JP6515826B2 - Toner for developing electrostatic latent image - Google Patents

Description

  The present invention relates to a toner for electrostatic latent image development.

  In Patent Document 1, in order to obtain a toner excellent in heat resistance storage stability, fixability and grindability, a toner which is subjected to heat treatment for a specific time at a specific temperature with respect to a toner composition containing a crystalline polyester resin A method of making is disclosed. By such heat treatment, the crystalline polyester resin in the toner composition is allowed to grow minute crystals and increase the degree of crystallinity.

JP, 2009-128652, A

  However, the toner manufacturing method disclosed in Patent Document 1 requires a special heat treatment. Therefore, even if the crushability of the toner is improved, the productivity of the toner is not necessarily improved.

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a toner for developing an electrostatic latent image which is excellent in heat resistance storage stability, fixability, charge decay characteristics, and productivity.

The toner for developing an electrostatic latent image according to the present invention includes a plurality of toner particles containing a binder resin. The toner particles each contain a crystalline polyester resin and a non-crystalline polyester resin containing terephthalic acid as an acid component as the binder resin. The glass transition point of the toner obtained by differential scanning calorimetry is 55 ° C. or more and 65 ° C. or less. Maximum intensity of the absorbance peak appearing at a wavenumber 701cm ^-1 ± 1cm ^-1 in FT-IR spectra of the toner obtained by FT-IR analysis is 0.0100 or more 0.0250 or below ATR method. In the differential molecular weight distribution curve of the toner obtained by GPC measurement, the maximum peak in the range of molecular weight 1.0 × 10 ² or more and 1.0 × 10 ⁶ or less is in the range of molecular weight 4500 or more and 5500 or less, and the molecular weight 1.0 × Of the total peak areas in the range of 10 ² or more and 1.0 × 10 ⁶ or less, the ratio of the total peak area in the range of the molecular weight 2.5 × 10 ⁴ or more and 1.0 × 10 ⁶ or less is 20% or more and 45% or less is there.

  According to the present invention, it is possible to provide a toner for developing an electrostatic latent image which is excellent in heat resistant storage stability, fixability, charge decay characteristics, and productivity.

It is a spectrum chart which shows the example of a FT-IR spectrum. It is a figure which shows the example of a differential molecular weight distribution curve. It is a figure for demonstrating the measuring method of Mp (melting | fusing point). It is a figure for demonstrating the measuring method of Tg (glass transition point). It is a figure for demonstrating the measuring method of Tm (softening point).

  Embodiments of the present invention will be described. The evaluation results (values indicating the shape, physical properties, etc.) of the powder (more specifically, toner base particles, external additives, or toner, etc.) are not limited, and the average value of the powder A significant number of particles are picked and the number average of the values measured for each of the average particles.

The number average particle diameter of the powder is the number average value of the circle equivalent diameter of the primary particles (diameter of a circle having the same area as the projected area of the particles) measured using a microscope if nothing is specified. . In addition, if the measured value of the volume median diameter (D ₅₀ ) of the powder is not specified at all, the Coulter principle (pore electrical resistance method) using “Coulter Counter Multisizer 3” manufactured by Beckman Coulter, Inc. It is the value measured based on Moreover, each measured value of an acid value and a hydroxyl value is a value measured according to "JIS (Japanese Industrial Standard) K0070-1992", if it does not prescribe at all. Moreover, each measured value of a number average molecular weight (Mn) and a mass average molecular weight (Mw) is a value measured using gel permeation chromatography, if it does not prescribe at all.

  Hereinafter, “system” may be added after the compound name to generically generically refer to the compound and its derivative. When a “system” is added after the compound name to represent a polymer name, it means that the repeating unit of the polymer is derived from the compound or its derivative. Moreover, acryl and methacryl may be generically called "(meth) acryl" generically.

  The toner according to the present embodiment can be suitably used, for example, as a positively chargeable toner for developing an electrostatic latent image. The toner of the present embodiment is a powder including a plurality of toner particles (particles each having a configuration to be described later). The toner may be used as a one-component developer. Alternatively, the two-component developer may be prepared by mixing the toner and the 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 as a carrier. Moreover, 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 even if the carrier core is formed of a resin in which magnetic particles are dispersed. Good. In addition, magnetic particles may be dispersed in a resin layer that covers 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 the friction with the carrier.

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

  First, an electrostatic latent image is formed on a photosensitive member (for example, a surface layer portion of a photosensitive drum) based on image data. Next, the formed electrostatic latent image is developed using a developer containing toner. In the developing step, toner (for example, toner charged by friction with a carrier or a blade) on a developing sleeve (for example, a surface portion of a developing roller in a developing device) disposed in the vicinity of the photosensitive member is formed into an electrostatic latent image Adhere to form a toner image on the photoreceptor. Then, in the subsequent transfer step, after the toner image on the photosensitive member is transferred to the intermediate transfer member (for example, transfer belt), the toner image on the intermediate transfer member is further transferred to the 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. For example, a full color image can be formed by superposing four color toner images of black, yellow, magenta and cyan.

  The toner according to the present embodiment includes a plurality of toner particles. The toner particles may be provided with an external additive. When the toner particles include an external additive, the toner particles include toner base particles 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 optionally contain, in addition to the binder resin, an internal additive (for example, at least one of a release agent, a colorant, a charge control agent, and a magnetic powder). If necessary, external additives may be omitted. When the external additive is omitted, toner base particles correspond to toner particles.

  The toner particles contained in the toner according to the exemplary embodiment may be toner particles having no shell layer (hereinafter referred to as non-capsulated toner particles), or toner particles having a shell layer (hereinafter, capsule toner particles) It may be described). In the encapsulated toner particles, the toner mother particles comprise a core and a shell layer covering the surface of the core. The shell layer is substantially made of resin. For example, by covering the core that melts at a low temperature with a shell layer having excellent heat resistance, it is possible to achieve both heat resistance storage stability and low temperature fixability of the toner. The additive may be dispersed in the resin constituting the shell layer. The shell layer may cover the entire surface of the core or may partially cover the surface of the core. In order to improve the fixability of the toner, it is preferable that the core of the capsule toner particles be substantially made of a thermoplastic resin. The shell layer may be substantially composed of a thermosetting resin, may be composed substantially of a thermoplastic resin, or contain both a thermoplastic resin and a thermosetting resin. Good. As a thermoplastic resin, the below-mentioned suitable thermoplastic resin can be used. As a thermosetting resin, for example, melamine resin, urea resin, sulfonamide resin, glyoxal resin, guanamine resin, aniline resin, polyimide resin (more specifically, maleimide polymer or bismaleimide resin) And the like, or a xylene-based resin can be suitably used.

  The toner according to the present embodiment is a toner for developing an electrostatic latent image having the following basic configuration.

(Basic configuration of toner)
The toner contains a plurality of toner particles containing a binder resin. The toner particles each contain a crystalline polyester resin and a non-crystalline polyester resin containing terephthalic acid as an acid component as binder resins. The glass transition point (Tg) of the toner obtained by differential scanning calorimetry (DSC) is 55 ° C. or more and 65 ° C. or less. Absorbance peak appearing in FT-IR spectra obtained at the FT-IR analysis by ATR method wavenumber 701cm ^-1 ± 1cm ^-1 (hereinafter referred to as specific absorbance peak) Maximum intensity of 0.0100 or more 0.0250 or less is there. In a differential molecular weight distribution curve (hereinafter referred to as GPC molecular weight distribution) obtained by GPC (gel permeation chromatography) measurement, the molecular weight is 1.0 × 10 ² (= 100) or more and 1.0 × 10 ⁶ (= 1000000) The maximum peak in the following range (hereinafter referred to as GPC main peak) is in the range of molecular weight 4500 to 5500 and the total peak area in the range of molecular weight 1.0 × 10 ^{2 to} 1.0 × 10 ⁶ The ratio of the total peak area in the molecular weight range of 2.5 × 10 ⁴ (= 25000) to 1.0 × 10 ⁶ (hereinafter referred to as the GPC peak area ratio) is 20% to 45%. In addition, the measuring method of FT-IR spectrum and GPC molecular weight distribution is the same method as the Example mentioned later, or its alternative method.

