JP2006065047A - Toner for electrostatic image development and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner for electrostatic image development excellent in negative charging characteristics, low-temperature fixability, hot offset resistance and hot storage resistance and excellent also in environment resistance, and to provide a dry developer. <P>SOLUTION: The toner for electrostatic image development is obtained by dissolving or dispersing a binder resin containing at least a modified polyester resin, a colorant and a release agent in an organic solvent, dispersing the resulting solution or dispersion in an aqueous medium, granulating, removing the organic solvent and carrying out washing and drying, wherein ends of the modified polyester resin are blocked by a phenolic hydroxyl-containing compound and a hydroxyl value of the modified polyester resin is 10-80. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a toner for developing an electrostatic image that visualizes an electrostatic image formed on the surface of a photoreceptor in electrophotography and electrostatic recording, and a method for producing the same.

  In electrophotography, after uniformly charging the photoconductor, the photoconductor is exposed to a light image based on the original drawing, and the charge on the light irradiated portion is extinguished or reduced so that the electrostatic charge corresponding to the original drawing is applied to the photoconductor. A method of forming a development and then visualizing it with a so-called two-component dry developer composed of carrier particles and toner particles to obtain a copy is well known. In this two-component dry developer, minute toner particles are held on the surface of relatively large carrier particles by the electrostatic force generated by friction between both particles. The attracting force in the direction of the latent image with respect to the toner particles by the electric field to be formed overcomes the binding force between the toner particles and the carrier particles, and the toner particles are attracted and adhered onto the electrostatic latent image to visualize the electrostatic latent image. Is. The properties required for this toner include chargeability, hygroscopicity, stability over time, fluidity, etc. Among these properties, chargeability, hygroscopicity, and stability over time are the charge contained in the toner. It is greatly influenced by the control agent. The charge control agent is one of important toner constituent materials added for the purpose of imparting a necessary charge amount to the toner. Depending on whether the toner is charged positively or negatively according to the characteristics of the developer, a positively chargeable charge control agent and a negatively chargeable charge control agent are selectively used.

  Conventional toner charge control agents include, for example, positive charge control agents such as nigrosine dye salts (Japanese Patent Laid-Open No. 56-22441), various quaternary ammonium salts (Japanese Patent Laid-Open No. 59-136747), imidazole derivatives ( However, toners using these charge control agents are not sufficiently charged, hygroscopic and stable over time, and are compatible with the binder of the charge control agent itself. Is not enough.

  Further, as negative charge control agents, Cr-containing, Co complexes (Japanese Patent Laid-Open Nos. 61-217061 and 63-216061), nitrohumic acids (Japanese Patent Laid-Open No. 50-133838), phthalocyanine pigments (Japanese Patent Laid-Open No. 60-258560), carboxylic acid derivatives (JP-A-5-297737), urea derivatives (JP-A-5-313418), boron complexes (JP-A-5-265257) and the like are known. Among these negatively chargeable charge control agents, many of the Cr-containing and Co complexes are excellent in charging characteristics (charge amount, rising of charge, environmental stability, etc.).

  However, pollution, toxicity and safety due to heavy metals have become problems as ecological measures in recent years, and from the standpoint of environmental protection, the social demand that the use of these materials must be regulated or avoided. Seems to be stronger. Many of the negative charge control agents described above are colored and cannot be used for color toners, particularly full color toners for creating full-color images of the three primary colors, or they can only be used for low-quality images with poor reproducibility. There was a drawback that it could not be obtained. Further, among the negative charge control agents, colorless ones have the disadvantage that the ability to impart negative charge to the toner is not sufficient, and the environmental stability of toner charging and the long-term charge stability during repeated use are lacking. Under such circumstances, the use of a less negative charge control agent is strongly desired, and for this purpose, the negative chargeability of the electrostatic charge image developing toner comprising a binder resin, a colorant, and a wax is increased. is required.

  In recent years, the market has demanded smaller particle size for higher image quality and low-temperature fixing for energy saving. In particular, image formation after the image forming apparatus can be used for energy saving. In order to reduce as much as possible the amount of power required for the standby time (warm-up time of the apparatus) until it becomes possible, there is a strong demand for shortening the standby time. However, the toner obtained by the usual kneading and pulverization method has various problems such as difficulty in reducing the particle size, irregular shape, broad particle size distribution, and high fixing energy. Particularly in fixing, the kneading and pulverizing toner produced by the pulverization method is cracked at the interface of the release agent (wax) due to pulverization, and there are many on the surface. Adhesion to the surface easily occurs, and the performance was insufficient.

  On the other hand, in order to overcome the above-mentioned problems caused by the kneading and pulverization method, a toner production method by a polymerization method has been actively proposed. This method makes it easy to reduce the particle size of the toner, and the particle size distribution is sharper than the particle size distribution of the toner obtained by the pulverization method. In addition, wax can be included.

  Production of polymerized toner by suspension polymerization in an aqueous medium such as Patent Document 1 (Japanese Patent Laid-Open No. 2001-296700) and Patent Document 2 (Japanese Patent Laid-Open No. 2001-305797). Many reports on the production of polymerized toners by the emulsion aggregation method have been made, such as JP-A No. 305797), and it is known that a sharp particle size distribution can be obtained as the particle size of the toner is reduced. However, the binder resin component of the polymerized toner by these suspension polymerization method and emulsion aggregation method is a styrene-acrylic resin obtained by radical polymerization, and there remains a problem with respect to a high level of low-temperature fixability. In order to achieve low-temperature fixability, it is indispensable to reduce the molecular weight of the binder resin. When the styrene-acrylic resin used as the binder resin in the above polymerized toner is reduced in molecular weight, the toner is reduced in performance. The durability of is insufficient. In addition, since a large amount of catalyst and chain transfer agent are used to reduce the molecular weight, it is necessary not only to affect the toner performance due to residual impurities but also to solve productivity problems such as reaction control and cost. is there.

Also, dry toners excellent in all of heat-resistant storage stability, low-temperature fixability and hot offset resistance are disclosed in Patent Document 3 (Japanese Patent Laid-Open No. 2002-287400) and Patent Document 4 (Japanese Patent Laid-Open No. 2002-351143). The toner production methods described in these publications include a high molecular weight process in which an isocyanate group-containing polyester prepolymer is subjected to a polyaddition reaction with an amine in an organic solvent and an aqueous medium. However, in this production method, the sharp melt property of the polyester resin as the base resin is insufficient to satisfy the low-temperature fixability.
JP 2001-296700 A JP 2001-305797 A JP 2002-287400 A JP 2002-351143 A

  The present invention has been made in view of the above points, and in an electrostatic charge image developing toner, it is excellent in negative charge characteristics, low-temperature fixability, high-temperature offset resistance, heat-resistant storage stability, and environmental resistance characteristics. It is an object to provide a toner for developing a charge image and a dry developer.

  As a result of intensive studies by the present inventors, it is important to use a polyester resin containing a phenolic hydroxyl group that is essentially negatively charged in the binder resin, and the polyester resin has a phenolic hydroxyl group content. It came to the conclusion that the target performance can be obtained by setting the amount within the specified range.

