent is 65 ° C. or more and 75 ° C. or less, it is possible to prevent the toner melting point from becoming too high. Therefore, the low temperature fixability of the toner is likely to be improved. More specifically, it is easy to reliably fix the toner at a low temperature. The lower the melting point of the release agent, the lower the melting point of the toner. When the release agent contains two or more kinds of waxes, the melting point of the release agent is 65 ° C. or more and 75 ° C. or less. The melting point of the mixture of two or more waxes is 65 ° C. or more and 75 ° C. or less. It means that there is.

  In recent years, it has been found that if the release agent contains one or more kinds of synthetic ester wax, the release property of the toner is easily improved as compared with the case where the release agent is composed of only natural wax. The release agent may be composed of one or more kinds of synthetic ester waxes, and may further contain a natural wax.

  If the dispersion diameter of the release agent domain is 0.5 μm or more and 1.5 μm or less, the occupation ratio of the release agent domain in the toner particles can be within a desired range. Specifically, if the dispersion diameter of the release agent domain is 0.5 μm or more and 1.5 μm or less, the occupancy of the release agent domain can be prevented from becoming too low, so that the content of the release agent is easily secured. . Thereby, the toner releasability is easily improved. The larger the dispersion diameter of the release agent domain, the higher the occupation ratio of the release agent domain.

  In addition, if the dispersion diameter of the release agent domain is 0.5 μm or more and 1.5 μm or less, it is possible to prevent the release agent domain occupancy from becoming too high, so that the release agent domain is exposed on the surface of the toner particles. It is possible to prevent the rate from becoming too high. Generally, the melting point of the release agent is lower than the melting point of the binder resin. Therefore, if the exposure rate of the release agent domain can be prevented from becoming too high, the heat resistance of the toner is likely to be improved, and the adhesion resistance of the toner is likely to be improved. When the adhesion resistance of the toner is improved, it becomes difficult for the toner to adhere to a member (for example, a photoreceptor or a developing sleeve) or a carrier constituting the image forming apparatus during image formation, so that the toner is easily charged to a desired charge amount. For example, even when an image is formed in a high-temperature and high-humidity environment using the toner according to the present embodiment, the toner can be effectively prevented from being contaminated, so that the toner can be charged to a desired charge amount. . Therefore, the charging stability of the toner is likely to be improved.

  In addition, if the exposure rate of the release agent domain can be prevented from becoming too high, the release agent is prevented from detaching from the toner particles even when mechanical stress is applied to the toner particles. it can. For example, even when the toner is agitated in the developing device, the release agent can be prevented from being detached, so that the fluidity of the toner particles in the developing device is easily ensured. This also makes it easy to charge the toner to a desired charge amount, so that the charging stability of the toner is likely to be improved. The smaller the dispersion diameter of the release agent domain, the lower the occupation ratio of the release agent domain. The dispersion diameter of the release agent domain is measured by the method described in the examples below or a method analogous thereto.

  If the surface adsorption force of the toner particles is 15 nN or more and 35 nN or less, the adhesion force of the toner to the recording medium can be ensured, so that the low-temperature fixability of the toner is easily improved. As the surface adsorption force of the toner particles is larger, the adhesion force of the toner to the recording medium tends to be ensured. Further, when the surface adsorption force of the toner particles is 15 nN or more and 35 nN or less, the toner adhesion resistance is easily improved. As a result, since the toner is easily charged to a desired charge amount, the charging stability of the toner is easily improved. As the surface adsorption force of the toner particles is smaller, the toner adhesion resistance tends to be improved. The surface adsorption force of the toner particles is measured by the method described in Examples described later or a method analogous thereto.

[Example of material constituting toner]
The toner particles preferably have toner base particles, and may further have an external additive. The toner base particles may be capsule toner particles, but are preferably non-capsule toner particles. When the toner base particles are capsule toner particles, the toner base particles have a toner core and a shell layer that covers the surface of the toner core. When the toner base particles are non-capsule toner particles, the toner base particles have a toner core but no shell layer.

<Toner base particles>
(Toner core)
In the toner core, the binder resin generally 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 core. By using a combination of a plurality of types of resins as the binder resin, the properties of the binder resin (more specifically, the hydroxyl value, acid value, glass transition point, softening point, etc.) can be adjusted. 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 core tends to be anionic, and when the binder resin has an amino group, the toner core Tends to be cationic.

  The toner core further includes a colorant and a release agent as well as the binder resin. The toner core may further include a charge control agent. Hereinafter, it demonstrates in order.

(Binder resin)
The binder resin preferably contains an amorphous polyester resin having a mass average molecular weight of 10,000 or more and less than 50,000. Thereby, the surface adsorption force of the toner particles tends to be 15 nN or more and 35 nN or less. As the mass average molecular weight of the amorphous polyester resin is smaller, the surface adsorption force of the toner particles tends to be smaller. As the mass average molecular weight of the amorphous polyester resin is larger, the surface adsorption force of the toner particles tends to increase. More preferably, the binder resin contains an amorphous polyester resin having a mass average molecular weight of 15000 or more and 45000 or less.

  The physical properties of the amorphous polyester resin will be further described. The acid value of the amorphous polyester resin is preferably 5 mgKOH / g or more and 30 mgKOH / g or less, and the hydroxyl value of the amorphous polyester resin is preferably 15 mgKOH / g or more and 80 mgKOH / g or less. The mass average molecular weight of the amorphous polyester resin is 10,000 or more and 50000 or less, and the molecular weight distribution of the amorphous polyester resin (ratio Mw / Mn of the mass average molecular weight (Mw) to the number average molecular weight (Mn)) is 8. If it is 50 or more, the fixing property of the toner is easily secured. When the mass average molecular weight of the amorphous polyester resin is too large, high temperature offset is likely to occur. This can be said even when the molecular weight distribution (= Mw / Mn) of the amorphous polyester resin is too large. If the mass average molecular weight of the amorphous polyester resin is too small, it may be difficult to reliably fix the toner at a low temperature. This can be said even when the molecular weight distribution (= Mw / Mn) of the amorphous polyester resin is too small.

  The binder resin may further contain a crystalline polyester resin. Thereby, since the toner core tends to have a sharp melt property, a toner excellent in both low-temperature fixability and heat resistance is easily obtained. The amount of the crystalline polyester resin contained in the toner core is preferably 1% by mass or more and 50% by mass or less, and more preferably 5% by mass or more and 25% by mass or less with respect to the total amount of the polyester resin contained in the toner core. For example, when the total amount of the polyester resin contained in the toner core is 100 g, the amount of the crystalline polyester resin contained in the toner core is preferably 1 g or more and 50 g or less, more preferably 5 g or more and 25 g or less. Here, “the total amount of the polyester resin contained in the toner core” means the sum of the amount of the crystalline polyester resin contained in the toner core and the amount of the amorphous polyester resin contained in the toner core.