  In the present embodiment, a resin having a crystallinity index of 0.90 or more and less than 1.15 is referred to as a crystalline resin. The crystallinity index of the resin corresponds to the ratio of the softening point (Tm) of the resin to the melting point (Mp) of the resin (= Tm / Mp). For non-crystalline resins, it is often not possible to measure a clear Mp. The Mp and Tm of the resin can be measured in the same manner as in the examples described later, or in an alternative thereof. The crystallinity index of the polyester resin can be adjusted by changing the type or amount of the material (eg, alcohol and / or carboxylic acid) for synthesizing the polyester resin. The toner particles may contain only one type of crystalline polyester resin, or may contain two or more types of crystalline polyester resin.

In the above basic configuration, the GPC peak area ratio is the sum of the peak areas of all the peaks in the molecular weight range of 2.5 × 10 ^{4 to} 1.0 × 10 ⁶ in the GPC molecular weight distribution (hereinafter referred to as the high molecular weight peak area and It corresponds to the value which divided (divided) with the sum total of the peak area of all the peaks in the range of molecular weight 1.0 * 10 < ² > or more and 1.0 * 10 < ⁶ > or less. In the case where one peak exists inside or outside the range of molecular weight 2.5 × 10 ⁴ or more and 1.0 × 10 ⁶ or less, among the peaks, the molecular weight is 2.5 × 10 ⁴ or more and 1.0 or less. Only the area of the part in the range of × 10 ⁶ or less is added as the high molecular weight peak area.

  In the above-described basic configuration, the toner particles each contain a crystalline polyester resin and a non-crystalline polyester resin containing terephthalic acid as an acid component as binder resins. By incorporating the crystalline polyester resin in the toner particles, it becomes possible to improve the low temperature fixability of the toner. Further, when the toner particles contain a non-crystalline polyester resin in addition to the crystalline polyester resin, it is easy to ensure sufficient heat-resistant storage stability of the toner. Furthermore, in the toner having a GPC main peak and a GPC peak area ratio defined in the above basic configuration, sufficient pulverization of the toner is carried out when the non-crystalline polyester resin contained in the toner particles contains terephthalic acid as an acid component. It becomes easy to secure the In order to ensure sufficient toner crushability, the amount of terephthalic acid in the non-crystalline polyester resin is preferably 10% by mass or more based on the entire non-crystalline polyester resin.

  In the above basic configuration, the glass transition point (Tg) of the toner obtained by differential scanning calorimetry (DSC) is 55 ° C. or more and 65 ° C. or less. The toner having such a Tg tends to be excellent in both the heat resistant storage stability and the low temperature fixability. Specifically, when the Tg of the toner is too small, the heat resistant storage stability of the toner tends to deteriorate. When the Tg of the toner is too large, the low temperature fixability of the toner tends to deteriorate. The measuring method of Tg (glass transition point) is the same method as the Example mentioned later, or its alternative method.

In the above basic configuration, the specific absorbance peak (the absorbance peak appearing at wave number 701 cm ⁻¹ ± 1 cm ⁻¹ ) is considered to be a peak derived from an aromatic ring (for example, styrene). The inventors have found that the maximum intensity (Abs) of the specific absorbance peak is in the range defined by the above-mentioned basic configuration in the toner which is excellent in all of the heat resistant storage property, the fixing property and the charge decay characteristics. Specifically, when the maximum intensity of the specific absorbance peak is too small, the toner tends to be susceptible to charge decay. It is considered that this charge decay is due to the crystalline polyester resin having a structure that is difficult to hold a charge. If the maximum intensity of the specific absorbance peak is too large, the heat resistant storage stability of the toner tends to be deteriorated.

FIG. 1 is a spectrum chart showing an example of an FT-IR spectrum. Lines L11 to L13 in FIG. 1 indicate examples of FT-IR spectra measured for the toner according to the present embodiment. Line L14 in FIG. 1 shows an example of an FT-IR spectrum in which the maximum intensity (Abs) of the absorbance peak appearing at wavenumber 701 cm ⁻¹ ± 1 cm ⁻¹ is not within the range defined by the above basic configuration. .

  In the above basic configuration, the position where the GPC main peak appears in the GPC molecular weight distribution is in the range of the molecular weight of 4500 or more and 5500 or less. The toner having such a GPC main peak tends to be excellent in hot offset resistance, toner adhesion, and grindability of toner base particles (in the case of capsule toner particles, core). Specifically, when the position (molecular weight) at which the GPC main peak appears is too small, the hot offset resistance and the toner adhesion of the toner tend to be deteriorated. The reason is presumed to be that the molecules move easily in the resin constituting the toner base particles (in the case of the capsule toner particles, the core) and the molecules move at a low temperature. When the position (molecular weight) at which the GPC main peak appears is too large, the crushability of the toner tends to deteriorate. The reason is presumed to be that the resin constituting the toner base particles (in the case of the capsule toner particles, the core) becomes excessively hard. In order to obtain a toner that is excellent in hot offset resistance, toner adhesion resistance, and toner mother particles (core in the case of capsule toner particles), the position where the GPC main peak appears in the GPC molecular weight distribution is molecular weight 4500 It is more preferable to be in the range of 5000 or more.

  In the above basic configuration, the GPC peak area ratio is 20% or more and 45% or less. The toner having such a GPC peak area ratio tends to be excellent in hot offset resistance, toner adhesion resistance, and crushability of toner base particles (core for capsule toner particles). Specifically, if the GPC peak area ratio is too small, hot offset is likely to occur at high temperatures. The reason is presumed to be that the elasticity of the toner base particles (the core in the case of the capsule toner particles) becomes insufficient and the plasticity by the influence of the crystalline polyester resin becomes relatively strong. On the other hand, when the GPC peak area ratio is too large, the resin constituting the toner base particles (in the case of the capsule toner particles, the core) becomes excessively hard, and the grindability tends to be deteriorated.

  FIG. 2 is a view showing an example of GPC molecular weight distribution (differential molecular weight distribution curve). In the GPC molecular weight distribution of FIG. 2, the horizontal axis represents the logarithmic value (Log M) of the molecular weight M, and the vertical axis represents the value (dw / dLog M) obtained by differentiating the concentration fraction w by the logarithmic value of the molecular weight M. In the example of FIG. 2, the position where the GPC main peak appears is the molecular weight 4800, and the GPC peak area ratio is 28%.

  The toner having the above-described basic configuration can be manufactured without any special heat treatment. In addition, the toner having the above-described basic configuration is excellent in the crushability. That is, in the toner having the above-described basic configuration, the toner base particles (in the case of the capsule toner particles, the core) are easily pulverized. For this reason, the toner having the above-described basic configuration is excellent in productivity. The molecular weight of the resin can be adjusted by changing the polymerization conditions of the resin (more specifically, the amount used of the polymerization initiator, the polymerization temperature, the polymerization time, etc.). For example, the molecular weight of the resin can be reduced by lowering the polymerization temperature (the reaction temperature at the time of polymerization), reducing the amount of the solvent dissolving the materials used for the synthesis of the resin, or reducing the amount of the polymerization initiator used. Can.

The volume median diameter (D ₅₀ ) of the toner base particles is preferably 4 μm or more and 9 μm or less in order to achieve both heat resistant storage stability and low temperature fixability of the toner.

  Resins suitable for forming toner particles are as follows.