That is, the present invention
(1) In an organic solvent, at least a binder resin containing a modified polyester resin, a colorant, and a release agent are dissolved or dispersed, and the solution or dispersion is dispersed in an aqueous medium and granulated. In the toner after removing the organic solvent, washing and drying, the terminal of the modified polyester resin is sealed with a phenolic hydroxyl group-containing compound, and the hydroxyl value is 10 to 80. Toner for charge image development.
(2) At least a polymer having a site capable of reacting with a compound having an active hydrogen group, a binder resin, a colorant, and a release agent are dissolved or dispersed in an organic solvent, and the solution or dispersion is dispersed into resin fine particles. In the toner which is dispersed in the aqueous medium and reacted with the polymer having a site capable of reacting with the compound having an active hydrogen group, or while reacting, the organic solvent is removed, washed and dried. A toner for developing electrostatic images, wherein the binder resin contains at least a polyester resin, the terminal of the polyester resin is sealed with a phenolic hydroxyl group-containing compound, and the hydroxyl value thereof is 10 to 80.
(3) The electrostatic image developing toner according to (1) or (2) above, wherein the polyester resin has a THF-soluble component having a weight average molecular weight of 1,000 to 30,000.
(4) The toner for developing an electrostatic charge image according to any one of (1) to (3), wherein the polyester resin has a glass transition point of 35 to 65 ° C.
(5) The electrostatic image developing toner according to any one of (1) to (4), wherein the polyester resin has an acid value of 1.0 to 50.0 KOHmg / g.
(6) The toner for developing an electrostatic charge image according to any one of (1) to (5), wherein the toner has an acid value of 0.5 to 40.0 KOHmg / g.
(7) The toner for developing an electrostatic charge image according to any one of (1) to (6), wherein the toner has a glass transition point of 40 to 70 ° C.
(8) The toner for developing an electrostatic charge image according to any one of (1) to (7), wherein the toner has a volume average particle diameter of 3 to 8 μm.
(9) The toner for developing an electrostatic charge image according to any one of (1) to (8), wherein Dv / Dn of the toner is 1.25 or less.
(10) The electrostatic image developing toner according to any one of (1) to (9), wherein the toner has an average circularity of 0.92 to 1.00.
(11) The electrostatic image developing toner according to any one of (1) to (10), wherein the toner has a BET specific surface area of 1.0 to 6.0 m ² / g.
(12) Dissolve or disperse at least a polymer having a site capable of reacting with a compound having an active hydrogen group, an acidic group-containing binder resin, a colorant, and a release agent in an organic solvent, and the solution or dispersion Is dispersed in an aqueous medium containing an active hydrogen-containing compound and a resin fine particle, and the active hydrogen-containing compound is reacted with a polymer having a site capable of reacting with the compound having an active hydrogen group, or while reacting, The present invention relates to the method for producing a toner for developing an electrostatic charge according to the above (1) to (11), wherein the organic solvent is removed, washed and dried.

  According to the present invention, it is possible to obtain an electrostatic image developing toner having sufficient low-temperature fixing, high-temperature offset resistance, and heat-resistant storage stability while realizing excellent negative chargeability.

  The present invention is described in detail below. The polyester resin that is a binder resin preferably has a phenolic hydroxyl group in the molecule of 10 to 80 as the phenolic hydroxyl value. When the phenolic hydroxyl value is less than 0.5, the negative charging effect derived from the phenolic hydroxyl group is reduced, and when it exceeds 80, the hygroscopicity is increased and the toner performance is deteriorated. Furthermore, the phenolic hydroxyl value is preferably 20 to 60 from the viewpoint of stably obtaining a large negative charge amount.

  The polymer having a site capable of reacting with the compound having an active hydrogen group used in the present invention is preferably an isocyanate group-containing polyester-based prepolymer, and the reaction between the prepolymer and the active hydrogen-containing compound involves the reaction of the prepolymer with a diamine. A high molecular weight reaction in which the reaction is extended or crosslinked is preferred. Offset resistance can be imparted by increasing the molecular weight of the prepolymer.

  According to a further study of the present invention, the acidic group-containing polyester can be used to effectively exhibit low-temperature fixability while maintaining heat-resistant storage stability and to impart offset resistance by increasing the molecular weight of the prepolymer. The weight-average molecular weight of the THF soluble part of the resin is preferably 1,000 to 30,000. This is because when the amount is less than 1,000, the oligomer component increases, the heat-resistant storage stability deteriorates, and when it exceeds 30,000, the high molecular weight reaction due to the prepolymer becomes insufficient due to steric hindrance and the offset resistance deteriorates. is there.

The molecular weight according to the present invention is measured by GPC (gel permeation chromatography) as follows. Stabilize the column in a heat chamber at 40 ° C., flow THF at a flow rate of 1 ml / min through the column at this temperature, and prepare a THF sample solution of resin prepared at a sample concentration of 0.05 to 0.6% by weight. Is measured by injecting 50 to 200 μl. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of the prepared calibration curve and the count using several types of monodisperse polystyrene standard samples. As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical Co. Alternatively, the molecular weights of Toyo Soda Kogyo Co., Ltd. are 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9. It is appropriate to use x10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ , and use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.

  In addition, by setting the acid value of the polyester resin to 1.0 to 50.0 (KOHmg / g), toner properties such as low-temperature fixability, high-temperature offset resistance, heat-resistant storage stability, and charge stability are improved. Is possible. That is, when the acid value exceeds 50.0 (KOHmg / g), the extension or crosslinking reaction of the modified polyester becomes insufficient, and the high-temperature offset resistance is affected, and when it is less than 1.0 (KOHmg / g) This is because the extension or crosslinking reaction of the modified polyester is likely to proceed, causing problems in production stability.

  The acid value measuring method of the present invention is based on a method based on JIS K0070. However, when the sample does not dissolve, a solvent such as dioxane or THF is used as the solvent.

  In the present invention, since the heat resistant storage performance of the polyester resin depends on the glass transition point of the polyester before modification, it is preferable to design the glass transition point of the polyester resin at 35 ° C. to 65 ° C. That is, if it is less than 35 ° C., the heat-resistant storage stability is insufficient, and if it exceeds 65 ° C., it adversely affects low-temperature fixing.

  The glass transition point of the present invention is measured with a Rigaku THRMOFLEX TG8110 manufactured by Rigaku Corporation at a temperature increase rate of 10 ° C./min.

  According to a further study of the present invention, the toner acid value is more important than the acid value of the polyester resin for low temperature fixability and high temperature offset resistance. The toner acid value of the present invention is preferably 0.5 to 40.0 (KOHmg / g) in order to control the fixing characteristics (fixing lower limit temperature, hot offset occurrence temperature, etc.). That is, when the toner acid value exceeds 40.0 (KOHmg / g), the modified polyester is insufficiently stretched or cross-linked, affecting high-temperature offset resistance, and 0.5 (KOHmg / g). If the ratio is less than 1, the elongation or cross-linking reaction of the modified polyester is likely to proceed, causing a problem in production stability.

  The glass transition point of the toner of the present invention is preferably 40 to 70 ° C. in order to obtain low temperature fixability, heat resistant storage stability and high durability. That is, when the glass transition point is less than 40 ° C., blocking in the developing machine and filming to the photoreceptor are liable to occur, and when it exceeds 70 ° C., the low-temperature fixability tends to deteriorate.

  The toner of the present invention preferably has a volume average particle diameter (Dv) of 3 to 8 μm, and the ratio (Dv / Dn) to the number average particle diameter (Dn) is Dv / Dn ≦ 1.25. More preferably it is. By defining Dv / Dn in this way, it is possible to obtain a toner with high resolution and high image quality. In order to obtain a higher quality image, the volume average particle diameter (Dv) of the toner is 3 to 7 μm, and the ratio (Dv / Dn) to the number average particle diameter (Dn) is Dv / Dn ≦ 1.20. In addition, the number of particles of 3 μm or less is preferably 1 to 10% by number, and more preferably, the volume average particle diameter is 3 to 6 μm and Dv / Dn is Dv / Dn ≦ 1.15. Is good. Such a toner is excellent in all of heat-resistant storage stability, low-temperature fixability, and hot offset resistance, and particularly excellent in image gloss when used in a full-color copying machine. Even if the toner balance is extended over a long period, the toner particle size fluctuations in the developer are reduced, and good and stable developability can be obtained even with long-term stirring in the developing device.

  For the average particle size and particle size distribution of the toner of the present invention, a Coulter Counter TA-II type is used, and an interface (manufactured by Nikka Giken) that outputs number distribution and volume distribution is connected to a PC 9801 personal computer (manufactured by NEC). And measured.