  In order for the toner core to have an appropriate sharp melt property, the toner core preferably contains a crystalline polyester resin having a crystallinity index of 0.90 or more and less than 1.10, and the crystallinity index of 0.98 or more and 1 More preferably, it contains a crystalline polyester resin that is less than .05. The crystallinity index of the resin corresponds to the ratio (= Tm / Mp) of the softening point (Tm) of the resin to the melting point (Mp) of the resin. For non-crystalline resins, it is often not possible to measure a clear melting point. The crystallinity index of the crystalline polyester resin can be adjusted by changing the type or amount of a material (for example, alcohol and / or carboxylic acid) for synthesizing the crystalline polyester resin. The toner core may contain one type of crystalline polyester resin, or may contain two or more types of crystalline polyester resin. More preferably, the toner core contains a crystalline polyester resin having a melting point of 50 ° C. or higher and 100 ° C. or lower.

  In order to ensure toner fixability even during high-speed fixing, the glass transition point of the binder resin (the most common binder resin when the toner core contains multiple types of binder resins) is 30 ° C. or higher. It is preferably 60 ° C. or lower, and more preferably 35 ° C. or higher and 55 ° C. or lower. Further, in order to ensure the toner fixability even during high-speed fixing, the softening point of the binder resin (the most binder resin when the toner core contains a plurality of types of binder resins) is 60 ° C. The temperature is preferably 150 ° C. or lower and more preferably 70 ° C. or higher and 140 ° C. or lower.

  The polyester resin is a copolymer of one or more alcohols and one or more carboxylic acids. As alcohol for synthesizing a polyester resin, the following dihydric alcohol or trihydric or higher alcohol can be used, for example. As the dihydric alcohol, for example, diols or bisphenols can be used. As the carboxylic acid for synthesizing the polyester resin, for example, the following divalent carboxylic acids or trivalent or higher carboxylic acids can be used.

  Preferable examples of diols include aliphatic diols. Suitable examples of the aliphatic diol include diethylene glycol, triethylene glycol, neopentyl glycol, 1,2-propanediol, α, ω-alkanediol, 2-butene-1,4-diol, 1,4-cyclohexanedi Examples include methanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, or polytetramethylene glycol. α, ω-alkanediol includes, for example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1, 8-octanediol, 1,9-nonanediol, or 1,12-dodecanediol is preferred.

  Preferable examples of the 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, α, ω-alkane dicarboxylic acid, unsaturated dicarboxylic acid, and cycloalkane dicarboxylic acid. The aromatic dicarboxylic acid is preferably, for example, phthalic acid, terephthalic acid, or isophthalic acid. The α, ω-alkanedicarboxylic acid is preferably, for example, malonic acid, succinic acid, succinic anhydride, succinic acid derivative, adipic acid, suberic acid, azelaic acid, sebacic acid, or 1,10-decanedicarboxylic acid. . The succinic acid derivative is preferably, for example, alkyl succinic acid or alkenyl succinic acid. The alkyl succinic acid is preferably, for example, n-butyl succinic acid, isobutyl succinic acid, n-octyl succinic acid, n-dodecyl succinic acid, or isododecyl succinic acid. Alkyl succinic acid includes these anhydrides. The alkenyl succinic acid is preferably, for example, n-butenyl succinic acid, isobutenyl succinic acid, n-octenyl succinic acid, n-dodecenyl succinic acid, or isododecenyl succinic acid. Alkenyl succinic acid includes these anhydrides. The unsaturated dicarboxylic acid is preferably, for example, maleic acid, fumaric acid, citraconic acid, itaconic acid, or glutaconic acid. The cycloalkane dicarboxylic acid is preferably, for example, cyclohexane dicarboxylic acid.

  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.

  The amorphous polyester resin preferably contains bisphenols as an alcohol component. The bisphenol is preferably at least one of, for example, a bisphenol A ethylene oxide adduct and a bisphenol A propylene oxide adduct.

  The amorphous polyester resin preferably contains at least one of an aromatic dicarboxylic acid and an unsaturated dicarboxylic acid as an acid component. The aromatic dicarboxylic acid is preferably terephthalic acid, for example. The unsaturated dicarboxylic acid is preferably fumaric acid, for example.

  The amorphous polyester resin is composed of one or more bisphenols, one or more divalent carboxylic acids and one or more trivalent carboxylic acids (more specifically, trimellitic acid or trimellitic anhydride). It is preferable to contain a copolymer. As a result, even when the binder resin contains not only an amorphous polyester resin but also a crystalline polyester resin, the crystalline polyester resin and the amorphous polyester resin can be appropriately mixed in the toner core. it can.

  The crystalline polyester resin preferably contains α, ω-alkanediol having 2 to 8 carbon atoms as an alcohol component. The α, ω-alkanediol is preferably, for example, 1,4-butanediol (carbon number: 4) or 1,6-hexanediol (carbon number: 6).

  In order to sufficiently secure the crystallinity of the crystalline polyester resin, it is preferable that the ratio of the most abundant component (single component) in the alcohol component of the crystalline polyester resin is 70 mol% or more. It is more preferably at least mol%, particularly preferably 100 mol%. In order to sufficiently ensure the crystallinity of the crystalline polyester resin, it is preferable that 80 mol% or more of the alcohol component contained in the crystalline polyester resin is an aliphatic diol having 2 to 8 carbon atoms. More preferably, 90 mol% or more of the component is an aliphatic diol having 2 to 8 carbon atoms.

  The crystalline polyester resin preferably contains α, ω-alkanedicarboxylic acid having 2 to 16 carbon atoms (including carbon of two carboxyl groups) as an acid component. The α, ω-alkanedicarboxylic acid is preferably, for example, succinic acid having 4 carbon atoms or 1,10-decanedicarboxylic acid having 12 carbon atoms.

  In order to sufficiently secure the crystallinity of the crystalline polyester resin, it is preferable that the ratio of the most abundant component (single component) among the acid components of the crystalline polyester resin is 70 mol% or more. It is more preferably at least mol%, particularly preferably 100 mol%. In order to sufficiently secure the crystallinity of the crystalline polyester resin, it is preferable that 80 mol% or more of the acid component contained in the crystalline polyester resin is an aliphatic dicarboxylic acid having 2 to 16 carbon atoms. Preferably, 90 mol% or more of the component is an aliphatic dicarboxylic acid having 2 to 16 carbon atoms.

  The binder resin may contain a resin (other resin) that is not a polyester resin. The other resin is preferably a thermoplastic resin that is not a polyester resin. More specifically, the other resin is preferably, for example, a styrene resin, an acrylic acid resin, an olefin resin, a vinyl resin, a polyamide resin, or a urethane resin. As the acrylic resin, for example, an acrylic ester polymer or a methacrylic ester polymer can be used. As the olefin resin, for example, a polyethylene resin or a polypropylene resin can be used. As the vinyl resin, for example, vinyl chloride resin, polyvinyl alcohol, vinyl ether resin, or N-vinyl resin can be used. Further, a copolymer of each of these resins, that is, a copolymer in which any repeating unit is introduced into the above-described resin may be used as another thermoplastic resin. For example, a styrene-butadiene resin may be used as another thermoplastic resin.