<Suitable Thermoplastic Resin>
Examples of thermoplastic resins that constitute toner particles (particularly, toner base particles) include styrene resins, acrylic acid resins (more specifically, acrylic acid ester polymers or methacrylic acid ester polymers, etc.), olefins System resin (more specifically, polyethylene resin or polypropylene resin etc.), vinyl resin (more specifically, vinyl chloride resin, polyvinyl alcohol, vinyl ether resin or N-vinyl resin etc.), polyester resin, polyamide resin, Or a urethane resin can be used conveniently. In addition, the copolymer of each of these resins, that is, a copolymer in which an arbitrary repeating unit is introduced into the above resin (more specifically, a styrene-acrylic acid resin or a styrene-butadiene resin, etc.) It can be used suitably as a thermoplastic resin which constitutes particles.

  The thermoplastic resin is obtained by addition polymerization, copolymerization or condensation polymerization of one or more thermoplastic monomers. The thermoplastic monomer is a monomer that becomes a thermoplastic resin by homopolymerization (more specifically, an acrylic acid monomer, a styrenic monomer, etc.), or a monomer that becomes a thermoplastic resin by condensation polymerization (for example, by condensation polymerization) A combination of polyhydric alcohol and polyhydric carboxylic acid to be a polyester resin.

  The styrene-acrylic acid resin is a copolymer of one or more styrene monomers and one or more acrylic monomers. In order to synthesize a styrene-acrylic acid-based resin, for example, styrene-based monomers and acrylic acid-based monomers as shown below can be suitably used. A carboxyl group can be introduced into a styrene-acrylic acid resin by using an acrylic acid monomer having a carboxyl group. Further, by using a monomer having a hydroxyl group (more specifically, p-hydroxystyrene, m-hydroxystyrene, or (meth) acrylic acid hydroxyalkyl ester), the hydroxyl group can be introduced into the styrene-acrylic acid resin. .

  Preferred examples of the styrenic monomer include styrene, alkylstyrene (more specifically, α-methylstyrene, p-ethylstyrene or 4-tert-butylstyrene etc.), p-hydroxystyrene, m-hydroxystyrene And vinyl toluene, α-chlorostyrene, o-chlorostyrene, m-chlorostyrene or p-chlorostyrene.

  Preferred examples of the acrylic acid-based monomer include (meth) acrylic acid, (meth) acrylic acid alkyl ester, or (meth) acrylic acid hydroxyalkyl ester. Preferred examples of (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, (meth) acrylic Examples include n-butyl acid, iso-butyl (meth) acrylate, or 2-ethylhexyl (meth) acrylate. Preferred examples of (meth) acrylic acid hydroxyalkyl ester include 2-hydroxyethyl (meth) acrylic acid, 3-hydroxypropyl (meth) acrylic acid, 2-hydroxypropyl (meth) acrylic acid, or (meth) acrylic The acid 4-hydroxybutyl is mentioned.

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

  Preferred examples of diols are ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, di1,2-propanediol, polyethylene glycol, poly1,2-propanediol, or polytetramethylene glycol.

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

  Preferred examples of trihydric or higher alcohols include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, and 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.

  Preferred examples of the divalent carboxylic acid include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, adipic acid, sebacic acid, azelaic acid, malonic acid , Succinic acid, alkylsuccinic acid (more specifically, n-butylsuccinic acid, isobutylsuccinic acid, n-octylsuccinic acid, n-dodecylsuccinic acid, or isododecylsuccinic acid, etc.), or alkenylsuccinic acid (more specifically Examples thereof include n-butenylsuccinic acid, isobutenylsuccinic acid, n-octenylsuccinic acid, n-dodecenylsuccinic acid, and isododecenylsuccinic acid).

  Preferred examples of trivalent or higher carboxylic acids 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 (methylene carboxyl) Methane, 1,2,7,8-octane tetracarboxylic acid, pyromellitic acid, or Empol trimer acid can be mentioned.

  Hereinafter, preferred examples of the configuration of non-capsulated toner particles will be described. The toner base particles and the external additive will be described in order. Components (for example, internal additives or external additives) which are not necessary may be omitted depending on the use of the toner.

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

(Binder resin)
In the toner base particles, in general, the binder resin occupies most (for example, 85% by mass or more) of the components. For this reason, it is considered that the properties of the binder resin greatly affect the properties of the entire toner matrix 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 the binder resin has an amino group or an amide group. In that case, the toner base particles tend to be cationic.

  The toner according to the present embodiment has the above-described basic configuration. In the toner according to the exemplary embodiment, the toner base particles contain, as a binder resin, a crystalline polyester resin and a non-crystalline polyester resin (specifically, a non-crystalline polyester resin containing terephthalic acid as an acid component). The at least one non-crystalline polyester resin contained in the toner matrix particles has a repeating unit derived from terephthalic acid. The toner base particles may contain, as a binder resin, a resin other than polyester resin (more specifically, the above-mentioned suitable thermoplastic resin etc.).

  In order to improve the charge decay characteristics of the toner (specifically, to make it difficult for the toner to charge decay), the toner base particles preferably contain a crystalline polyester resin having a repeating unit derived from a styrenic monomer. Further, in order for the toner to have the above-described basic configuration, the toner base particles contain, as crystalline polyester resin, at least one alcohol monomer (more specifically, diols in the above-mentioned preferred thermoplastic resins, Bisphenols, or trivalent or higher alcohols, etc.) and one or more carboxylic acid monomers (more specifically, divalent carboxylic acids or trivalent or higher carboxylic acids, etc. in the above-mentioned preferred thermoplastic resins) and 1 Species or more styrenic monomers (more specifically, styrenic monomers and the like in the preferred thermoplastic resin described above) and one or more acrylic acid based monomers (more specifically, the preferred thermoplastic resin described above) It is preferable to contain a polymer with an acrylic acid-based monomer, etc.), 1,4-butanediol, 1,6-hexanediol, fumaric acid and styrene It is particularly preferred containing a polymer of methacrylic acid alkyl esters. When the toner base particles contain, as a crystalline polyester resin, a polymer of one or more alcohol monomers, one or more carboxylic acid monomers, one or more styrenic monomers, and one or more acrylic acid monomers, In order to improve the heat-resistant storage stability of the toner, the amount of the styrenic monomer in the polymer is preferably 1 to 20 parts by mol with respect to 100 parts by mol of the carboxylic acid monomer, and 2.5 It is more preferable that the amount is equal to or more than 12 parts by mol.

  When the toner base particles contain, as a crystalline polyester resin, a polymer of one or more alcohol monomers, one or more carboxylic acid monomers, one or more styrenic monomers, and one or more acrylic acid monomers In order to make the crystalline polyester resin and the non-crystalline polyester resin compatible with each other in the toner base particles appropriately, the toner base particles may contain at least one bisphenol and at least one kind of bisphenol as the non-crystalline polyester resin. Preferably containing a polymer of a carboxylic acid and one or more trivalent carboxylic acids, and a polymer of bisphenol A-EO adduct, bisphenol A-PO adduct, dodecenyl succinic acid, terephthalic acid and trimellitic acid It is particularly preferred to contain

(Colorant)
The toner mother particles may contain a colorant. As the colorant, known pigments or dyes may be used in accordance with the color of the toner. The amount of the colorant is preferably 1 part by mass or more and 20 parts by mass or less, and more preferably 3 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the binder resin.

  The toner mother particles may contain a black colorant. Examples of black colorants include carbon black. The black colorant may be a colorant toned to black using a yellow colorant, a magenta colorant, and a cyan colorant.

  The toner matrix particles may comprise color colorants such as yellow colorants, magenta colorants, or cyan colorants.

  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 yellow colorants include C.I. I. Pigment yellow (3, 12, 13, 14, 15, 17, 62, 74, 83, 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. Bat yellow can be suitably used.