  The toner of the present invention preferably has a specific shape and shape distribution. When the average circularity is less than 0.92, it is difficult to obtain satisfactory transferability and high-quality images free from dust. As a method for measuring the shape, an optical detection band method is suitable in which a suspension containing particles is passed through an imaging unit detection band on a flat plate, and a particle image is optically detected and analyzed by a CCD camera. Toner having an average circularity of 0.92 to 1.00, which is a value obtained by dividing the perimeter of an equivalent circle having the same projected area obtained by this method by the perimeter of the actual particle, has high reproducibility with an appropriate density reproducibility. It is preferable for forming a clear image.

  The average circularity of the toner of the present invention can be measured by a flow type particle image analyzer FPIA-2000 (manufactured by Toa Medical Electronics Co., Ltd.). As a specific measuring method, 0.1 to 0.5 ml of a surfactant, preferably alkylbenzene sulfonate is added as a dispersant to 100 to 150 ml of water from which impure solids have been removed in advance, and further measurement is performed. Add about 0.1-0.5g of sample. The suspension in which the sample is dispersed is obtained by performing dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and measuring the shape and distribution of the toner with the above apparatus at a dispersion concentration of 3000 to 10,000 / μl. .

The toner of the present invention preferably has a BET specific surface area of 1.0 to 6.0 (m ² / g), and if the BET specific surface area is less than 1.0 (m ² / g), the presence or addition of coarse particles When the amount exceeds 6.0 (m ² / g), the image quality is likely to be affected by the presence of fine particles, the presence of additives, and surface irregularities.

  The BET specific surface area of the toner of the present invention can be obtained by measuring using a device capable of complying with JIS standards (Z8830 and R1626) such as NOVA series manufactured by Yuasa Ionics.

  Furthermore, the method for producing the toner used in the present invention includes an isocyanate group as a polymer having a site capable of reacting with a compound having an active hydrogen group dispersed in an aqueous medium containing inorganic fine particles and / or fine polymer particles. It is preferable to include a high molecular weight process in which the polyester prepolymer A is reacted with amine B as an active hydrogen-containing compound.

  Next, materials used for the toner of the present invention will be described in detail. In the present invention, the organic solvent is not particularly limited as long as it is a solvent capable of dissolving and / or dispersing the toner composition. As a preferable thing, it is preferable from the point that removal is easy that the boiling point of this solvent is less than 150 degreeC. Examples of the solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, methyl acetate, ethyl acetate, methyl ethyl ketone, acetone. , Tetrahydrofuran or the like can be used alone or in combination of two or more. The amount of solvent used is usually 40 to 300 parts, preferably 60 to 140 parts, and more preferably 80 to 120 parts with respect to 100 parts of the toner composition.

  The resin fine particles used in the present invention are not particularly limited as long as the resin fine particles can form an aqueous dispersion in an aqueous medium, and can be appropriately selected from known resins according to the purpose. Or a thermosetting resin, for example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer Examples thereof include a resin and a polycarbonate resin. These may be used individually by 1 type and may use 2 or more types together. Among these, it is preferable that it is formed of at least one selected from vinyl resins, polyurethane resins, epoxy resins, and polyester resins in that an aqueous dispersion of fine spherical resin particles can be easily obtained. The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer. For example, a styrene- (meth) acrylic acid ester resin, a styrene-butadiene copolymer, a (meth) acrylic acid-acrylic acid ester polymer. Styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- (meth) acrylic acid copolymer, and the like.

The binder resin used in the present invention contains at least a polyester resin, and the end of the polyester resin is sealed with a phenolic hydroxyl group-containing compound.
Thus, the polyester resin used in the present invention is characterized by using a phenolic hydroxyl group-containing carboxylic acid in order to seal the terminal end with a phenolic hydroxyl group-containing compound. Examples of the phenolic hydroxyl group-containing carboxylic acid include salicylic acid, 1,4-dihydroxy-2-naphthoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4-hydroxyphenyl-4 ^, -carboxylic acid, and 5-hydroxy. Examples include isophthalic acid, p-hydroxyphenylacetic acid, and p-hydroxyphenylpropionic acid. For other materials, alcohols and carboxylic acids used in normal polycondensation are used. Examples of the alcohol include glycols such as ethylene glycol, diethylene glycol, triethylene glycol and propylene glycol, etherified bisphenols such as 1.4-bis (hydroxymethyl) cyclohexane and bisphenol A, and other dihydric alcohols. Mention may be made of monomers and trihydric or higher polyhydric alcohol monomers. Examples of carboxylic acids include divalent organic acid monomers such as maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, and malonic acid, 1,2,4-benzenetricarboxylic acid, 1 , 2,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methylenecarboxy Mention may be made of trivalent or higher polyvalent carboxylic acid monomers such as propane and 1,2,7,8-octanetetracarboxylic acid.

  In the present invention, the polyester resin having the phenolic hydroxyl group is used as the binder resin, but other general binder resins may be mixed with the resin. Such resins include polystyrene, chloropolystyrene, poly α-methylstyrene, styrene / chlorostyrene copolymer, styrene / propylene copolymer, styrene / butadiene copolymer, styrene / vinyl chloride copolymer, styrene / Vinyl acetate copolymer, styrene / maleic acid copolymer, styrene / acrylic acid ester copolymer (styrene / methyl acrylate copolymer, styrene / ethyl acrylate copolymer, styrene / butyl acrylate copolymer, Styrene / octyl acrylate copolymer, styrene / phenyl acrylate copolymer, etc.), styrene / methacrylic acid ester copolymer (styrene / methyl methacrylate copolymer, styrene / ethyl methacrylate copolymer, styrene / methacrylic acid) Acid butyl copolymer, styrene / methacrylic acid Styrene resins such as phenyl copolymers, styrene / α-chloroacrylate copolymers, styrene / acrylonitrile / acrylate esters copolymers (homopolymers or copolymers containing styrene or substituted styrene) , Vinyl chloride resin, styrene / vinyl acetate copolymer, rosin-modified maleic acid resin, phenol resin, epoxy resin, polyethylene resin, polypropylene resin, ionomer resin, polyurethane resin, silicone resin, ketone resin, ethylene / ethyl acrylate copolymer , Xylene resin, polyvinyl butyral resin, etc., petroleum resins, hydrogenated petroleum resins and the like. As the binder resin, such a resin can be used in the range of 5 wt% to 95 wt% with respect to the polyester resin having a phenolic hydroxyl group.

The polymer having a site capable of reacting with the compound having an active hydrogen group used in the present invention is a prepolymer.
The prepolymer used in the present invention is preferably a polyester-based prepolymer A containing an isocyanate group, and a polyisocyanate which is a polycondensate of a polyol (PO) and a polycarboxylic acid (PC) and has an active hydrogen group. It can be obtained by reacting with (PIC). In this case, examples of the active hydrogen group of the polyester include a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group, and the like. Among these, an alcoholic hydroxyl group is preferable.

  Examples of the polyol (PO) include diol (DIO) and trivalent or higher polyol (TO), and (DIO) alone or a mixture of (DIO) and a small amount of (TO) is preferable. Diol (DIO) includes alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol, triethylene glycol, Ethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F, Bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above alicyclic diol; Alkylene oxide phenol compound (ethylene oxide, propylene oxide, butylene oxide, etc.), etc. adducts. Among them, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use. Trivalent or higher polyols (TO) include 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trivalent or higher phenols (Tris) Phenol PA, phenol novolak, cresol novolak, etc.); alkylene oxide adducts of the above trivalent or more polyphenols.

  Examples of the polycarboxylic acid (PC) include dicarboxylic acid (DIC) and trivalent or higher polycarboxylic acid (TC), and (DIC) alone and a mixture of (DIC) and a small amount of (TC) are preferable. Dicarboxylic acids (DIC) include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, naphthalene) Dicarboxylic acid and the like). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Examples of the trivalent or higher polycarboxylic acid (TC) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid). In addition, as polycarboxylic acid (PC), you may make it react with a polyol (PO) using the above-mentioned acid anhydride or lower alkyl ester (Methyl ester, ethyl ester, isopropyl ester, etc.).