(Coloring agent)
The colorant contains a cyan pigment X and a green pigment Y. The cyan pigment X is preferably, 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. The number average particle size of the cyan pigment X is preferably 500 nm or less, more preferably 50 nm or more and 400 nm or less, and further preferably 100 nm or more and 300 nm or less.

  The green pigment Y is preferably a copper phthalocyanine compound, for example. The number average particle diameter of the green pigment Y is preferably 500 nm or less. Thereby, since the dispersibility of the green pigment Y in the binder resin is easily ensured, the color developability of the toner is easily improved. As the number average particle size of the green pigment Y is smaller, the color developability of the toner tends to be improved. In addition, since the toner according to the exemplary embodiment has the above-described basic configuration, even when the number average particle diameter of the green pigment Y is 500 nm or less, the toner releasability can be prevented from being lowered. The number average particle size of the green pigment Y is more preferably 50 nm or more and 400 nm or less, and further preferably 100 nm or more and 300 nm or less.

  When the content of the green pigment Y is too large, the toner may exhibit a color different from a blue color (for example, light blue). For example, the content of the green pigment Y is preferably 70% by mass or less, more preferably 1% by mass or more and 60% by mass or less with respect to the total of the content of the cyan pigment X and the content of the green pigment Y. More preferably, it is 5 mass% or more and 40 mass% or less. The number average particle size of cyan pigment X is 500 nm or less, the number average particle size of green pigment Y is 500 nm or less, and the content of green pigment Y is the content of cyan pigment X and the content of green pigment Y. If it is 70 mass% or less with respect to the sum total, color reproducibility and color developability are easy to improve.

  The colorant may further contain a pigment that is not the cyan pigment X and the green pigment Y, or may further contain a dye. 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. Thereby, an image excellent in image quality is easily formed.

(Release agent)
The release agent is used, for example, for the purpose of improving the fixing property of the toner or the high-temperature offset resistance of the toner. The release agent contains one or more synthetic ester waxes. It is preferable that at least one of the synthetic ester waxes contained in the release agent is a synthetic ester wax having a melting point of 65 ° C. or higher and 75 ° C. or lower. Thereby, melting | fusing point of a mold release agent tends to be 65 degreeC or more and 75 degrees C or less. As long as the melting point of the release agent is 65 ° C. or higher and 75 ° C. or lower, the release agent may further contain a synthetic ester wax having a melting point of less than 65 ° C., or a synthetic ester having a melting point higher than 75 ° C. A wax may be further contained, or a natural wax may be further contained.

  The synthetic ester wax having a melting point of 65 ° C. or higher and 75 ° C. or lower is preferably, for example, a wax mainly composed of a fatty acid ester or a wax obtained by deoxidizing a part or all of the fatty acid ester. Waxes mainly composed of fatty acid esters are preferably, for example, montanic acid ester wax or caster wax. As the synthetic ester wax having a melting point of 65 ° C. or higher and 75 ° C. or lower, a commercially available product may be used. Examples of commercially available products include “Nissan Electol (registered trademark) WEP-3” (melting point: 73 ± 1 ° C.) manufactured by NOF Corporation, and “Nissan Electol WEP-4” (melting point: 71 manufactured by NOF CORPORATION). ± 1 ° C.) or “Nissan Electol WEP-7” (melting point: 70 ± 1 ° C.) manufactured by NOF Corporation can be used.

  The release agent may further contain at least one selected from the group consisting of an aliphatic hydrocarbon wax, a vegetable wax, an animal wax, and a mineral wax. The aliphatic hydrocarbon wax is preferably, for example, low molecular weight polyethylene, low molecular weight polypropylene, polyolefin copolymer, polyolefin wax, microcrystalline wax, paraffin wax, or Fischer-Tropsch wax. Aliphatic hydrocarbon waxes also contain these oxides. The vegetable wax is preferably, for example, candelilla wax, carnauba wax, wood wax, jojoba wax, or rice wax. The animal wax is preferably, for example, beeswax, lanolin, or whale wax. The mineral wax is preferably, for example, ozokerite, ceresin, or petrolatum. Among the waxes described above, vegetable waxes, animal waxes and mineral waxes are included in the natural waxes. As the natural wax, carnauba wax is preferably used.

  In order to improve the compatibility between the binder resin and the release agent, a compatibilizer may be added to the toner core.

(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 containing a positively chargeable charge control agent in the toner core, the cationic property of the toner core can be increased. By adding a negatively chargeable charge control agent to the toner core, the anionicity of the toner core can be enhanced.

(Shell layer)
The shell layer preferably contains a thermoplastic resin. This makes it easy to obtain a toner that is excellent in both low-temperature fixability and heat resistance. When the shell layer contains a styrene-acrylic acid resin, the charging stability of the toner is easily improved in addition to the improvement of the low-temperature fixability of the toner and the improvement of the heat resistance of the toner.

  If the toner base particles do not have a shell layer, the surface adsorption force of the toner particles can be easily adjusted by adjusting the mass average molecular weight of the amorphous polyester resin contained in the toner core. Therefore, in this embodiment, it is preferable that the toner base particles do not have a shell layer. That is, in this embodiment, the toner base particles are preferably non-capsule toner particles.

<External additive>
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). 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 can be adjusted by the stirring conditions, the particle diameter of the external additive particles, the shape of the external additive particles, the surface state of the external additive particles, and the like. The stirring conditions include, for example, the stirring time and the rotation speed of stirring.

  In order to sufficiently exert the function of the external additive while suppressing the detachment of the external additive particles from the toner particles, the amount of the external additive is 0.5 parts by mass with respect to 100 parts by mass of the toner base particles. The amount is preferably 10 parts by mass or less. When the toner particles include two or more kinds of external additive particles, the total amount of the 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. More preferably, the external additive particles are silica particles or metal oxide particles. Here, the metal oxide is preferably alumina, titanium oxide, magnesium oxide, zinc oxide, strontium titanate, or barium titanate. However, particles of an organic acid compound such as a fatty acid metal salt or resin particles may be used as the external additive particles. The fatty acid metal salt is preferably, for example, zinc stearate. 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.

  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. Further, in order to make the external additive function as a spacer between the toner particles to improve the heat-resistant storage property of the toner, the external additive particles are resin particles (powder having a number average primary particle diameter of 50 nm to 100 nm). Body).

[Toner Production Method]
The toner manufacturing method according to the present embodiment includes a toner base particle manufacturing process, and may further include an external addition process. In order to efficiently produce the toner, it is preferable to produce a large number of toner particles simultaneously. In addition, the toner particles produced at the same time are considered to have substantially the same configuration.

<Manufacturing process of toner base particles>
The toner mother particle manufacturing process preferably includes a toner core manufacturing process, and may further include a shell layer forming process.

(Manufacturing process of toner core)
The toner core is preferably produced by a known aggregation method or a known pulverization method. Thereby, the toner core can be easily manufactured. More specifically, when the toner core is produced by a known agglomeration method or a known pulverization method, the toner core can be easily produced because the internal additive is easily dispersed well in the binder resin.