  The magenta colorant is selected, for example, from the group consisting of condensation 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 magenta colorants include C.I. I. Pigment red (2, 3, 5, 6, 7, 19, 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 suitably 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 suitably used.

(Release agent)
The toner mother particles may contain a release agent. The release agent is used, for example, for the purpose of improving the fixing property or the offset resistance of the toner. In order to improve the fixing property or offset resistance of the toner, the amount of the releasing agent is preferably 1 part by mass or more and 30 parts by mass or less, and 3 parts by mass or more with respect to 100 parts by mass of the binder resin. More preferably, it is 15 parts by mass or less.

  As a mold release agent, for example, 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 block thereof Oxides of aliphatic hydrocarbon waxes such as copolymers; vegetable waxes such as candelilla wax, carnauba wax, wax wax, jojoba wax, or rice wax; animal nature such as bees wax, lanolin or wax wax Waxes; mineral waxes such as ozokerite, ceresin, or petrolatum; waxes based on fatty acid esters such as montanic acid ester wax or castor wax; fatty acids such as deacidified 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 two or more types of release agents may be used in combination.

  A compatibilizer may be added to the toner base particles in order to improve the compatibility between the binder resin and the release agent.

(Charge control agent)
The toner mother 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 rise characteristics of the toner. The charge rising characteristic of the toner is an indicator of whether or not the toner can be charged to a predetermined charge level in a short time.

  By including the negatively chargeable charge control agent in the toner base particles, it is possible to intensify the anionic property of the toner base particles. In addition, by including a positively chargeable charge control agent in the toner base particles, it is possible to intensify the cationicity of the toner base particles. However, when sufficient chargeability is ensured in the toner, the toner base particles do not need to contain a charge control agent.

(Magnetic powder)
The toner base particles may contain magnetic powder. As the magnetic powder, for example, iron (more specifically, ferrite or magnetite etc.), ferromagnetic metal (more specifically cobalt, nickel etc.), alloy containing iron and / or ferromagnetic metal, ferromagnetic Ferromagnetic alloys which have been subjected to chemical treatment (more specifically, heat treatment etc.) or chromium dioxide can be suitably used. One type of magnetic powder may be used alone, or two or more types of magnetic powder may be used in combination.

[External additive]
An external additive may be attached to the surface of the toner base particles. The external additive is used, for example, to improve the flowability or the handleability of the toner. In order to improve the flowability or handleability of the toner, the amount of the external additive 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. Further, in order to improve the flowability or the handleability of the toner, the particle diameter of the external additive is preferably 0.01 μm or more and 1.0 μm or less.

  As the external additive, inorganic particles are preferable, and particles of silica particles or metal oxides (more specifically, alumina, titanium oxide, magnesium oxide, zinc oxide, strontium titanate, barium titanate, etc.) are particularly preferable. preferable. One type of external additive may be used alone, or a plurality of external additives may be used in combination.

[Method of producing toner]
In order to easily and suitably manufacture the toner according to the exemplary embodiment, a method of manufacturing a toner having the following configuration is particularly preferable. The toner production method includes a preparation step, a melt-kneading step, and a grinding step. In the preparation step, a condensation product is obtained by subjecting one or more alcohols and one or more carboxylic acids to a condensation reaction, and then the obtained condensate, one or more styrenic compounds, and one or more acrylic acids. The compound is reacted to obtain a crystalline polyester resin. In the melt-kneading step, a toner material containing at least a crystalline polyester resin and a non-crystalline polyester resin is melt-kneaded to obtain a melt-kneaded product. In the pulverizing step, the melt-kneaded product is pulverized.

  Hereinafter, the method of manufacturing the toner will be further described based on more specific examples.

(Preparation process)
Hereinafter, an example of the preparation process will be described. In the preparation step, materials used for producing the toner are prepared. For example, after condensation reaction of one or more alcohols and one or more carboxylic acids to obtain a condensate, the resulting condensate, one or more styrenic compounds, and one or more acrylic acid compounds To give a crystalline polyester resin. In addition, a non-crystalline polyester resin is obtained by condensation reaction of one or more alcohols and one or more carboxylic acids. The obtained crystalline polyester resin and non-crystalline polyester resin are respectively used as a binder resin.

(Melt kneading process)
Hereinafter, an example of a melt-kneading process is demonstrated. In the melt-kneading step, a toner material (for example, a binder resin, a colorant, a release agent, and a charge control agent) containing a binder resin is mixed to obtain a mixture. Subsequently, the obtained mixture is melt-kneaded to obtain a melt-kneaded product. A mixing apparatus (for example, an FM mixer) can be suitably used to mix the toner materials. For melt-kneading the mixture, a twin-screw extruder, a three-roll kneader, or a two-roll kneader can be suitably used. As the toner material, a master batch containing a binder resin and a colorant may be used.

(Crushing process)
Hereinafter, an example of a crushing process is demonstrated. First, the melt-kneaded product is solidified by cooling using a cooling / solidifying device such as a drum flaker. Subsequently, the obtained solidified material is roughly crushed using a first grinding device. Thereafter, the resulting coarsely pulverized material is further pulverized using a second pulverizing apparatus to obtain a pulverized material having a desired particle size.

(Washing process)
After the grinding process, for example, water may be used to wash the toner base particles. As a method for washing toner base particles, for example, solid-liquid separation of a dispersion liquid containing toner base particles is carried out to collect wet cake-like toner base particles, and the collected wet cake-like toner base particles are washed with water. Method is preferred. Further, as a method of washing toner base particles, a method is preferable in which toner base particles in a dispersion liquid containing toner base particles are sedimented, the supernatant liquid is replaced with water, and toner base particles are redispersed in water after replacement.

(Drying process)
After the washing step, the toner base particles may be dried. For example, the toner base particles can be dried using a drier (more specifically, a spray drier, a fluid bed drier, a vacuum freeze drier, a vacuum drier, etc.). In order to suppress aggregation of toner base particles during drying, it is preferable to dry the toner base particles using a spray dryer. In the case of using a spray dryer, for example, a dispersion liquid in which an external additive (more specifically, silica particles etc.) is dispersed is sprayed onto the toner base particles to simultaneously carry out the drying step and the external addition step described later. It will be possible to do.

(External addition process)
An external additive may be attached to the surface of the toner base particles. The external additive can be adhered to the surface of the toner base particle by mixing the toner base particle and the external additive under the condition that the external additive is not embedded in the toner base particle using a mixer. .

  According to the above-described process, it is possible to manufacture a toner containing a large number of toner particles. Note that unnecessary steps may be omitted. For example, when a commercially available product can be used as a material as it is, the step of preparing the material can be omitted by using the commercially available product. Further, in the case where the external additive is not attached to the surface of the toner base particles (the external addition step is omitted), the toner base particles correspond to toner particles. Moreover, in order to obtain a predetermined compound, a salt, an ester, a hydrate, or an anhydride of the compound may be used as a raw material. In order to produce the toner efficiently, it is preferable to simultaneously form a large number of toner particles. The toner particles produced simultaneously are considered to have substantially the same configuration.

  An embodiment of the present invention will be described. Table 1 shows toners TA-1 to TA-7 and TB-1 to TB-11 (toner for developing electrostatic latent image) according to Examples or Comparative Examples. Further, in Tables 2 and 3, crystalline polyester resins A1 to A5 and noncrystalline polyester resins B1 to B4 used for producing any one of toners TA-1 to TB-11 are shown. "Proportion" in Table 2 indicates the amount (mol part) of each material when the amount of fumaric acid is 100 mol parts. “Proportion” in Table 3 indicates the amount (mol part) of each material when the total amount of the bisphenol A propylene oxide adduct and the bisphenol A ethylene oxide adduct is 100 mol parts.