  The ratio of the polyol (PO) and the polycarboxylic acid (PC) is usually 2/1 to 1/1, preferably 1 as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 5/1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.

  Examples of the polyisocyanate (PIC) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); Aromatic diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; the polyisocyanates are phenol derivatives, oximes, caprolactams And a combination of two or more of these.

  When obtaining a polyester-based prepolymer having an isocyanate group, the ratio of the polyisocyanate (PIC) to the polyester-based resin (PE) having active hydrogen is such that the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group are The equivalent ratio [NCO] / [OH] is usually 5/1 to 1/1, preferably 4/1 to 1.2 / 1, and more preferably 2.5 / 1 to 1.5 / 1. The content of the polyisocyanate (PIC) component in the prepolymer A having an isocyanate group at the terminal is usually 0.5 to 40% by weight, preferably 1 to 30% by weight, more preferably 2 to 20% by weight. .

  As the amine B, polyamines and / or amines having an active hydrogen-containing group are used. In this case, the active hydrogen-containing group includes a hydroxyl group and a mercapto group. Such amines include diamine (B1), tri- or higher polyamine (B2), aminoalcohol (B3), aminomercaptan (B4), amino acid (B5), and amino acids B1-B5 blocked ( B6) and the like. Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, Isophorone diamine etc.); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine etc.) and the like. Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine. Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline. Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan. Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid. Examples of the B1 to B5 amino group blocked (B6) include ketimine compounds and oxazoline compounds obtained from the B1 to B5 amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these amines B, (B1) and a mixture of (B1) and a small amount of (B2) are preferable.

  Furthermore, when the prepolymer A and the amine B are reacted, the molecular weight of the polyester can be adjusted by using an elongation terminator if necessary. Examples of the elongation terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds). The addition amount is appropriately selected in relation to the molecular weight desired for the urea-modified polyester to be produced.

  The ratio of the amine B and the prepolymer A having an isocyanate group is the ratio of the isocyanate group [NCO] in the prepolymer A having an isocyanate group to the amino group [NHx] in the amine B (x is a number from 1 to 2). ) Equivalent ratio [NCO] / [NHx] is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. It is.

  As the coloring agent of the present invention, all known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide , Ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan fast yellow ( 5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red , Fais red, parachlorol Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine B, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Tolujing Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake , Thioindigo red B, thioindigo maroon, oil red, quinacridone red, pyrazolone , Polyazo red, chrome vermillion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkali blue rake, peacock blue rake, Victoria blue rake, metal free phthalocyanine blue, phthalocyanine blue, fast sky blue, in Dunslen Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake Phthalocyanine green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by weight, preferably 3 to 10% by weight, based on the toner.

  The colorant used in the present invention can also be used as a master batch combined with a resin. As the binder resin kneaded together with the production of the masterbatch or the masterbatch, in addition to the above-described polyester resin, styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, and its substituted polymers; styrene-p-chlorostyrene Copolymer, Styrene-propylene copolymer, Styrene-vinyltoluene copolymer, Styrene-vinylnaphthalene copolymer, Styrene-methyl acrylate copolymer, Styrene-ethyl acrylate copolymer, Styrene-butyl acrylate Copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer Coalesce, styrene-ax Ronitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester Styrene copolymers such as copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid Resins, rosins, modified rosins, terpene resins, aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, paraffin waxes and the like can be used, and these can be used alone or in combination.

  This master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under a high shear force to obtain a master batch. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. Also, a so-called flushing method called watering paste containing water of a colorant is mixed and kneaded together with a resin and an organic solvent, and the colorant is transferred to the resin side to remove moisture and organic solvent components. Since it can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

  Further, a wax may be contained together with the toner binder and the colorant. Known waxes can be used as the wax of the present invention, such as polyolefin wax (polyethylene wax, polypropylene wax, etc.); long chain hydrocarbon (paraffin wax, sasol wax, etc.); carbonyl group-containing wax, etc. It is done. Of these, carbonyl group-containing waxes are preferred. Carbonyl group-containing waxes include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18. -Octadecandiol diol distearate, etc.); polyalkanol esters (tristearyl trimellitic acid, distearyl maleate, etc.); polyalkanoic acid amides (ethylene diamine dibehenyl amide, etc.); polyalkylamides (trimellitic acid tristearyl amide, etc.) And dialkyl ketones (such as distearyl ketone). Among these carbonyl group-containing waxes, polyalkanoic acid esters are preferred. The melting point of the wax of the present invention is usually 40 to 160 ° C, preferably 50 to 120 ° C, more preferably 60 to 90 ° C. A wax having a melting point of less than 40 ° C. has an adverse effect on heat resistant storage stability, and a wax having a melting point of more than 160 ° C. tends to cause a cold offset when fixing at a low temperature. Further, the melt viscosity of the wax is preferably 5 to 1000 cps, more preferably 10 to 100 cps as a measured value at a temperature 20 ° C. higher than the melting point. Waxes exceeding 1000 cps have poor effects for improving hot offset resistance and low-temperature fixability. The content of the wax in the toner is usually 0 to 40% by weight, preferably 3 to 30% by weight.

  The toner of the present invention may contain a charge control agent as necessary. All known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified). Quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of a phenol-based condensate (manufactured by Orient Chemical Industry Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP-415 (manufactured by Hodogaya Chemical Industry Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit), copper phthalocyanine, perylene, quinaclide And azo pigments, and other high molecular compounds having a functional group such as a sulfonic acid group, a carboxyl group, and a quaternary ammonium salt.

  In the present invention, the amount of charge control agent used is determined by the toner production method including the type of binder resin, the presence or absence of additives used as necessary, and the dispersion method, and is uniquely limited. However, it is preferably used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin. The range of 0.2 to 5 parts by weight is preferable. When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attractive force with the developing roller is increased, the flowability of the developer is reduced, and the image density is reduced. Incurs a decline. These charge control agents can be dissolved and dispersed after being melt-kneaded with a masterbatch and resin, and of course, they can be added directly when dissolved and dispersed in an organic solvent, or fixed on the toner surface after preparation of toner particles. May be.

As the external additive for assisting the fluidity, developability and chargeability of the colored particles obtained in the present invention, inorganic fine particles can be preferably used. The primary particle diameter of the inorganic fine particles is preferably 5 mμ to 2 μm, and particularly preferably 5 mμ to 500 mμ. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The proportion of the inorganic fine particles used is preferably 0.01 to 5% by weight of the toner, and particularly preferably 0.01 to 2.0% by weight. Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.

  Other polymer fine particles such as polystyrene obtained by soap-free emulsion polymerization, suspension polymerization and dispersion polymerization, methacrylic acid ester and acrylic acid ester copolymer, polycondensation system such as silicone, benzoguanamine and nylon, and thermosetting resin Examples include polymer particles.

  Such a fluidizing agent can be surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. .

  Examples of the cleaning property improver for removing the developer after transfer remaining on the photoreceptor or the primary transfer medium include, for example, zinc stearate, calcium stearate, fatty acid metal salts such as stearic acid, such as polymethyl methacrylate fine particles, polystyrene fine particles, etc. And polymer fine particles produced by soap-free emulsion polymerization. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.

  Furthermore, the toner of the present invention can be used as a magnetic toner containing a magnetic substance. Examples of the magnetic material contained in the toner include iron oxides such as magnetite, hematite, and ferrite, metals such as iron, cobalt, and nickel, These metals include alloys of metals such as aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, and mixtures thereof. Magnetite is particularly preferable from the viewpoint of magnetic properties. These ferromagnetic materials preferably have an average particle size of about 0.1 to 2 μm. The amount of the ferromagnetic material to be contained in the toner is about 15 to 200 parts by weight, particularly preferably 100 parts by weight of the resin component, relative to 100 parts by weight of the resin component. 20 to 100 parts by weight per part.