  In an example of the pulverization method, first, a binder resin, a colorant, and a release agent are mixed. A charge control agent may be further mixed. The obtained mixture is melt-kneaded using a melt-kneading apparatus (for example, a uniaxial or biaxial extruder). The obtained melt-kneaded product is pulverized and 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.

  The lower the temperature at which the mixture is melt-kneaded (melt-kneading temperature), the smaller the dispersion diameter of the release agent domain in the produced toner base particles. The higher the melt kneading temperature, the larger the dispersion diameter of the release agent domain in the produced toner base particles.

  In an example of the aggregation method, first, these fine particles are aggregated in an aqueous medium containing fine particles of the binder resin, the release agent, and the colorant until a desired particle diameter is obtained. Thereby, aggregated particles containing the binder resin, the release agent, and the colorant are formed. The obtained aggregated particles are heated to unitize the components contained in the aggregated particles. Thereby, toner mother particles having a desired particle diameter are obtained.

(Shell layer formation process)
For example, the shell layer can be formed by using any one of an in-situ polymerization method, a submerged cured coating method, and a coacervation method.

<External addition process>
The toner base particles and the external additive are mixed using a mixer (for example, an FM mixer manufactured by Nippon Coke Kogyo Co., Ltd.). As a result, the external additive is physically bonded to the surface of the toner base particles. Thus, a toner containing a large number of toner particles is obtained.

  Examples of the present invention will be described. Table 1 shows the configuration of the toner according to the example or the comparative example.

  Table 2 shows the configuration of the binder resin in the examples or comparative examples. In Table 2, “Mw” represents the mass average molecular weight of the amorphous polyester resin.

  Table 3 shows the composition of the pigments in Examples or Comparative Examples. In Table 3, the “particle diameter” of the cyan pigment is the number average particle diameter of the cyan pigment. The “particle diameter” of the green pigment is the number average particle diameter of the green pigment. In the “blending ratio”, [cyan pigment content (unit: parts by mass)]: [green pigment content (unit: parts by mass)] is described. “C.I.P.B 15: 3” describes C.I.P.B. 15: 3. I. Pigment Blue 15: 3. “C.I.P.G 36” is C.I. I. It means CI Pigment Green 36. "C.I.P.G 7" I. It means CI Pigment Green 7.

  Both the cyan pigment and the green pigment had a sharp particle size distribution. More specifically, C.I. I. Pigment Blue 15: 3 substantially contained particles (cyan pigment) having a particle size of about 150 nm. In addition, C.I. I. Pigment Green 36 substantially contained particles (green pigment) having a particle size of about 200 nm. In addition, C.I. I. Pigment Green 7 substantially contained particles (green pigment) having a particle size of about 220 nm.

  Table 4 shows the constitution of the release agent in the examples or comparative examples. In Table 4, “WEP-3”, “WEP-2”, and “WEP-7” are “Nissan Electol WEP-3” manufactured by NOF Corporation and “Nissan Elektor WEP” manufactured by NOF Corporation, respectively. -2 "and" Nissan Electol WEP-7 "manufactured by NOF Corporation. Carnauba wax means carnauba wax ("Carnauba wax No. 1" manufactured by Hiroyuki Kato). “FT-100” means Fischer-Tropsch wax (“FT100” manufactured by Nippon Seiwa Co., Ltd.). “Rice wax” means rice wax (manufactured by Toa Kasei Co., Ltd.).

  Hereinafter, first, the synthesis method of the binder resin in the examples or comparative examples, the measurement method of the mass average molecular weight of the non-crystalline polyester resin, the preparation method of the pigment, the preparation method of the release agent, and the measurement of the melting point of the release agent The method will be described in order. Next, a method for producing toners according to Examples or Comparative Examples (more specifically, TA-1 to TA-10 and TB-1 to TB-8) will be described. Subsequently, a physical property value measurement method, an evaluation method, and an evaluation result of the obtained toner 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.

[Binder resin synthesis method]
(Synthesis method of non-crystalline polyester resin PES-11)
To a four-necked flask (volume: 5 L) equipped with a thermometer (more specifically, a thermocouple), a dehydrating tube, a nitrogen introducing tube, and a stirrer, 1575 g of bisphenol A propylene oxide adduct (BPA-PO) and 163 g of bisphenol A ethylene oxide adduct (BPA-EO), 377 g of fumaric acid and 4 g of dibutyltin oxide. Nitrogen was introduced into the flask to create a nitrogen atmosphere in the flask. While stirring the contents of the flask, the temperature in the flask was raised to 220 ° C. using an oil bath. The contents of the flask were allowed to react for 8 hours while distilling off by-product water while maintaining the inside of the flask in a nitrogen atmosphere and keeping the temperature inside the flask at 220 ° C.

  The internal pressure of the flask was lowered to about 60 mmHg. The contents of the flask were further reacted for 1 hour under high temperature and reduced pressure (temperature 220 ° C. and pressure 60 mmHg). After the temperature in the flask was lowered to 210 ° C., 336 g of trimellitic anhydride was added to the flask. The contents of the flask were reacted under high temperature and reduced pressure (temperature 210 ° C. and pressure 60 mmHg) until the physical properties of the reaction product (non-crystalline polyester resin PES-11) were as follows. Thereafter, the contents of the flask were removed from the flask and then cooled. In this way, an amorphous polyester resin PES-11 was obtained. In the amorphous polyester resin PES-11, the softening point is 100 ° C., the glass transition point is 50 ° C., the mass average molecular weight is 30000, the acid value is 15 mgKOH / g, and the hydroxyl value is 30 mgKOH / g. Met.

(Synthesis method of non-crystalline polyester resin PES-12 to PES-15)
According to the synthesis method of the amorphous polyester resin PES-11, except that the reaction conditions of the contents of the flask under high temperature reduced pressure (temperature 210 ° C. and pressure 60 mmHg) were changed, respectively, the amorphous polyester resin PES- 12 to PES-15 were synthesized. In the obtained non-crystalline polyester resin PES-12, the mass average molecular weight was 15000. In the obtained non-crystalline polyester resin PES-13, the mass average molecular weight was 45,000. In the obtained non-crystalline polyester resin PES-14, the mass average molecular weight was 9000. In the obtained non-crystalline polyester resin PES-15, the mass average molecular weight was 50000. In each of the non-crystalline polyester resins PES-12 to PES-15, the physical property values excluding the mass average molecular weight showed the same values as the non-crystalline polyester resin PES-11.

(Synthesis Method of Crystalline Polyester Resin PES-21)
A four-necked flask (volume: 5 L) equipped with a thermometer (more specifically, a thermocouple), a dehydrating tube, a nitrogen introducing tube, and a stirring device was set in an oil bath. A flask is charged with 132.0 g of 1,6-hexanediol, 230.0 g of 1,10-decanedicarboxylic acid, 0.3 g of 1,4-benzenediol, and 1.0 g of dibutyltin oxide. It was. Nitrogen was introduced into the flask to create a nitrogen atmosphere in the flask. While stirring the contents of the flask, the temperature in the flask was raised to 200 ° C. using an oil bath. The contents of the flask were allowed to react for 5 hours while distilling off by-product water while maintaining the inside of the flask in a nitrogen atmosphere and maintaining the temperature inside the flask at 200 ° C.