  Hereinafter, the manufacturing method, the evaluation method, and the evaluation result of the toners TA-1 to TA-7 and TB-1 to TB-11 will be described in order. In addition, in the evaluation which an error produces, the measurement value of a considerable number which an error becomes small enough was obtained, and the arithmetic mean of the obtained measurement value was made into the evaluation value. The measurement methods of Tg (glass transition point), Mp (melting point), and Tm (softening point) are as follows, if they are not specified at all.

<Method of measuring Tg and Mp>
A differential scanning calorimeter ("DSC-6220" manufactured by Seiko Instruments Inc.) was used as a measurement device. The Tg and Mp of the sample were determined by measuring the endothermic curve of the sample using a measuring device. Specifically, about 15 mg of a sample (for example, a polyester resin) was placed in an aluminum pan (a container made of aluminum), and the aluminum pan was set in the measurement unit of the measurement apparatus. Also, an empty aluminum plate was used as a reference. In the measurement of the endothermic curve, the temperature of the measurement portion was raised from a measurement start temperature of 10 ° C. to 150 ° C. at a rate of 10 ° C./minute (RUN 1). Thereafter, the temperature of the measurement part was lowered from 150 ° C. to 10 ° C. at a rate of 10 ° C./minute. Subsequently, the temperature of the measurement unit was raised again from 10 ° C. to 150 ° C. at a rate of 10 ° C./min (RUN 2). An endothermic curve (vertical axis: heat flow (DSC signal), horizontal axis: temperature) of the sample was obtained by RUN2. From the resulting endothermic curve, the Mp and Tg of the sample were read. For example, as shown in FIG. 3, in the endothermic curve, the maximum peak temperature due to the heat of fusion corresponds to the Mp (melting point) of the sample. In addition, as shown in FIG. 4, in the endothermic curve, the temperature (onset temperature) of the change point of the specific heat (the intersection point of the extrapolation line of the base line and the extrapolation line of the falling line) is Tg of the sample (glass transition) Corresponds to the point).

<Method of measuring Tm>
A sample (for example, a polyester resin) is set in a high-rise flow tester ("CFT-500D" manufactured by Shimadzu Corporation), and the die pore diameter is 1 mm, the plunger load is 20 kg / cm ² , the temperature rise rate is 6 ° C / min. Under the conditions, a 1 cm ³ sample was melted and flowed out, and the S-curve (vertical axis: stroke, horizontal axis: temperature) of the sample was determined. Subsequently, the Tm of the sample was read from the obtained S-shaped curve. For example, in the S-curve shown in FIG. 5, assuming that the maximum value of the stroke is S ₁ and the stroke value of the low-temperature side baseline is S ₂ , the value of the stroke in the S-curve is “(S ₁ + S ₂ The temperature corresponding to 2) corresponds to the Tm (softening point) of the sample.

[Method of Manufacturing Toner TA-1]
(Synthesis of crystalline polyester resin A1)
In a 5-liter four-necked flask equipped with a thermometer (thermocouple), a dehydration tube, a nitrogen introduction tube, and a stirrer, 990 g (84 molar parts) of 1,4-butanediol (a1 component: alcohol component) 242 g (11 parts by mol) of 1,6-hexanediol (component a1: alcohol), 1480 g (100 parts by mol) of fumaric acid (component a2: acid), and 2.5 g of 1,4-benzenediol I put it in. Subsequently, the contents of the flask were reacted at a temperature of 170 ° C. for 5 hours. Subsequently, the contents of the flask were reacted at a temperature of 210 ° C. for 1.5 hours. Subsequently, the contents of the flask were allowed to react for 1 hour under the conditions of a reduced pressure atmosphere (pressure 8 kPa) and a temperature of 210.degree. Subsequently, the pressure is returned to the normal pressure atmosphere, and 69 g (2.8 mol parts) of styrene (s-a component: styrene-acrylic acid component) and n-butyl methacrylate (s-a component: styrene) are contained in the flask. 54 g (2.2 mol parts) of an acrylic acid-based component) was added. Subsequently, the contents of the flask were reacted at a temperature of 210 ° C. for 1.5 hours. Subsequently, the contents of the flask were allowed to react for 1 hour under the conditions of a reduced pressure atmosphere (pressure 8 kPa) and a temperature of 210.degree. As a result, crystalline polyester resin A1 was obtained. Crystalline polyester resin A1 has physical properties shown in Table 2 (Tm: 88.8 ° C., Mp: 82 ° C., acid value: 3.1 mg KOH / g, hydroxyl value: 19 mg KOH / g, Mw: 27500, Mn: 3620) Had.

(Synthesis of non-crystalline polyester resin B1)
In a 5-liter four-necked flask equipped with a thermometer (thermocouple), a dehydration tube, a nitrogen introducing tube, and a stirrer, 1700 g (70 parts of bisphenol A-PO (propylene oxide) adduct (component b1: alcohol component) Molar part), 650 g (30 molar parts) of bisphenol A-EO (ethylene oxide) adduct (component b1: alcohol component), 975 g (46 molar parts) of n-dodecenyl succinic anhydride (component b2: acid component) Then, 670 g (31 parts by mole) of terephthalic acid (component b2: acid component), 160 g (7 parts by mole) of trimellitic acid (component b2: acid component), and 4 g of dibutyltin oxide were added. Subsequently, the contents of the flask were reacted at a temperature of 220 ° C. for 9 hours. Subsequently, the contents of the flask were reacted in a reduced pressure atmosphere (pressure 8 kPa) to obtain a non-crystalline polyester resin B1 having a softening point (131.1 ° C.) shown in Table 3. The non-crystalline polyester resin B1 has physical properties shown in Table 3 (Tm: 131.1 ° C., Tg: 60.8 ° C., acid value: 14 mg KOH / g, hydroxyl value: 31 mg KOH / g, Mw: 76297, Mn: 3660 ) Had.

(Preparation of toner base particles)
10 parts by mass of a first binder resin (crystalline polyester resin A1) and a second binder resin (noncrystalline polyester resin B1) using an FM mixer ("FM-20B" manufactured by Japan Coke Industry Co., Ltd.) 80 Parts by mass, 5 parts by mass of a coloring agent ("MA-100" manufactured by Mitsubishi Chemical Corporation, carbon black), mold release agent ("Nissan Electol (registered trademark) WEP-9" manufactured by NOF Corporation), ester wax 4 parts by mass was mixed with 1 part by mass of a charge control agent ("BONTRON (registered trademark) P-51" manufactured by Orient Chemical Industries Co., Ltd., quaternary ammonium salt).

Subsequently, the obtained mixture was melt-kneaded using a twin-screw extruder ("PCM-30" manufactured by Ikegai Co., Ltd.) at a material supply rate of 6 kg / hour, a shaft rotational speed of 160 rpm, and a cylinder temperature of 120 ° C. . Thereafter, the obtained kneaded product was cooled. Subsequently, the cooled kneaded material was roughly crushed under the conditions of a set particle diameter (volume median diameter) of 1 mm using a grinder (“ROTPLEX (registered trademark) 16/8 type” manufactured by Hosokawa Micron Corporation) . Subsequently, using the pulverizer (“Turbo Mill RS type” manufactured by Freund Turbo Co., Ltd.), the obtained coarsely pulverized material is fed under the conditions of a material feed rate of 6 kg / hour and a set particle diameter (volume median diameter) of 7 μm. Finely ground. Subsequently, the obtained pulverized material was classified using a classifier ("Elbow Jet EJ-LABO type" manufactured by Nittetsu Mining Co., Ltd.). As a result, toner base particles having a volume median diameter (D ₅₀ ) of 7 μm were obtained.