  The toner of the present invention can be used as a one-component developer or a two-component developer combined with a carrier. As the carrier when the toner of the present invention is used as a two-component developer, all known ones can be used. For example, magnetic powder such as iron powder, ferrite powder, nickel powder, glass beads, and the like, and these And the like which have been treated with a resin or the like. Examples of the resin powder that can be coated on the carrier in the present invention include a styrene-acrylic copolymer, a silicone resin, a maleic acid resin, a fluorine resin, a polyester resin, and an epoxy resin. In the case of a styrene-acrylic copolymer, those having a styrene content of 30 to 90% by weight are preferred. In this case, when the styrene content is less than 30% by weight, the development characteristics are low, and when it exceeds 90% by weight, the coating film becomes hard and easily peeled, and the life of the carrier is shortened. Moreover, the resin coating of the carrier in the present invention may contain an adhesion-imparting agent, a curing agent, a lubricant, a conductive material, a charge control agent and the like in addition to the resin.

  EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. Hereinafter, a part shows a weight part. The hydroxyl value of the phenolic hydroxyl group was measured according to the following method.

(Measurement of phenolic hydroxyl value)
Weigh accurately 10 g of resin into a 100 ml volumetric flask and add 50 ml of dioxane to dissolve. After complete dissolution, dioxane was further added to adjust to a 100 ml mark to prepare a sample solution. Next, 5 ml of the sample solution is added to a 50 ml beaker, and 5 ml of dioxane is added to make the total liquid volume 10 ml. Into this, 2 ml of a 0.5 wt% 3-methyl-2-benzothiazolinone hydrazine methanol solution, 0.4 ml of 25 wt% aqueous ammonia and 2 ml of 2 wt% aqueous potassium ferricyanide solution are sequentially added and left for 30 minutes. After filtering insolubles with 5C filter paper, the absorbance is measured with a spectrophotometer (wavelength 510 nm, cell capacity 10 ml). A blank test is performed on a blank solution obtained by performing the same operation without adding a sample. The amount of phenolic hydroxyl group in the resin is obtained from an absorbance calibration curve prepared in advance using bisphenol A as a standard substance, and converted to a hydroxyl value.

Production Example 1
(Production example of resin fine particle dispersion)
In a reaction vessel equipped with a stirrer and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 83 parts of styrene, 83 parts of methacrylic acid, When 110 parts of butyl acrylate and 1 part of ammonium persulfate were added and stirred at 400 rpm for 15 minutes, a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and an aqueous vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). A dispersion [resin fine particle dispersion 1] was obtained. The volume average particle diameter of [resin fine particle dispersion 1] measured with LA-920 was 105 nm. A portion of [resin fine particle dispersion 1] was dried to isolate the resin component. The resin content had a Tg of 59 ° C. and a weight average molecular weight of 150,000.

(Example of polyester production)
66 parts of bisphenol A ethylene oxide 2-mole adduct, 535 parts of bisphenol A propylene oxide 2-mole adduct, 231 parts of terephthalic acid, and 41 parts of isophthalic acid are charged into a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe. The condensation reaction was performed at 210 ° C. for 10 hours under a normal pressure nitrogen stream. Subsequently, 127 parts of salicylic acid was added, and the condensation reaction was continued at 210 ° C. for 5 hours. Further, the reaction was continued for 5 hours while dehydrating under a reduced pressure of 0 to 15 mmHg, followed by cooling to obtain [Polyester 1]. The polyester resin obtained had a weight-average molecular weight of 3,800, an acid value of 19 KOH mg / g, a hydroxyl value of 55 KOH mg / g, a hydroxyl value of phenolic hydroxyl group of 50, and a glass transition point of 53 ° C.

(Prepolymer production example)
Into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 795 parts of bisphenol A ethylene oxide 2-mole adduct, 200 parts of isophthalic acid, 65 parts of terephthalic acid, and 2 parts of dibutyltin oxide were added at normal pressure. Under a nitrogen stream, condensation reaction was performed at 210 ° C. for 8 hours. Next, the reaction was continued for 5 hours while dehydrating under a reduced pressure of 10 to 15 mmHg, then cooled to 80 ° C., and reacted with 170 parts of isophorone diisocyanate in ethyl acetate to obtain [Prepolymer 1]. The obtained prepolymer had a weight average molecular weight of 5,000 and an average number of functional groups of 2.25.

(Production example of ketimine compound)
About a stir bar and a thermometer, 30 parts of isophorodiamine and 70 parts of methyl ethyl ketone were charged into a reaction vessel, and reacted at 50 ° C. for 5 hours to obtain [ketimine compound 1].

(Dispersion adjustment)
In a beaker, 33 parts of [Prepolymer 1], 132 parts of [Polyester 1] and 80 parts of ethyl acetate were stirred and dissolved. Separately, 15 parts of carnauba wax as a release agent, 20 parts of carbon black pigment, and 120 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12000 rpm using a TK homomixer, and then dispersed for 10 minutes with a bead mill to obtain [Oil Material Dispersion Liquid 1].

(Example of toner production)
In a beaker, 529.5 parts of ion-exchanged water, 70 parts of [resin fine particle dispersion 1] and 0.5 part of sodium dodecylbenzenesulfonate are added, and the above-mentioned aqueous dispersion is added to this aqueous dispersion while stirring at 12000 rpm with a TK homomixer. [Toner material oil dispersion 1] 400 parts and [ketimine compound 1] 8.4 parts were added and reacted while stirring for 30 minutes. Subsequently, the contents were transferred to a flask equipped with a cooling pipe and aged using a hot water bath. The organic solvent was removed from the ripened dispersion, followed by filtration, washing and drying, followed by air classification to obtain a spherical toner base. 100 parts of the obtained base particles and 0.25 part of a charge control agent (Bontron E-84 manufactured by Orient Chemical Co., Ltd.) were charged into a Q-type mixer (Mitsui Mining Co., Ltd.), and the peripheral speed of the turbine blades was set to 50 m / sec. And mixed. In this case, the mixing operation was performed for 2 minutes, 5 cycles of 1 minute pause, and the total treatment time was 10 minutes. Further, 0.5 part of hydrophobic silica (H2000, manufactured by Clariant Japan) was added and mixed. In this case, the mixing operation was performed at a peripheral speed of 15 m / sec, and 30 seconds of mixing and rest for 1 minute were carried out for 5 cycles to obtain the final [Toner-1].

Production Example 2
(Example of polyester production)
71 parts of bisphenol A ethylene oxide 2-mole adduct, 570 parts of bisphenol A propylene oxide 2-mole adduct, 245 parts of terephthalic acid, and 44 parts of isophthalic acid are charged into a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe. The condensation reaction was performed at 210 ° C. for 10 hours under a normal pressure nitrogen stream. Subsequently, 70 parts of p-hydroxybenzoic acid was added, and the condensation reaction was continued at 210 ° C. for 5 hours. Further, the reaction was continued for 5 hours while dehydrating under a reduced pressure of 0 to 15 mmHg, followed by cooling to obtain [Polyester 2]. The obtained polyester resin had a weight-average molecular weight of 4,200, an acid value of 8 KOH mg / g, a hydroxyl value of 60 KOH mg / g, a hydroxyl value of phenolic hydroxyl group of 30, and a glass transition point of 45 ° C.

(Dispersion adjustment)
33 parts of [Prepolymer 1], 132 parts of [Polyester 2] and 80 parts of ethyl acetate were placed in a beaker and dissolved by stirring. Separately, 15 parts of carnauba wax as a release agent, 20 parts of carbon black pigment, and 120 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12000 rpm using a TK homomixer, and then dispersed for 10 minutes with a bead mill to obtain [Oil Material Dispersion Liquid 2].

(Example of toner production)
[Toner 2] was obtained in the same manner as in Example 1, except that [Toner material oil dispersion 2] was used instead of [Toner material oil dispersion 1].