  The internal pressure of the flask was lowered to about 12 mmHg. The contents of the flask were reacted under high temperature and reduced pressure (temperature 200 ° C. and pressure 12 mmHg) until the physical properties of the reaction product (crystalline polyester resin PES-21) were as follows. Thereafter, the contents of the flask were removed from the flask and then cooled. In this way, a crystalline polyester resin PES-21 was obtained. In the crystalline polyester resin PES-21, the softening point is 80 ° C., the melting point is 70 ° C., the crystallinity index is 1.0, the acid value is 3.6 mgKOH / g, and the hydroxyl value is 18 mgKOH / g.

[Method for measuring mass average molecular weight of non-crystalline polyester resin]
The mass average molecular weight of the amorphous polyester resin (more specifically, each of the amorphous polyester resins PES-11 to PES-15) was measured by gel permeation chromatography (GPC). The measurement conditions were as shown below.

(Measurement condition)
Measuring device: GPC (gel permeation chromatography) device (“HLC-8220GPC” manufactured by Tosoh Corporation)
Column: Column for organic solvent SEC (size exclusion chromatography) (“TSKgel GMHXL” manufactured by Tosoh Corporation, packing material: styrenic polymer, column size: inner diameter 7.8 mm × length 30 cm, packing particle diameter: 9 μm) Polystyrene gel column detector combined in series: RI (refractive index) detector

  A measurement object was prepared by the following method. Specifically, an amorphous polyester resin (more specifically, each of the amorphous polyester resins PES-11 to PES-15) was added to THF (tetrahydrofuran) so that the concentration was 3.0 mg / mL. The resulting liquid was allowed to stand for 1 hour to dissolve the amorphous polyester resin in THF. The obtained THF solution was filtered with a non-aqueous sample pretreatment filter (“Chromatodisc 25N” manufactured by Kurashiki Boseki Co., Ltd., membrane pore diameter: 0.45 μm). In this way, a measurement object was obtained.

[Pigment preparation method]
70 parts by weight of C.I. I. Pigment Blue 15: 3 (number average particle diameter: 150 nm) and 30 parts by mass of C.I. I. Pigment Green 36 (number average particle size: 200 nm) was mixed to obtain Pigment P-1.

  50 parts by weight of C.I. I. Pigment Blue 15: 3 (number average particle diameter: 150 nm) and 50 parts by mass of C.I. I. Pigment Green 36 (number average particle size: 200 nm) was mixed to obtain Pigment P-2.

  30 parts by weight of C.I. I. Pigment Blue 15: 3 (number average particle diameter: 150 nm) and 70 parts by mass of C.I. I. Pigment Green 36 (number average particle diameter: 200 nm) was mixed to obtain Pigment P-3.

  70 parts by weight of C.I. I. Pigment Blue 15: 3 (number average particle diameter: 150 nm) and 30 parts by mass of C.I. I. Pigment Green 7 (number average particle size: 220 nm) was mixed to obtain Pigment P-4.

[Method for Preparing Release Agent]
As a release agent W-1, “Nissan Electol WEP-3” manufactured by NOF Corporation was prepared. As the release agent W-4, “Nissan Electol WEP-2” manufactured by NOF Corporation was prepared. As the release agent W-6, carnauba wax (“Carnauba Wax No. 1” manufactured by Hiroyuki Kato Co., Ltd.) was prepared. Rice wax (manufactured by Toa Kasei Co., Ltd.) was used as the release agent W-7.

  4 parts by mass of “Nissan Electol WEP-3” manufactured by NOF Corporation and 4 parts by mass of “Nissan Electol WEP-2” manufactured by NOF Corporation were mixed to obtain a release agent W-2. .

  4 parts by mass of “Nissan Electol WEP-7” manufactured by NOF Corporation and 4 parts by mass of Carnauba wax (“Carnauba Wax No. 1” manufactured by Hiroyuki Kato Co., Ltd.) were mixed to obtain a release agent W-3. Got.

  4 parts by mass of “Nissan Electol WEP-3” manufactured by NOF Corporation and 4 parts by mass of Fischer-Tropsch wax (“FT100” manufactured by Nippon Seiwa Co., Ltd.) are mixed to obtain a release agent W-5. It was.

[Method for measuring melting point of release agent]
About 15 mg of a measurement target (more specifically, each of the release agents W-1 to W-7) is placed in an aluminum dish, and the aluminum dish is subjected to a differential scanning calorimeter (“DSC-6220” manufactured by Seiko Instruments Inc.). ). In addition, an empty aluminum dish was used as a reference. In the measurement of the endothermic curve, the temperature of the measurement part was increased from a measurement start temperature of 30 ° C. to 170 ° C. at a rate of 10 ° C./min. During the temperature increase, the endothermic curve [vertical axis: heat flow (DSC signal), horizontal axis: temperature] was measured. The melting point of the measurement object was read from the obtained endothermic curve. In the endothermic curve, the maximum peak temperature due to the heat of fusion corresponds to the melting point of the object to be measured.

[Toner Production Method]
<Method for Producing Toner TA-1>
Using an FM mixer (Nihon Coke Kogyo Co., Ltd.), 75 parts by mass of amorphous polyester resin PES-11, 15 parts by mass of crystalline polyester resin PES-21, 5 parts by mass of pigment P-1 5 parts by mass of release agent W-1 was mixed.

Using the twin screw extruder ("PCM-30" manufactured by Ikegai Co., Ltd.), the obtained mixture was melted according to the material supply speed 6 kg / hour, the shaft rotation speed 160 rpm, and the set temperature (cylinder temperature, Table 1). The kneading temperature was 120 ° C. The obtained melt-kneaded product was cooled. The cooled melt-kneaded material was coarsely pulverized using a pulverizer (“Rotoplex (registered trademark)” manufactured by Hosokawa Micron Corporation). The obtained coarsely pulverized product was finely pulverized using a pulverizer (“Turbomill RS type” manufactured by Freund Turbo Co., Ltd.). The obtained finely pulverized product was classified using a classifier (“Elbow Jet EJ-LABO type” manufactured by Nippon Steel Mining Co., Ltd.). In this way, toner base particles were obtained. The obtained toner base particles had a volume median diameter (D ₅₀ ) of 6.0 μm and a triboelectric charge with a standard carrier of −20 μC / g.

  100.0 parts by mass of toner base particles and 1 part by mass of positively-charged silica particles (“AEROSIL (registered trademark) REA90 manufactured by Nippon Aerosil Co., Ltd.) ”Content: dry silica particles imparted with positive chargeability by surface treatment, number average primary particle diameter: about 20 nm). Using an FM mixer (“FM-10B” manufactured by Nippon Coke Industries Co., Ltd.), toner base particles and positively-charged silica particles under the conditions of a rotational speed of 3000 rpm, a set temperature (jacket temperature) of 20 ° C., and a processing time of 5 minutes. And mixed. Thereafter, sieving was performed using a 200-mesh sieve (aperture 75 μm). Thus, toner TA-1 containing a large number of toner particles was obtained.