(External addition process)
100 parts by mass of toner base particles and hydrophobic silica fine particles (manufactured by Nippon Aerosil Co., Ltd.) using an FM mixer ("FM-10B" manufactured by Japan Coke Industry Co., Ltd.) at a rotational speed of 3000 rpm and a jacket temperature of 20 ° C. 1.5 parts by mass of AEROSIL (registered trademark) RA-200H ′ ′) and 0.8 parts by mass of conductive titanium oxide fine particles (“EC-100” manufactured by titanium industry Co., Ltd.) were mixed for 2 minutes. Thereby, the external additive adhered to the surface of the toner base particles. Then, it sifted using the sieve of 300 mesh (48 micrometers of openings). As a result, toner TA-1 containing a large number of toner particles was obtained.

[Method of Manufacturing Toners TA-2, TA-3, TB-4, and TB-5]
Crystalline polyester resins shown in Table 1 (crystalline polyester resins A2 to A5 shown in Table 1) are used instead of the crystalline polyester resin A1 for producing the toners TA-2, TA-3, TB-4, and TB-5, respectively. The production method was the same as that of Toner TA-1 except that any one was used. The synthesis method of the crystalline polyester resins A2 to A5 was the same as the synthesis method of the crystalline polyester resin A1 except that the amounts of the respective materials were changed as shown in Table 2. In the synthesis method of crystalline polyester resin A5, neither styrene nor butyl methacrylate was used. The crystalline polyester resins A2 to A5 each had the physical properties shown in Table 2.

[Method of Manufacturing Toners TA-4, TA-5, TB-1, and TB-7 to TB-9]
Non-crystalline polyester resin shown in Table 1 (non-crystalline polyester resin (non-crystalline) shown in Table 1 in place of non-crystalline polyester resin B1 for producing toners TA-4, TA-5, TB-1 and TB-7 to TB-9 respectively Except that any one of the polyester resins (B2 to B7) was used. The synthesis method of the non-crystalline polyester resins B2 to B7 was the same as the synthesis method of the non-crystalline polyester resin B1 except that the amounts of the respective materials were changed as shown in Table 3. Fumaric acid was used in the synthesis method of the non-crystalline polyester resin B4, and n-dodecenyl succinic anhydride and terephthalic acid were not used. The non-crystalline polyester resins B2 to B7 had the physical properties shown in Table 3, respectively.

[Method of Manufacturing Toners TA-6, TA-7, TB-2, and TB-3]
The production methods of toners TA-6, TA-7, TB-2 and TB-3 are the same except that the mass ratio of crystalline polyester resin A1 to non-crystalline polyester resin B1 is changed as shown in Table 1 respectively. , The same as the manufacturing method of the toner TA-1.

[Method of Manufacturing Toner TB-6]
As shown in Table 1, the method of producing the toner TB-6 was the same as the method of producing the toner TA-1 except that the crystalline polyester resin A1 was not used.

[Method of Manufacturing Toner TB-10]
The production method of Toner TB-10 was the same as the production method of Toner TA-5 except that the mass ratio of crystalline polyester resin A1 to non-crystalline polyester resin B3 was changed as shown in Table 1.

[Method of Manufacturing Toner TB-11]
The production method of Toner TB-11 was the same as the production method of Toner TA-4 except that the mass ratio of the crystalline polyester resin A1 to the non-crystalline polyester resin B2 was changed as shown in Table 1.

  With respect to the toners TA-1 to TA-7 and TB-1 to TB-11 obtained as described above, each of Tg (glass transition point), FT-IR spectrum, and GPC molecular weight distribution (differential molecular weight distribution curve) The measurement results of were as shown in Table 4. For example, for toner TA-1, the maximum intensity of the specific absorbance peak is 0.0114, the Tg is 58.7 ° C., the position of the GPC main peak is 4900, and the GPC peak area ratio is 31%. there were.

  The toner Tg was measured by the above-mentioned differential scanning calorimetry. The methods of measuring the FT-IR spectrum of the toner and the GPC molecular weight distribution were as follows.

<Method of measuring FT-IR spectrum>
As a measuring device, FT-IR (Fourier transform infrared spectrometer) ("Frontier" manufactured by Perkin Elmer Co., Ltd.) was used. The measurement mode was ATR (total reflection measurement) mode. Diamond (refractive index 2.4) was used as the ATR crystal.

The ATR crystal was mounted on a measuring device, and 1 mg of a sample (toner) was placed on the ATR crystal. Subsequently, the sample was pressurized with a load of 60 N or more and 80 N or less using the pressure arm of the measuring device. Subsequently, the FT-IR spectrum of the sample was measured under the condition of an infrared incident angle of 45 °. In the resulting FT-IR spectrum, the maximum intensity of a specific absorption peak (absorbance peak appearing at a wavenumber 701cm ^-1 ± 1cm ^-1): was obtained (baseline 690cm ^-1 ~710cm ^-1).

<Method of measuring GPC molecular weight distribution>
In a container, 5 mL of THF (tetrahydrofuran) and 10 mg of a sample (toner) were placed, and allowed to stand at room temperature (about 25 ° C.) for 2 hours. Thereafter, the contents of the container were shaken to thoroughly mix THF and the sample in the container. Subsequently, using a sample processing filter (“TITAN 2” manufactured by Tomsick, filter: PTFE (polytetrafluoroethylene) membrane (non-water type), size (diameter): 30 mm, pore diameter: 0.45 μm), the contents of the container The product was filtered to obtain a THF solution of the THF soluble component of the sample (toner) as a filtrate (liquid which passed through the filter). The obtained THF solution (hereinafter referred to as a sample solution) was used as a measurement target.

As a measuring apparatus, the GPC (gel permeation chromatography) apparatus (Tosoh Corp. "HLC-8220GPC") was used. As the column, a 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 x length 30 cm, packing material particle diameter: 9 μm A polystyrene gel column in which two columns were combined in series was used. An RI (refractive index) detector was used as a detector. The measurement range was a molecular weight of 1.0 × 10 ² or more and 1.0 × 10 ⁶ or less.

  The column was set in the heat chamber of the measuring device. The column was stabilized in the heat chamber at a temperature of 40 ° C. while controlling the temperature of the heat chamber at 40 ° C. Subsequently, the solvent (THF) was flowed through a column at a temperature of 40 ° C. at a flow rate of 1 mL / min, and about 150 μL of a sample solution (target of measurement: THF solution prepared by the above method) was introduced to the column. Then, an elution curve (vertical axis: detection intensity (count number), horizontal axis: elution time) was measured for the sample solution introduced into the column. GPC of a sample (toner) based on the obtained elution curve and a calibration curve obtained as described below (a graph showing the relationship between logarithmic value of molecular weight and elution time for each standard substance of known molecular weight) Molecular weight distribution (differential molecular weight distribution curve) was determined. Then, based on the obtained GPC molecular weight distribution, the position of the GPC main peak and the GPC peak area ratio were determined.

The calibration curve was prepared using monodispersed polystyrene (standard substance). The monodispersed polystyrene used as the standard substance was 10 types of standard polystyrene (made by Tosoh Corp.) having a predetermined molecular weight. The molecular weight of each standard polystyrene was determined according to the measurement range (molecular weight 1.0 × 10 ² or more and 1.0 × 10 ⁶ or less).

[Evaluation method]
The evaluation method of each sample (toner TA-1 to TB-11) is as follows.

(Fixability)
100 parts by mass of a carrier for developer (carrier for FS-C5250DN) and 5 parts by mass of a sample (toner) were mixed for 30 minutes using a ball mill to prepare a two-component developer.

  Images were formed using the two-component developer prepared as described above to evaluate the minimum fixing temperature and the maximum fixing temperature. As an evaluation machine, a color printer having a roller-roller type heat and pressure fixing device (an evaluation machine capable of changing the fixing temperature by modifying “FS-C5250DN” manufactured by KYOCERA Document Solutions Inc.) was used. The two-component developer prepared as described above was loaded into the developing device of the evaluation machine, and a sample (toner for replenishment) was loaded into the toner container of the evaluation machine.