Production Example 3
(Example of polyester production)
156 parts of bisphenol A ethylene oxide 2-mole adduct, 453 parts of bisphenol A propylene oxide 2-mole adduct, 278 parts of terephthalic acid, and 55 parts of isophthalic acid are charged into a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe. The condensation reaction was performed at 210 ° C. for 10 hours under a normal pressure nitrogen stream. Subsequently, 58 parts of p-hydroxyphenylacetic acid was added, and the condensation reaction was continued at 210 ° C. for 5 hours. Further, the reaction was continued for 5 hours while dehydrating under a reduced pressure of 0 to 15 mmHg, followed by cooling to obtain [Polyester 3]. The obtained polyester resin had a weight-average molecular weight of 8,500, an acid value of 30 KOH mg / g, a hydroxyl value of 22 KOH mg / g, a hydroxyl value of phenolic hydroxyl group of 20, and a glass transition point of 60 ° C.

(Dispersion adjustment)
In a beaker, 33 parts of [Prepolymer 1], 132 parts of [Polyester 3] and 80 parts of ethyl acetate were stirred and dissolved. Separately, 15 parts of carnauba wax as a release agent, 20 parts of carbon black pigment, and 120 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed, stirred for 5 minutes at a rotation speed of 12000 rpm using a TK homomixer, and then dispersed for 10 minutes with a bead mill to obtain [toner material oil dispersion 3].

(Example of toner production)
[Toner 3] was obtained in the same manner as in Example 1 except that [Toner material oil dispersion 3] was used instead of [Toner material oil dispersion 1].

Production Example 4
(Example of polyester production)
671 parts of bisphenol A propylene oxide 2-mole adduct, 273 parts of terephthalic acid, and 12 parts of trimellitic anhydride are introduced into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe. The condensation reaction was carried out at 210 ° C. for 10 hours.
Subsequently, 45 parts of salicylic acid was added, and the condensation reaction was continued at 210 ° C. for 5 hours. Further, the reaction was continued for 5 hours while dehydrating under reduced pressure of 10 to 15 mmHg, and then cooled to obtain [Polyester 4]. The weight average molecular weight of THF-soluble matter of the obtained polyester resin was 12,500, acid value 25 KOHmg / g, hydroxyl value 60 KOHmg / g, hydroxyl value 18 of phenolic hydroxyl group, and glass transition point 51 ° C.

(Dispersion adjustment)
In a beaker, 33 parts of [Prepolymer 1], 132 parts of [Polyester 4] and 80 parts of ethyl acetate were stirred and dissolved. Separately, 15 parts of carnauba wax as a release agent, 20 parts of carbon black pigment, and 120 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed, stirred for 5 minutes at 12000 rpm using a TK homomixer, and then dispersed for 10 minutes with a bead mill to obtain [Oil Material Dispersion Liquid 4].

(Example of toner production)
[Toner 4] was obtained in the same manner as in Example 1 except that [Toner material oil dispersion 4] was used instead of [Toner material oil dispersion 1].

Production Example 5
(Example of polyester production)
163 parts of bisphenol A ethylene oxide 2-mole adduct, 470 parts of bisphenol A propylene oxide 2-mole adduct, 277 parts of terephthalic acid and 18 parts of isophthalic acid are charged into a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe. The condensation reaction was performed at 210 ° C. for 10 hours under a normal pressure nitrogen stream.
Subsequently, 73 parts of salicylic acid was added, and the condensation reaction was continued at 210 ° C. for 5 hours. Further, the reaction was continued for 5 hours while dehydrating under a reduced pressure of 10 to 15 mmHg, and then cooled to obtain [Polyester 5]. The polyester resin obtained had a weight-average molecular weight of 7,500, an acid value of 20 KOH mg / g, a hydroxyl value of 37 KOH mg / g, a hydroxyl value of phenolic hydroxyl group of 37, and a glass transition point of 50 ° C.

(Dispersion adjustment)
In a beaker, 33 parts of [Prepolymer 1], 132 parts of [Polyester 5] and 80 parts of ethyl acetate were stirred and dissolved. Separately, 15 parts of carnauba wax as a release agent, 20 parts of carbon black pigment, and 120 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12000 rpm using a TK homomixer, and then dispersed for 10 minutes with a bead mill to obtain [Oil Material Dispersion Liquid 5].

(Example of toner production)
[Toner 5] was obtained in the same manner as in Example 1 except that [Toner material oil dispersion 5] was used instead of [Toner material oil dispersion 1].

Production Example 6
(Example of polyester production)
Into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 668 parts of bisphenol A propylene oxide 2-mole adduct, 304 parts of terephthalic acid, and 5 parts of trimellitic anhydride are introduced, and under an atmospheric pressure nitrogen stream. The condensation reaction was carried out at 210 ° C. for 10 hours.
Subsequently, 23 parts of salicylic acid was added, and the condensation reaction was continued at 210 ° C. for 5 hours. Furthermore, the reaction was continued for 5 hours while dehydrating under reduced pressure of 10 to 15 mmHg, and then cooled to obtain [Polyester 6]. The polyester resin obtained had a weight-average molecular weight of 25,000, an acid value of 5 KOH mg / g, a hydroxyl value of 10 KOH mg / g, a hydroxyl value of 10 phenolic hydroxyl groups, and a glass transition point of 63 ° C.

(Dispersion adjustment)
In a beaker, 33 parts of [Prepolymer 1], 132 parts of [Polyester 6] and 80 parts of ethyl acetate were stirred and dissolved. Separately, 15 parts of carnauba wax as a release agent, 20 parts of carbon black pigment, and 120 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12000 rpm using a TK homomixer, and then dispersed for 10 minutes with a bead mill to obtain [toner material oil dispersion 6].

(Example of toner production)
[Toner 6] was obtained in the same manner as in Example 1 except that [Toner material oil dispersion 6] was used instead of [Toner material oil dispersion 1].

Production Example 7
(Example of polyester production)
Into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 583 parts of bisphenol A propylene oxide 2-mole adduct, 235 parts of terephthalic acid, and 9 parts of trimellitic anhydride were introduced, and under an atmospheric pressure nitrogen stream. The condensation reaction was carried out at 210 ° C. for 10 hours.
Next, 174 parts of salicylic acid was added, and the condensation reaction was continued at 210 ° C. for 5 hours. Further, the reaction was continued for 5 hours while dehydrating under reduced pressure of 10 to 15 mmHg, and then cooled to obtain [Polyester 7]. The obtained polyester resin had a weight-average molecular weight of 13,000, an acid value of 15 KOH mg / g, a hydroxyl value of 80 KOH mg / g, a hydroxyl value of phenolic hydroxyl group of 80, and a glass transition point of 51 ° C.

(Dispersion adjustment)
In a beaker, 33 parts of [Prepolymer 1], 132 parts of [Polyester 7] and 80 parts of ethyl acetate were stirred and dissolved. Separately, 15 parts of carnauba wax as a release agent, 20 parts of carbon black pigment, and 120 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12000 rpm using a TK homomixer, and then dispersed for 10 minutes with a bead mill to obtain [Toner Material Oily Dispersion 7].

(Example of toner production)
[Toner 7] was obtained in the same manner as in Example 1 except that [Toner material oil dispersion 1] was used instead of [Toner material oil dispersion 1].

  Table 1 shows the physical properties relating to the above-described polyester from [Toner 1] to [Toner 7].

Example 1
[Toner 1] obtained in Production Example 1 was used to evaluate low-temperature fixability, high-temperature offset resistance, heat-resistant storage stability, and chargeability.

Example 2
[Toner 2] obtained in Production Example 1 was used to evaluate low-temperature fixability, high-temperature offset resistance, heat-resistant storage stability, and chargeability.

Example 3
[Toner 3] obtained in Production Example 1 was used to evaluate low-temperature fixability, high-temperature offset resistance, heat-resistant storage stability, and chargeability.

Example 4
[Toner 4] obtained in Production Example 1 was used to evaluate low-temperature fixability, high-temperature offset resistance, heat-resistant storage stability, and chargeability.

Example 5
Using [Toner 5] obtained in Production Example 1, the low-temperature fixability, the high-temperature offset resistance, the heat-resistant storage stability, and the chargeability were evaluated.