<Method for Producing Toners TA-2 to TA-4>
Toners TA-2 to TA-4 were obtained in accordance with the production method of the toner TA-1, except that the pigments P-2 to P-4 were used.

<Method for Producing Toner TA-5 and TA-6>
Toners TA-5 and TA-6 were obtained according to the production method of the toner TA-1, except that the release agents W-2 and W-3 were used.

<Method for Producing Toner TA-7 and TA-8>
A toner TA-7 was obtained according to the production method of the toner TA-1, except that the melt kneading temperature (more specifically, the cylinder temperature) was 90 ° C. A toner TA-8 was obtained according to the production method of the toner TA-1, except that the melt kneading temperature (more specifically, the cylinder temperature) was 140 ° C.

<Method for Producing Toner TA-9 and TA-10>
Toner TA-9 was obtained according to the production method of toner TA-1, except that amorphous polyester resin PES-12 was used. Toner TA-10 was obtained according to the production method of toner TA-1, except that amorphous polyester resin PES-13 was used.

<Method for Producing Toners TB-1 to TB-3>
Toners TB-1 to TB-3 were obtained in accordance with the production method of the toner TA-1, except that the release agents W-4 to W-6 were used.

<Method for Producing Toner TB-4 and TB-5>
Toner TB-4 was obtained according to the production method of toner TA-1, except that the melt kneading temperature (more specifically, the cylinder temperature) was 80 ° C. A toner TB-5 was obtained according to the production method of the toner TA-1, except that the melt kneading temperature (more specifically, the cylinder temperature) was 155 ° C.

<Method for Producing Toner TB-6 and TB-7>
Toner TB-6 was obtained according to the production method of toner TA-1, except that amorphous polyester resin PES-14 was used. Toner TB-7 was obtained according to the production method of toner TA-1, except that amorphous polyester resin PES-15 was used.

<Method for Producing Toner TB-8>
A toner TB-8 was obtained according to the production method of the toner TA-1, except that the release agent W-7 was used.

[Measurement method of physical properties of toner]
<Method for measuring triboelectric charge amount between toner base particles and standard carrier>
Before mixing the toner base particles and the positively chargeable silica particles, the triboelectric charge amount between the toner base particles and the standard carrier was measured. Specifically, 100 parts by mass of a standard carrier N-01 (standard carrier for negatively charged polarity toner) provided by the Imaging Society of Japan and 7 parts by mass of a measurement target (more specifically, toner base particles) are mixed with a mixer ( Using a “Turbler (registered trademark) mixer T2F” manufactured by Willy et Bakkofen (WAB), mixing was performed for 30 minutes at a rotation speed of 96 rpm. 0.10 g of the obtained mixture was placed in a measurement cell of a Q / m meter (“MODEL 210HS-2A” manufactured by Trek). Of the mixture placed in the measurement cell, only the measurement object was sucked through a sieve (wire mesh) for 10 seconds. Then, based on the formula “total amount of electricity sucked in measurement target (unit: μC) / mass of sucked measurement target (unit: g)”, the charge amount of measurement target (unit: μC / g) is calculated. did.

<Method for measuring dispersion diameter of release agent domain>
Toner (more specifically, each of toners TA-1 to TA-10 and TB-1 to TB-8) is made of visible light curable resin (“Aronix (registered trademark) D-800” manufactured by Toagosei Co., Ltd.). It was embedded to obtain a cured product. A knife for making ultra-thin sections (“Sumiknife (registered trademark)” manufactured by Sumitomo Electric Industries, Ltd .: a diamond knife having a blade width of 2 mm and a blade edge angle of 45 °) and an ultramicrotome (“EM UC6” manufactured by Leica Microsystems) Using this, the cured product was cut at a cutting speed of 0.3 mm / sec to produce a thin piece having a thickness of 150 nm. The resulting flakes were dyed on a copper mesh by exposure for 10 minutes in the vapor of an aqueous ruthenium tetroxide solution. The cross section of the dyed thin piece was photographed at a magnification of 10,000 using a scanning transmission electron microscope (STEM) (“JSM-7600F” manufactured by JEOL Ltd.). The obtained TEM image was analyzed using image analysis software (“WinROOF” manufactured by Mitani Corporation). In this way, the dispersion diameter (diameter) of the release agent domain in the cross section of the toner particles was measured. An average toner particle was selected from the toner particles included in the TEM image, and the selected toner particle was used as a measurement target. The cross section of the toner particles to be measured had a maximum diameter of 5.5 μm or more. When the cross section of the release agent domain was not a perfect circle, the equivalent circle diameter (the diameter of a circle having the same area as the projected area of the particles) was taken as the measured value of the dispersion diameter. Table 5 shows the measurement results.

<Measurement method of toner particle surface adsorption force>
As a measuring device, an SPM probe station (“NanoNaviReal” manufactured by Hitachi High-Tech Science Co., Ltd.) equipped with a scanning probe microscope (SPM) (“Multifunctional Unit AFM5200S” manufactured by Hitachi High-Tech Science Co., Ltd.) was used. Prior to the measurement, toners (more specifically, toners TA-1 to TA-10 and TB-1 to TB) are obtained using a scanning electron microscope (SEM) (“JSM-6700F” manufactured by JEOL Ltd.). Among the toner particles contained in each of (8) to (8), an average toner particle was selected, and the selected toner particle was used as a measurement target.

(SPM measurement conditions)
・ Moveable range of measurement unit (size of sample that can be measured): 100 μm (Small Unit)
Measurement probe: Cantilever ("SI-DF3-R" manufactured by Hitachi High-Tech Science Co., Ltd., tip radius: 30 nm, probe coating material: rhodium (Rh), spring constant: 1.6 N / m, resonance frequency: 26 kHz)
Measurement mode: SIS-DFM (SIS: sampling intelligent scan, DFM: dynamic force mode)
・ Measurement range (one field of view): 1μm × 1μm
・ Resolution (X data / Y data): 256/256

  Under an environment of temperature 25 ° C. and humidity 50% RH, the measurement range (XY plane: 1 μm × 1 μm) of the surface to be measured is scanned horizontally with a cantilever in the measurement mode (SIS-DFM) to obtain an AFM force curve. Measurement was performed to obtain a mapping image regarding the surface adsorption force. The AFM force curve is a curve showing the relationship between the distance between the probe (tip end of the cantilever) and the measurement target and the force (deflection amount) acting on the cantilever. From the AFM force curve, the surface adsorption force of the measurement target (force necessary for the cantilever to move away from the surface of the toner particles) is obtained. In the measurement apparatus, the pressing force (deflection signal) of the cantilever is detected by an optical lever method. Specifically, the semiconductor laser device emits laser light toward the back surface of the cantilever, and the position sensor detects the laser light (flex signal) reflected from the back surface of the cantilever.