Using the above evaluation machine, the line speed of 200 mm / sec, the amount of applied toner on the portion from the rear end of paper (“C ² 90”: A4 size, 90 g / m ² plain paper made by Fuji Xerox Co., Ltd.) to 10 mm A solid image of 25 mm × 25 mm in size was formed under the condition 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.

  In the evaluation of the lowest fixing temperature, the setting range of the fixing temperature was 100 ° C. or more and 200 ° C. or less. The fixing temperature of the fixing device was raised from 100 ° C. by 5 ° C., and the minimum temperature (minimum fixing temperature) at which a solid image (toner image) could be fixed to paper was measured. Whether or not the toner could be fixed was confirmed by a rubbing test as shown below. More specifically, the evaluation sheet passed through the fixing device was folded so that the surface on which the image was formed was inside, and the image on the fold was rubbed back and forth five times using a 1 kg weight coated with a fabric. Subsequently, the paper was unfolded, and the folded part of the paper (the part where the solid image was formed) was observed. Then, the peeling length (peeling length) of the toner at the bent portion was measured. The lowest temperature of the fixing temperatures at which the peeling length is 1 mm or less was taken as the lowest fixing temperature. When the lowest fixing temperature was 150 ° C. or less, it was evaluated as ○ (good), and when the lowest fixing temperature exceeded 150 ° C., it was evaluated as × (not good).

  In the evaluation of the maximum fixing temperature, the setting range of the fixing temperature was 150 ° C. or more and 250 ° C. or less. The fixing temperature of the fixing device was raised by 5 ° C. from 150 ° C., and the maximum temperature (maximum fixing temperature) at which no offset occurred was measured. With regard to the evaluation sheet passed through the fixing device, it was visually confirmed whether an offset occurred (toner attached to the fixing roller). When the maximum fixing temperature was 185 ° C. or higher, it was evaluated as ○ (good), and when the maximum fixing temperature was less than 185 ° C., it was evaluated as × (not good).

  Based on the measured maximum fixing temperature and the minimum fixing temperature, the fixing temperature range represented by “fixing temperature range = maximum fixing temperature−minimum fixing temperature” was calculated. When the fixing temperature range was 50 ° C. or higher, it was evaluated as ○ (good), and when the fixing temperature range was less than 50 ° C., it was evaluated as × (not good).

(Heat resistant storage stability)
Two grams of the sample (toner) was placed in a 20 mL polyethylene container, and the container was allowed to stand in a thermostat set at 55 ° C. for 3 hours. Thereafter, the toner removed from the thermostat was cooled to room temperature (about 25 ° C.) to obtain a toner for evaluation.

Subsequently, the obtained evaluation toner was placed on a 200-mesh (75 μm mesh) sieve of known weight. Then, the mass of the sieve containing the toner was measured, and the mass of the toner before screening was determined. Subsequently, the sieve was set on a powder tester (manufactured by Hosokawa Micron Corporation), and the sieve was vibrated for 30 seconds under the condition of the rheostat graduation 5 according to the manual of the powder tester to sift the evaluation toner. Then, after sieving, the mass of the sieve containing the toner was measured to determine the mass of the toner remaining on the sieve. From the mass of the toner before sieving and the mass of the toner after sieving (the mass of the toner remaining on the sieve after sieving), the degree of aggregation (% by mass) was determined based on the following equation.
Cohesion degree (mass%) = 100 × mass of toner after sieving / mass of toner before sieving

  When the degree of aggregation was 10% by mass or less, it was evaluated as ((good), and when the degree of aggregation exceeded 10% by mass, it was evaluated as x (not good).

(Charge decay)
The charge decay constant (charge decay rate) of the sample (toner) in the non-externally added state, that is, the toner base particles (powder) of the sample (toner), was evaluated. As an evaluation machine, an electrostatic diffusivity measurement device ("NS-D100" manufactured by Nanoseeds, Inc.) was used. This evaluation machine can charge the object to be measured and monitor the state of charge decay of the charged object to be measured with a surface voltmeter. The evaluation method was a method in accordance with JIS (Japanese Industrial Standard) C 61340-2-1-2006. Hereinafter, the evaluation method of the charge decay constant will be described in detail.

  The measurement target (toner base particles) was placed in the measurement cell. The measurement cell was a metal cell in which a recess having an inner diameter of 10 mm and a depth of 1 mm was formed. The toner base particles were pressed from above using a slide glass, and the concave portions of the cells were filled with the toner base particles. By reciprocating the slide glass on the surface of the cell, toner mother particles overflowing from the cell were removed. The toner base particle loading was 50 mg.

Subsequently, the measurement cell filled with toner mother particles was allowed to stand for 24 hours in an environment of temperature 32.5 ° C. and humidity 80% RH. Subsequently, the grounded measurement cell was set to the evaluation machine, and the surface potentiometer of the evaluation machine was zeroed. Subsequently, toner base particles were charged by corona discharge under the conditions of a voltage of 10 kV and a charging time of 0.5 seconds. Then, after 0.7 seconds had elapsed after the end of the corona discharge, the surface potential of the toner base particles was continuously recorded under the conditions of a sampling frequency of 10 Hz and a maximum measurement time of 300 seconds. The charge decay constant α at a decay time of 2 seconds was calculated based on the data of the recorded surface potential and the equation “V = V ₀ exp (−αtt)”. In the equation, V represents a surface potential [V], V ₀ represents an initial surface potential [V], and t represents a decay time [seconds].

  When the charge decay constant was 0.020 or less, it was evaluated as ((good), and when the charge decay constant exceeded 0.020, it was evaluated as x (not good).

(Grindability)
In the production of each sample (toner TA-1 to TB-11), in the fine pulverizing step (set particle diameter: volume median diameter 7 μm) after coarsely pulverizing the kneaded material with a pulverizer (rhotoplex 16/8 type) The current value of the grinder (Turbo Mill RS type) (specifically, the current value of the following inverter) was measured.

  The crusher (turbo mill RS type) includes a rotor, a motor for driving the rotor, a belt for transmitting the power of the motor to the rotor, and an inverter for controlling the rotational operation of the motor. By controlling the rotational speed of the motor (and hence the rotational speed of the rotor), the particle size of the obtained pulverized material can be adjusted. In the evaluation of the crushability, a clamp type analog amperage meter was used to measure a current value corresponding to the torque of the motor at a predetermined point of the inverter (specifically, a 200 V power supply line).

  When the measured current value was 24 A or less, it was evaluated as ○ (good), and when it exceeded 24 A, it was evaluated as x (not good).

[Evaluation results]
Evaluation results for each sample (toner TA-1 to TB-11) (fixability: fixing temperature range (= maximum fixing temperature-minimum fixing temperature), grindability: current value, heat resistant storage stability: aggregation degree, charge decay: The charge decay constant) is shown in Table 5.

The toners TA-1 to TA-7 (toners according to Examples 1 to 7) had the above-described basic configuration. Specifically, in toners TA-1 to TA-7, as shown in Tables 1 to 3, respectively, toner particles include a crystalline polyester resin and a non-crystalline polyester resin containing terephthalic acid as an acid component, Each contained as a binder resin. Further, as shown in Table 4, the glass transition point (Tg) of the toner obtained by differential scanning calorimetry (DSC) was 55 ° C. or more and 65 ° C. or less. Further, as shown in Table 4, the maximum intensity of a particular absorbance peak (ATR method absorbance peak appearing at a wavenumber 701cm ^-1 ± 1cm ^-1 in FT-IR spectrum obtained by FT-IR analysis) 0.0100 It was above 0.0250. In addition, as shown in Table 4, in the GPC molecular weight distribution (differential molecular weight distribution curve), the GPC main peak (maximum peak in the range of molecular weight 1.0 × 10 ² or more and 1.0 × 10 ⁶ or less) has a molecular weight of 4500 or more Among the total peak areas in the range of 5500 or less and the GPC peak area ratio (molecular weight 1.0 × 10 ² or more and 1.0 × 10 ⁶ or less), the molecular weight is 2.5 × 10 ⁴ or more and 1.0 × 10 ⁶ or less. The ratio of the total peak area in the following range was 20% or more and 45% or less.