Example 6
[Toner 6] obtained in Production Example 1 was used to evaluate low-temperature fixability, high-temperature offset resistance, heat-resistant storage stability, and chargeability.

Example 7
[Toner 7] obtained in Production Example 1 was used to evaluate low-temperature fixability, high-temperature offset resistance, heat-resistant storage stability, and chargeability.

  The toner evaluation items and evaluation methods in the examples are shown below, and the evaluation results are shown in Table 2.

(Fixability evaluation)
A Ricoh Copier Co., Ltd. using a Teflon (registered trademark) roller as a fixing roller MF2200 A machine with a modified fixing part was used to set a Ricoh type 6200 paper for a copying test. The cold offset temperature (fixing lower limit temperature) and the hot offset temperature (hot offset resistant temperature) were determined by changing the fixing temperature. The minimum fixing temperature of the conventional low-temperature fixing toner is about 140 to 150 ° C. The evaluation conditions for low-temperature fixing are as follows: the paper feed linear speed is 120 to 150 mm / sec, the surface pressure is 1.2 kgf / cm ² , the nip width is 3 mm, and the high temperature offset is the paper feed linear speed of 50 mm / sec. The contact pressure was set to 2.0 kgf / cm ² and the nip width was 4.5 mm. The criteria for each characteristic evaluation are as follows.
Low-temperature fixability (5-level evaluation)
Good ◎: Less than 140 ° C., ○: 140-149 ° C., □: 150-159 ° C., Δ: 160-170 ° C .: 170 ° C. or higher Evil hot offset property (five-step evaluation)
Good: 201 ° C. or higher, ○: 200-191 ° C., □: 190-181 ° C., Δ: 180-171 ° C., X: 170 ° C. or lower

(Heat resistant storage stability evaluation)
20g of toner sample is put in a 20ml glass bottle, and the glass bottle is tapped about 50 times to harden the sample tightly, and then left in a high temperature bath at 50 ° C for 24 hours. I asked for it.
(Good) ◎: penetration, ○: ~ 26mm, □ 25-21mm, △: 20-16mm, x: 15mm or less (bad)

<Evaluation of charge amount>
1) Charge amount for 15 seconds stirring Charge 10 g of each toner and 100 g of ferrite carrier in a stainless steel pot up to 30% of the internal volume in an environment with a temperature of 28 ° C. and a humidity of 80%, and stir for 15 seconds at a stirring speed of 100 rpm. Then, the charge amount of the toner was measured by the blow-off method.
2) Charge amount when stirred for 5 minutes Charge amount when stirred for 5 minutes as in 1) 3) Charge amount when stirred for 10 minutes As in 1) Charge amount when stirred for 10 minutes

Production Example 8
(Example of polyester production)
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 76 parts of bisphenol A ethylene oxide 2-mole adduct, 613 parts of bisphenol A propylene oxide 2-mole adduct, 264 parts of terephthalic acid and 47 parts of isophthalic acid are charged. The condensation reaction was performed at 210 ° C. for 10 hours under a normal pressure nitrogen stream. Further, the reaction was continued for 5 hours while dehydrating under a reduced pressure of 10 to 15 mmHg, followed by cooling to obtain [Polyester 8]. The polyester resin thus obtained had a weight-average molecular weight of 3,700, an acid value of 19 KOH mg / g, a hydroxyl value of 55 KOH mg / g, and a glass transition point of 50 ° C.

(Dispersion adjustment)
In a beaker, 33 parts of [Prepolymer 1], 132 parts of [Polyester 8] and 80 parts of ethyl acetate were stirred and dissolved. Separately, 15 parts of carnauba wax as a release agent, 20 parts of carbon black pigment, and 120 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12000 rpm using a TK homomixer, and then dispersed for 10 minutes with a bead mill to obtain [toner material oil dispersion 8].

(Example of toner production)
[Toner 8] was obtained in the same manner as in Example 1 except that [Toner material oil dispersion 1] was used instead of [Toner material oil dispersion 1].

Production Example 9
(Example of polyester production)
76 parts of bisphenol A ethylene oxide 2-mole adduct, 631 parts of bisphenol A propylene oxide 2-mole adduct, 245 parts of terephthalic acid, and 40 parts of isophthalic acid are charged into a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe. The condensation reaction was performed at 210 ° C. for 10 hours under a normal pressure nitrogen stream. Further, the reaction was continued for 5 hours while dehydrating under a reduced pressure of 10 to 15 mmHg, and then cooled to obtain [Polyester 9]. The polyester resin thus obtained had a weight-average molecular weight of 4,000, an acid value of 8 KOH mg / g, a hydroxyl value of 60 KOH mg / g, and a glass transition point of 45 ° C.

(Dispersion adjustment)
33 parts of [Prepolymer 1], 132 parts of [Polyester 9] and 80 parts of ethyl acetate were placed in a beaker and dissolved by stirring. Separately, 15 parts of carnauba wax as a release agent, 20 parts of carbon black pigment, and 120 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12000 rpm using a TK homomixer, followed by dispersion treatment for 10 minutes with a bead mill to obtain [Toner Material Oily Dispersion 9].

(Example of toner production)
[Toner 9] was obtained in the same manner as in Example 1 except that [Toner material oil dispersion 1] was used instead of [Toner material oil dispersion 1].

Production Example 10
(Example of polyester production)
Bisphenol A ethylene oxide 2-mole adduct 166, bisphenol A propylene oxide 2-mole adduct 481 parts, terephthalic acid 296 parts, isophthalic acid 58 parts are charged into a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe. Under a normal pressure nitrogen stream, the condensation reaction was carried out at 210 ° C. for 10 hours. The condensation reaction was continued at 210 ° C. for 5 hours. Furthermore, the reaction was continued for 5 hours while dehydrating under reduced pressure of 10 to 15 mmHg, and then cooled to obtain [Polyester 10]. The obtained polyester resin had a weight-average molecular weight of 8,400, an acid value of 30 KOH mg / g, a hydroxyl value of 22 KOH mg / g, and a glass transition point of 58 ° C.

(Dispersion adjustment)
In a beaker, 33 parts of [Prepolymer 1], 132 parts of [Polyester 10] and 80 parts of ethyl acetate were stirred and dissolved. Separately, 15 parts of carnauba wax as a release agent, 20 parts of carbon black pigment, and 120 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12000 rpm using a TK homomixer, and then dispersed for 10 minutes with a bead mill to obtain [toner material oil dispersion 10].

(Example of toner production)
[Toner 10] was obtained in the same manner as in Example 1 except that [Toner material oil dispersion 1] was used instead of [Toner material oil dispersion 1].

Production Example 11
(Example of polyester production)
Into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 741 parts of bisphenol A propylene oxide 2-mole adduct, 37 parts of diethylene glycol and 222 parts of terephthalic acid were charged, and 210 ° C. under a normal pressure nitrogen stream. For 10 hours. Further, the reaction was continued for 1 hour while dehydrating under a reduced pressure of 10 to 15 mmHg, followed by cooling to obtain [Polyester 11]. The polyester resin obtained had a weight-average molecular weight of 800, an acid value of 5 KOH mg / g, a hydroxyl value of 99 KOH mg / g, and a glass transition point of 30 ° C.

(Dispersion adjustment)
In a beaker, 33 parts of [Prepolymer 1], 132 parts of [Polyester 11] and 80 parts of ethyl acetate were stirred and dissolved. Separately, 15 parts of carnauba wax as a release agent, 20 parts of carbon black pigment, and 120 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12000 rpm using a TK homomixer, and then dispersed for 10 minutes with a bead mill to obtain [toner material oil dispersion 11].

(Example of toner production)
[Toner 11] was obtained in the same manner as in Example 1 except that [Toner material oil dispersion 1] was used instead of [Toner material oil dispersion 1].