  Based on the mapping image regarding the surface adsorption force obtained as described above, the surface adsorption force of the toner base particles was obtained. In the above measurement, with the external additive attached to the surface of the toner base particle, a mapping image regarding the surface adsorption force is obtained by applying a cantilever to the surface area of the toner base particle where the external additive is not attached. Obtained. In addition, the arithmetic average value of the surface adsorption force measured for the toner was determined as follows. For the five toner particles contained in the measurement object, the surface adsorption force was measured at 10 locations per particle, and 50 measurement values were obtained per measurement object. And the arithmetic average of 50 measurement values was made into the surface adsorption | suction force of a measuring object. Table 5 shows the measurement results.

  Table 5 shows the measurement results of the physical properties of the toner. In Table 5, “Dispersion diameter” indicates the measurement result of the dispersion diameter of the release agent domain. The “surface adsorption force” indicates the measurement result of the surface adsorption force of the toner particles.

[Toner Evaluation Method]
<Evaluation method of charging stability of toner>
Using a ball mill for 30 minutes, 100 parts by mass of carrier (carrier for “ECOSYS (registered trademark) FS-C5300DN” manufactured by Kyocera Document Solutions Co., Ltd.) and 10 parts by mass of toner (more specifically, toner TA-1 ~ TA-10 and each of TB-1 to TB-8). Thus, the 1st evaluation object was obtained.

  Using the first evaluation object, the amount of charge after storage and the amount of charge after printing were measured. Specifically, the first evaluation object was allowed to stand for 24 hours in an environment of a temperature of 32.5 ° C. and a humidity of 80% RH. Thereafter, the charge amount of the toner (charge amount after storage) was measured according to the method described later.

The evaluation criteria are shown below. The evaluation results are shown in Table 6.
Good: Charge amount after storage was 15 μC / g or more and 25 μC / g or less.
Defect: Charge amount after storage was less than 15 μC / g or more than 25 μC / g.

  In addition, the first evaluation target (unused) was put in a developing device of a printer (“ECOSYS FS-C5300DN” manufactured by Kyocera Document Solutions Inc.), and replenishment toner (unused) was put in a toner container of the printer. In this embodiment, the same toner as the toner included in the first evaluation target is used as the replenishment toner. Thus, the 1st evaluation machine was prepared. Using the first evaluator, 10,000 images were continuously printed on printing paper (A4 size) in an environment of a temperature of 32.5 ° C. and a humidity of 80% RH on a printing paper (A4 size). Thereafter, the charge amount of the toner (charge amount after printing) was measured according to the method described later.

The evaluation criteria are shown below. The evaluation results are shown in Table 6.
Good: The charge amount after printing was 15 μC / g or more and 25 μC / g or less.
Poor: The charge amount after printing was less than 15 μC / g or more than 25 μC / g.

(Measurement method of toner charge)
A first evaluation object of 0.10 g was put in a measurement cell of a Q / m meter (“MODEL 210HS-1” manufactured by Trek). Of the first evaluation target, only the toner (more specifically, each of toners TA-1 to TA-10 and TB-1 to TB-8) was sucked through a sieve (metal mesh) for 10 seconds. Then, the charge amount of the toner was calculated based on the formula “total electric amount of sucked toner (unit: μC) / mass of sucked toner (unit: g)”.

<Evaluation method of low-temperature fixability of toner>
Using a ball mill, for 30 minutes, 100 parts by weight of carrier (carrier for “FS-C5250DN” manufactured by Kyocera Document Solutions Co., Ltd.) and 5 parts by weight of toner (more specifically, toner TA-1 to TA-10 and Each of TB-1 to TB-8) was mixed. Thus, the 2nd evaluation object was obtained.

  The printer (“FS-C5250DN” manufactured by Kyocera Document Solutions Inc.) was remodeled so that the fixing temperature could be adjusted. A second evaluation target (unused) was placed in the developing device of this printer, and replenishment toner (unused) was placed in the toner container of this printer. In this embodiment, the same toner as the toner included in the second evaluation target is used as the replenishment toner. Thus, the 2nd evaluation machine was prepared.

The lowest fixing temperature was determined using a second evaluator. The minimum fixing temperature means the lowest temperature among the fixing temperatures when it is determined that a low temperature offset has not occurred. Specifically, using a second evaluation machine under a temperature of 23 ° C. and a humidity of 55% RH, printing paper (“C ² ” manufactured by Fuji Xerox Co., Ltd., A4 size plain paper, basis weight: 90 g / m ² ) An unfixed solid image (size: 25 mm × 25 mm) was formed. At this time, the bias of the second evaluator was adjusted so that the amount of toner loaded on the recording paper was 1.0 mg / cm ² . Further, the printing paper was conveyed at a linear speed of 200 mm / second.

  The printing paper on which an unfixed solid image was formed was passed through the fixing device of the second evaluator (nip passing time: 40 ms). At this time, by increasing the temperature of the fixing device of the second evaluation machine (specifically, the temperature of the fixing roller included in the fixing device of the second evaluation machine) from 120 ° C. by 1 ° C., the fixing temperature is 120 ° C. From 1 ° C. In this way, a solid image fixed at each fixing temperature was obtained.

  Each of the obtained solid images was subjected to a rubbing test to determine whether or not a low temperature offset occurred. Specifically, the recording paper on which the solid image was fixed was folded in half so that the surface on which the solid image was fixed was inside. Using a 1 kg weight coated with a fabric, the recording paper was rubbed 10 times on the fold. Thereafter, the recording paper was expanded, and the length of toner peeling (hereinafter referred to as peeling width) in the portion where the solid image was fixed in the bent portion of the recording paper was measured. When the peeling width was less than 1.0 mm, it was determined that the low temperature offset did not occur, and when the peeling width was 1.0 mm or more, it was determined that the low temperature offset occurred. In this way, the minimum fixing temperature was determined.

The evaluation criteria are shown below. The evaluation results are shown in Table 6.
Good: The minimum fixing temperature was 140 ° C. or lower.
Poor: The minimum fixing temperature was higher than 140 ° C.

<Method for evaluating toner releasability>
Using a second evaluator, the releasability of the toner (more specifically, each of toners TA-1 to TA-10 and TB-1 to TB-8) was evaluated. In this example, the releasability of the toner was evaluated by evaluating the high temperature offset resistance of the toner. Specifically, first, an unfixed solid image was formed on a printing paper by the method described in <Method for evaluating low-temperature fixability of toner> described above. Next, the temperature of the fixing device of the second evaluation machine (specifically, the temperature of the fixing roller included in the fixing device of the second evaluation machine) was set to 170 ° C., and an unfixed solid image was formed. The printing paper was passed through the fixing device of the second evaluation machine (nip passing time: 40 ms). Thereafter, the fixing roller was taken out from the second evaluation machine, and it was visually confirmed whether or not the toner adhered to the peripheral surface of the fixing roller. When toner did not adhere to the peripheral surface of the fixing roller, it was determined to be acceptable. The temperature of the fixing device of the second evaluation machine was increased from 170 ° C. by 1 ° C., and the highest fixing temperature (maximum fixing temperature) when it was determined to be acceptable was obtained.