  The toners TA-1 to TA-7 (toners according to Examples 1 to 7) were excellent in heat resistance storage stability, fixing property, charge decay characteristic, and grinding property, respectively.

  The toner TB-1 (the toner according to Comparative Example 1) was inferior in the grinding property as compared with the toner according to Examples 1 to 7. The reason for this is considered that in the toner TB-1, the non-crystalline polyester resin B4 (binder resin) does not contain terephthalic acid as an acid component (see Table 3).

  The toner TB-2 (the toner according to Comparative Example 2) was inferior to the toner according to Examples 1 to 7 in the heat resistant storage stability, the charge attenuation characteristic, and the pulverization property. The reason for this is considered that in the toner TB-2, the amount of the crystalline polyester resin was too large relative to the amount of the entire binder resin, and the Tg of the toner became insufficient (too low). (See Tables 1 and 4).

  The toner TB-3 (the toner according to Comparative Example 3) was inferior in fixability to the toner according to Examples 1 to 7. The reason is that, in the toner TB-3, the amount of the crystalline polyester resin is too small relative to the amount of the entire binder resin, and the maximum intensity of the specific absorbance peak is in a suitable range (0.0100 or more and 0.0250 or less) It is thought that this is because it deviates from (see Table 1 and Table 4).

  Toner TB-4 (toner according to Comparative Example 4) was inferior in fixability, heat-resistant storage stability, and grindability to toners according to Examples 1 to 7. The reason for this is that, in toner TB-4, the amount of the styrene-acrylic acid type component is too large relative to the total component amount of the crystalline polyester resin A4 (see Table 2), and the crystalline polyester resin A4 and the noncrystalline polyester It is considered that this is because the resin B1 is excessively compatibilized and the maximum intensity of the specific absorbance peak deviates from the preferable range (0.0100 or more and 0.0250 or less) (see Table 4).

  The toner TB-5 (the toner according to Comparative Example 5) was inferior in fixability and charge decay characteristics to the toner according to Examples 1 to 7. The reason for this is that in the toner TB-5, the crystalline polyester resin A5 (binding resin) does not contain a styrene-acrylic acid-based component (repeating unit derived from a styrene-based monomer) (see Table 2), and the specific absorbance It is considered that this is because the maximum intensity of the peak deviates from the preferable range (0.0100 or more and 0.0250 or less) (see Table 4).

  The toner TB-6 (toner according to Comparative Example 6) was inferior in fixability to the toner according to Examples 1 to 7. The reason for this is considered that in the toner TB-6, the toner particles do not contain the crystalline polyester resin (see Table 1).

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

Claims (5)

A toner for developing an electrostatic latent image, comprising a plurality of toner particles containing a binder resin, comprising:
The toner particles each contain a crystalline polyester resin and a non-crystalline polyester resin containing terephthalic acid as an acid component as the binder resin,
The glass transition point obtained by differential scanning calorimetry is 55 ° C. or more and 65 ° C. or less,
Maximum intensity of the absorbance peak appearing at a wavenumber 701cm ^-1 ± 1cm ^-1 in FT-IR spectra obtained at the FT-IR analysis by ATR method is at 0.0100 or 0.0250 or less,
Molecular weight distribution 1.0 × 10 ² or more and 1.0 × 10 ⁶ in the molecular weight distribution obtained by GPC measurement, in which the logarithmic value of molecular weight is taken on the horizontal axis and the value obtained by differentiating the concentration fraction by the logarithmic value of molecular weight is taken on the vertical axis. maximum peak in the following ranges is in the molecular weight of 4500 or more 5500 or less in the range, of the area of the differential molecular weight distribution curve in the range of molecular weight 1.0 × 10 ² or more 1.0 × 10 ⁶ or less, molecular weight 2.5 the ratio of the area of the differential molecular weight distribution curve in the range of × 10 ⁴ or more 1.0 × 10 ⁶ or less is 45% or less than 20%
The toner for electrostatic latent image development, wherein the toner particles contain a crystalline polyester resin having a repeating unit derived from a styrenic monomer.   The electrostatic latent image developing toner according to claim 1, wherein the absorbance peak is a peak derived from an aromatic ring. A toner for developing an electrostatic latent image, comprising a plurality of toner particles containing a binder resin, comprising:
The toner particles each contain a crystalline polyester resin and a non-crystalline polyester resin containing terephthalic acid as an acid component as the binder resin,
The glass transition point obtained by differential scanning calorimetry is 55 ° C. or more and 65 ° C. or less,
Maximum intensity of the absorbance peak appearing at a wavenumber 701cm ^-1 ± 1cm ^-1 in FT-IR spectra obtained at the FT-IR analysis by ATR method is at 0.0100 or 0.0250 or less,
Molecular weight distribution 1.0 × 10 ² or more and 1.0 × 10 ⁶ in the molecular weight distribution obtained by GPC measurement, in which the logarithmic value of molecular weight is taken on the horizontal axis and the value obtained by differentiating the concentration fraction by the logarithmic value of molecular weight is taken on the vertical axis. maximum peak in the following ranges is in the molecular weight of 4500 or more 5500 or less in the range, of the area of the differential molecular weight distribution curve in the range of molecular weight 1.0 × 10 ² or more 1.0 × 10 ⁶ or less, molecular weight 2.5 the ratio of the area of the differential molecular weight distribution curve in the range of × 10 ⁴ or more 1.0 × 10 ⁶ or less is 45% or less than 20%
The toner particles contain, as the crystalline polyester resin, a polymer of at least one alcohol monomer, at least one carboxylic acid monomer, at least one styrenic monomer, and at least one acrylic acid monomer. , Toner for electrostatic latent image development.   The toner for developing an electrostatic latent image according to claim 3, wherein an amount of the styrene-based monomer in the polymer is 1 to 20 parts by mole with respect to 100 parts by mole of the carboxylic acid monomer. A toner for developing an electrostatic latent image, comprising a plurality of toner particles containing a binder resin, comprising:
The toner particles each contain a crystalline polyester resin and a non-crystalline polyester resin containing terephthalic acid as an acid component as the binder resin,
The glass transition point obtained by differential scanning calorimetry is 55 ° C. or more and 65 ° C. or less,
Maximum intensity of the absorbance peak appearing at a wavenumber 701cm ^-1 ± 1cm ^-1 in FT-IR spectra obtained at the FT-IR analysis by ATR method is at 0.0100 or 0.0250 or less,
Molecular weight distribution 1.0 × 10 ² or more and 1.0 × 10 ⁶ in the molecular weight distribution obtained by GPC measurement, in which the logarithmic value of molecular weight is taken on the horizontal axis and the value obtained by differentiating the concentration fraction by the logarithmic value of molecular weight is taken on the vertical axis. maximum peak in the following ranges is in the molecular weight of 4500 or more 5500 or less in the range, of the area of the differential molecular weight distribution curve in the range of molecular weight 1.0 × 10 ² or more 1.0 × 10 ⁶ or less, molecular weight 2.5 the ratio of the area of the differential molecular weight distribution curve in the range of × 10 ⁴ or more 1.0 × 10 ⁶ or less is 45% or less than 20%
The toner for electrostatic latent image development, containing the polymer of 1,4-butanediol, 1,6-hexanediol, fumaric acid, styrene and alkyl methacrylate as the crystalline polyester resin .

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