Production Example 12
(Example of polyester production)
695 parts of bisphenol A propylene oxide 2-mole adduct, 290 parts of terephthalic acid, and 15 parts of trimellitic anhydride are introduced into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe. The condensation reaction was carried out at 210 ° C. for 10 hours. Furthermore, the reaction was continued for 5 hours while dehydrating under reduced pressure of 10 to 15 mmHg, and then cooled to obtain [Polyester 12]. The obtained polyester resin had a weight-average molecular weight of 35,000, an acid value of 20 KOH mg / g, a hydroxyl value of 37 KOH mg / g, and a glass transition point of 70 ° C.

(Dispersion adjustment)
In a beaker, 33 parts of [Prepolymer 1], 132 parts of [Polyester 12] and 80 parts of ethyl acetate were stirred and dissolved. Separately, 15 parts of carnauba wax as a release agent, 20 parts of carbon black pigment, and 120 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12000 rpm using a TK homomixer, and then dispersed for 10 minutes with a bead mill to obtain [toner material oil dispersion 12].

(Example of toner production)
[Toner 12] was obtained in the same manner as in Example 1, except that [Toner material oil dispersion 12] was used instead of [Toner material oil dispersion 1].

Production Example 13
(Example of polyester production)
Into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 677 parts of bisphenol A propylene oxide 2-mole adduct, 308 parts of terephthalic acid, and 5 parts of trimellitic anhydride were added, The condensation reaction was carried out at 210 ° C. for 10 hours. Subsequently, 10 parts of salicylic acid was added, and the condensation reaction was continued at 210 ° C. for 5 hours. Further, the reaction was continued for 5 hours while dehydrating under a reduced pressure of 10 to 15 mmHg, and then cooled to obtain [Polyester 13]. The obtained polyester resin had a weight-average molecular weight of 24,000, an acid value of 5 KOH mg / g, a hydroxyl value of 10 KOH mg / g, a hydroxyl value of phenolic hydroxyl group of 5 KOH mg / g, and a glass transition point of 62 ° C.

(Dispersion adjustment)
In a beaker, 33 parts of [Prepolymer 1], 132 parts of [Polyester 13] and 80 parts of ethyl acetate were stirred and dissolved. Separately, 15 parts of carnauba wax as a release agent, 20 parts of carbon black pigment, and 120 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12000 rpm using a TK homomixer, and then dispersed for 10 minutes with a bead mill to obtain [toner material oil dispersion 13].

(Example of toner production)
[Toner 13] was obtained in the same manner as in Example 1 except that [Toner material oil dispersion 1] was used instead of [Toner material oil dispersion 1].

Production Example 14
(Example of polyester production)
576 parts of bisphenol A propylene oxide 2-mole adduct, 229 parts of terephthalic acid, and 8 parts of trimellitic anhydride are put into a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, under an atmospheric pressure nitrogen stream. The condensation reaction was carried out at 210 ° C. for 10 hours. Subsequently, 186 parts of salicylic acid was added, and the condensation reaction was continued at 210 ° C. for 5 hours. Further, the reaction was continued for 5 hours while dehydrating under a reduced pressure of 10 to 15 mmHg, followed by cooling to obtain [Polyester 14]. The polyester resin thus obtained had a weight-average molecular weight of 12,000 in THF, an acid value of 15 KOH mg / g, a hydroxyl value of 90 KOH mg / g, a hydroxyl value of phenolic hydroxyl group of 90, and a glass transition point of 49 ° C.

(Dispersion adjustment)
In a beaker, 33 parts of [Prepolymer 1], 132 parts of [Polyester 14] and 80 parts of ethyl acetate were stirred and dissolved. Separately, 15 parts of carnauba wax as a release agent, 20 parts of carbon black pigment, and 120 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed, stirred for 5 minutes at a rotation speed of 12000 rpm using a TK homomixer, and then dispersed for 10 minutes with a bead mill to obtain [toner material oil dispersion 14].

(Example of toner production)
[Toner 14] was obtained in the same manner as in Example 1, except that [Toner material oil-based dispersion 1] was used instead of [Toner material oil-based dispersion 1].

  As a comparative example, Table 3 shows the physical properties of the above-described polyesters [Toner 8] to [Toner 14].

Comparative Example 1
Using the toner 8 obtained in Production Example 8, the low temperature fixability, the high temperature offset resistance, the heat resistant storage stability, and the chargeability were evaluated.

Comparative Example 2
Using the toner 9 obtained in Production Example 9, the low temperature fixability, the high temperature offset resistance, the heat resistant storage stability, and the chargeability were evaluated.

Comparative Example 3
Using the toner 10 obtained in Production Example 10, the low temperature fixability, the high temperature offset resistance, the heat resistant storage stability, and the chargeability were evaluated.

Comparative Example 4
Using the toner 11 obtained in Production Example 11, the low-temperature fixing property, the high-temperature offset resistance, the heat-resistant storage property, and the charging property were evaluated.

Comparative Example 5
Using the toner 12 obtained in Production Example 12, the low-temperature fixing property, the high-temperature offset resistance, the heat-resistant storage property, and the charging property were evaluated.

Comparative Example 6
Using the toner 13 obtained in Production Example 13, the low temperature fixability, the high temperature offset resistance, the heat resistant storage stability, and the chargeability were evaluated.

Comparative Example 7
Using the toner 14 obtained in Production Example 14, the low temperature fixability, the high temperature offset resistance, the heat resistant storage stability, and the chargeability were evaluated.

  The evaluation results in the comparative example are shown in Table 4. Evaluation items and evaluation methods were performed according to the examples.

Claims (12)

  A binder resin containing at least a modified polyester resin, a colorant, and a release agent are dissolved or dispersed in an organic solvent, the solution or dispersion is dispersed in an aqueous medium, granulated, and then the organic solvent. Electrostatic image development, wherein the terminal of the modified polyester resin is sealed with a phenolic hydroxyl group-containing compound and the hydroxyl value thereof is 10 to 80 in the toner that has been removed, washed and dried Toner.   At least a polymer having a site capable of reacting with a compound having an active hydrogen group, a binder resin, a colorant, and a release agent are dissolved or dispersed in an organic solvent, and the solution or dispersion is used as an aqueous medium containing resin fine particles. In the toner, the organic solvent is removed, washed, and dried after the polymer having a site capable of reacting with the compound having an active hydrogen group is reacted or dispersed. A toner for developing an electrostatic charge image, wherein the toner comprises at least a polyester resin, the terminal of the polyester resin is sealed with a phenolic hydroxyl group-containing compound, and the hydroxyl value is 10 to 80.   The toner for developing an electrostatic charge image according to claim 1 or 2, wherein the polyester resin has a weight-average molecular weight of 1,000 to 30,000 in a THF-soluble component.   The electrostatic charge image developing toner according to claim 1, wherein the polyester resin has a glass transition point of 35 to 65 ° C.   The electrostatic charge image developing toner according to claim 1, wherein the polyester resin has an acid value of 1.0 to 50.0 KOH mg / g.   6. The toner for developing an electrostatic charge image according to claim 1, wherein the toner has an acid value of 0.5 to 40.0 KOHmg / g.   The toner for electrostatic image development according to any one of claims 1 to 6, wherein the toner has a glass transition point of 40 to 70 ° C.   The toner for developing an electrostatic charge image according to claim 1, wherein the toner has a volume average particle diameter of 3 to 8 μm.   9. The electrostatic charge image developing toner according to claim 1, wherein Dv / Dn of the toner is 1.25 or less.   The toner for developing an electrostatic charge image according to claim 1, wherein the toner has an average circularity of 0.92 to 1.00. The toner for developing an electrostatic charge image according to claim 1, wherein the toner has a BET specific surface area of 1.0 to 6.0 m ² / g.   At least a polymer having a site capable of reacting with a compound having an active hydrogen group, an acidic group-containing binder resin, a colorant, and a release agent are dissolved or dispersed in an organic solvent, and the solution or dispersion is dissolved in active hydrogen. The organic solvent is dispersed in a water-containing medium containing a compound and a resin fine particle, and the active hydrogen-containing compound and the polymer having a site capable of reacting with the compound having an active hydrogen group are reacted or reacted. The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein the toner is removed, washed and dried.