The evaluation criteria are shown below. The evaluation results are shown in Table 6.
Good: The maximum fixing temperature was 190 ° C. or higher.
Defect: The maximum fixing temperature was less than 190 ° C.

<Evaluation method of toner adhesion resistance>
Using a first evaluation machine under a temperature of 32.5 ° C and a humidity of 80% RH, a printing durability test was performed to print 10,000 sheets of sample images with a printing rate of 5% on printing paper (A4 size). It was. The developing sleeve was taken out from the first evaluation machine, and it was visually confirmed whether or not there was any deposit on the surface of the developing sleeve. Note that, on the surface of the developing sleeve, the color is different between the portion where the toner is attached and the portion where the toner is not attached.

The evaluation criteria are shown below. The evaluation results are shown in Table 6.
Good: Adherence was not confirmed on the surface of the developing sleeve.
Defect: The presence of deposits was confirmed on the surface of the developing sleeve.

<Method for evaluating heat resistance of toner>
2 g of toner (more specifically, each of toners TA-1 to TA-10 and TB-1 to TB-8) was placed in a polyethylene container (volume: 20 mL) and sealed. The sealed container was allowed to stand in a constant temperature bath (set temperature: 55 ° C.) for 3 hours. Then, the container was taken out from the thermostat and cooled to room temperature (about 25 ° C.). Thus, a toner for evaluation was obtained.

The toner for evaluation was placed on a sieve having a known mass of 200 mesh (aperture 75 μm). The mass of the sieve containing the evaluation toner was measured, and the mass of the toner before sieving was determined. A sieve was set on a powder tester (registered trademark, manufactured by Hosokawa Micron Corporation), and according to the manual of the powder tester, the sieve was vibrated for 30 seconds under the condition of the rheostat scale 5, and the evaluation toner was sieved. After sieving, the mass of the toner that did not pass through the sieve was measured. Based on the mass of the toner before sieving and the mass of the toner after sieving, the degree of aggregation (unit:%) was determined according to the following formula. The “mass of toner after sieving” in the following formula is the mass of toner that has not passed through the sieve, and is the mass of toner remaining on the sieve after sieving.
Aggregation degree = 100 × mass of toner after sieving / mass of toner before sieving

The evaluation criteria are shown below. The evaluation results are shown in Table 6.
Good: The degree of aggregation was 15% or less.
Poor: The degree of aggregation was more than 15%.

[Toner evaluation results]
Table 6 shows the evaluation results. In Table 6, “Sleeve Adhesion” indicates whether or not the presence of an adhering substance was confirmed on the surface of the developing sleeve. If there is no confirmed deposit on the surface of the developing sleeve, “No” is indicated. If the presence of deposits on the surface of the developing sleeve is confirmed, “Yes” is indicated.

  Toners TA-1 to TA-10 (toners according to Examples 1 to 10) each have the following configuration. Specifically, each of the toners TA-1 to TA-10 includes a plurality of toner particles. Each toner particle contained a binder resin, a colorant, and a release agent. The colorant contained cyan pigment X and green pigment Y. The release agent contained one or more synthetic ester waxes. The melting point of the release agent was 65 ° C. or higher and 75 ° C. or lower. In each of the toner particles, the release agent domain containing the release agent was dispersed in the binder resin. The dispersion diameter of the release agent domain was 0.5 μm or more and 1.5 μm or less. The surface adsorption force of the toner particles was 15 nN or more and 35 nN or less.

  As shown in Table 6, with toners TA-1 to TA-10, the charge amount of the toner could be within a desired range both after storage and after printing. In toners TA-1 to TA-10, the minimum fixing temperature was low and the maximum fixing temperature was high. Further, even when an image was formed using each of the toners TA-1 to TA-10 in a high temperature and high humidity environment, the presence of deposits on the surface of the developing sleeve was not confirmed. Further, even when each of the toners TA-1 to TA-10 was stored in a high temperature environment, the degree of aggregation could be kept low.

  On the other hand, toners TB-1 to TB-8 (more specifically, toners according to Comparative Examples 1 to 8) did not have the above-described configuration. Specifically, in toner TB-1, the melting point of the release agent was less than 65 ° C. When the toner TB-1 was stored in a high temperature environment, the degree of aggregation exceeded 15%.

  In toner TB-2, the melting point of the release agent exceeded 75 ° C. In toner TB-2, the minimum fixing temperature was higher than 140 ° C.

  In toner TB-3, the melting point of the release agent exceeded 75 ° C. In the toner TB-3, the release agent is composed of natural wax. In toner TB-3, the minimum fixing temperature was higher than 140 ° C., and the maximum fixing temperature was lower than 190 ° C.

  In Toner TB-4, the dispersion diameter of the release agent domain was less than 0.5 μm. In toner TB-4, the maximum fixing temperature was lower than 190 ° C.

  In Toner TB-5, the dispersion diameter of the release agent domain was larger than 1.5 μm. With toner TB-5, the charge amount of the toner after printing was less than the desired value. Further, when the toner TB-5 was stored in a high temperature environment, the aggregation degree exceeded 15%.

  In toner TB-6, the surface adsorption force of the toner particles was less than 15 nN. In toner TB-6, the minimum fixing temperature was higher than 140 ° C.

  In toner TB-7, the surface adsorption force of the toner particles was larger than 35 nN. When an image was formed using toner TB-7 in a high temperature and high humidity environment, the presence of deposits was confirmed on the surface of the developing sleeve.

  In the toner TB-8, the release agent was composed of natural wax. In toner TB-8, the maximum fixing temperature was lower than 190 ° C.

  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,
Each of the toner particles includes a binder resin, a colorant, and a release agent.
The colorant contains a cyan pigment and a green pigment,
The cyan pigment is C.I. I. Pigment Blue 15: 3,
The green pigment is C.I. I. Pigment green 7 and C.I. I. At least one selected from the group consisting of CI Pigment Green 36,
The release agent contains one or more synthetic ester waxes,
The melting point of the release agent is 65 ° C. or higher and 75 ° C. or lower,
In each of the toner particles, a release agent domain containing the release agent is dispersed in the binder resin,
A dispersion diameter of the release agent domain in a cross section of the toner particles is 0.5 μm or more and 1.5 μm or less;
A toner having a surface adsorption force of the toner particles of 15 nN or more and 35 nN or less. The binder resin contains an amorphous polyester resin,
The toner according to claim 1, wherein the amorphous polyester resin has a mass average molecular weight of 10,000 or more and less than 50,000.   The toner according to claim 2, wherein each of the toner particles is a non-capsule toner particle.   The toner according to claim 1, wherein the green pigment has a number average particle diameter of 500 nm or less. The number average particle size of the cyan pigment is 500 nm or less,
The toner according to claim 4, wherein the content of the green pigment is 70% by mass or less with respect to the total of the content of the cyan pigment and the content of the green pigment.   The toner according to claim 1, wherein at least one of the one or more types of synthetic ester wax is a synthetic ester wax having a melting point of 65 ° C. or higher and 75 ° C. or lower.