JP2007233030A - Toner for electrostatic charge image development - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner corresponding to a low temperature fixing system, having good offset resistance, free from contamination in a fixing device and an image, showing a sharp distribution of charge amounts and capable of forming a visible image with high sharpness for a long period of time. <P>SOLUTION: The toner for electrostatic charge image development is obtained by: dissolving or dispersing in an organic solvent a toner composition containing a toner binder resin source material comprising a modified polyester resin (i) or its precursor reactive with an active hydrogen group of a compound having an active hydrogen group; emulsifying and dispersing the dissolved or dispersed material in an aqueous medium containing resin fine particles; allowing the dispersion to react with a crosslinking agent and/or a chain extender; and removing the solvent from the obtained dispersion liquid. The resin fine particles have the weight average particle size of 20 to 50 nm, and a coating rate of 20 to 80% of the resin fine particles on the toner particle surfaces. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a toner used as a developer for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing, and the like, and an electrophotographic developing apparatus using the toner. More particularly, the present invention relates to an electrophotographic toner, an electrophotographic developer, and an electrophotographic developing apparatus used for a copying machine, a laser printer, a plain paper fax machine, and the like using a direct or indirect electrophotographic developing system. Furthermore, full-color copiers, full-color laser printers using direct or indirect electrophotographic multicolor development systems, electrophotographic toner agents and copiers used in full-color plain paper fax machines, and image forming apparatuses such as laser beam printers (development) Device).

  Conventionally, in an electrophotographic apparatus, an electrostatic recording apparatus, or the like, an electric or magnetic latent image is visualized with toner. For example, in electrophotography, an electrostatic charge image (latent image) is formed on a photoreceptor, and then the latent image is developed with toner to form a toner image. The toner image is usually transferred onto a transfer material such as paper and then fixed by a method such as heating.

  Toner used for electrostatic image development is generally colored particles in which a binder, a colorant, a charge control agent, and other additives are contained in a binder resin. There is a suspension polymerization method. In the pulverization method, a colorant, a charge control agent, an offset preventing agent and the like are melt-mixed in a thermoplastic resin and uniformly dispersed, and the resulting composition is pulverized and classified to produce a toner. According to the pulverization method, a toner having some excellent characteristics can be produced, but there is a limitation in the selection of the toner material. For example, the composition obtained by melt mixing must be capable of being pulverized and classified by economically usable equipment. From this requirement, the melt-mixed composition must be made sufficiently brittle. Therefore, when the above composition is actually pulverized into particles, a high-range particle size distribution is likely to be formed, and when attempting to obtain a copy image with good resolution and gradation, for example, the particle size There is a disadvantage that the fine powder of 5 μm or less and the coarse powder of 20 μm or more must be removed by classification, resulting in a very low yield. Further, in the pulverization method, it is difficult to uniformly disperse the colorant, the charge control agent, and the like in the thermoplastic resin. The uneven dispersion of the compounding agent adversely affects the fluidity, developability, durability, image quality and the like of the toner.

  In recent years, in order to overcome these problems in the pulverization method, a toner production method by a suspension polymerization method has been proposed and implemented. A technique for producing a toner for developing an electrostatic latent image by a polymerization method is known. For example, toner particles are obtained by a suspension polymerization method. However, the toner particles obtained by the suspension polymerization method are spherical and have a drawback of poor cleaning properties. Development / transfer with a low image area ratio results in a small amount of residual toner, and poor cleaning does not pose a problem. However, images with a high image area ratio such as photographic images and untransferred images formed due to poor paper feed Toner may be generated on the photoconductor as untransferred toner, and if accumulated, the image may be soiled. In addition, the charging roller that contacts and charges the photosensitive member is contaminated, and the original charging ability cannot be exhibited.

  For this reason, a method for obtaining irregularly shaped toner particles by associating resin fine particles obtained by an emulsion polymerization method is disclosed (Patent Document 1). However, the toner particles obtained by the emulsion polymerization method have a large amount of surfactant remaining not only on the surface but also inside the particles even after the water washing step, impairing the environmental stability of toner charging, and the charge amount distribution. The background of the obtained image becomes poor. Further, the remaining surfactant contaminates the photoreceptor, the charging roller, the developing roller, etc., and the original charging ability cannot be exhibited.

  On the other hand, in a fixing process using a contact heating method performed using a heating member such as a heat roller, the toner particles are required to release from the heating member (hereinafter referred to as “offset resistance”). Here, the offset resistance can be improved by the presence of a release agent on the toner particle surface. On the other hand, Patent Documents 2 and 3 disclose methods for improving offset resistance not only by containing resin fine particles in the toner particles but also by unevenly distributing the resin fine particles on the surface of the toner particles. Yes. However, the minimum fixing temperature increases, and the low temperature fixing property, that is, the energy saving fixing property is not sufficient.

In addition, the following problems occur in the method of obtaining irregularly shaped toner particles by associating resin fine particles obtained by an emulsion polymerization method.
That is, when releasing agent fine particles are associated with each other in order to improve offset resistance, the releasing agent fine particles are taken into the toner particles, and as a result, offset resistance can be sufficiently improved. I can't. Resin fine particles, release agent fine particles, colorant fine particles, etc. are randomly fused to constitute toner particles, so there is a variation in composition (content ratio of constituent components) and molecular weight of constituent resins among the obtained toner particles. As a result, the toner particles have different surface characteristics, and a stable image cannot be formed over a long period of time. Further, in a low-temperature fixing system requiring low-temperature fixing, fixing inhibition occurs due to resin fine particles unevenly distributed on the toner surface, and a fixing temperature range cannot be secured.

Japanese Patent No. 2537503 JP 2000-292773 A JP 2000-292978 A

The present invention has been made based on the above situation.
Accordingly, an object of the present invention is to provide a toner that is compatible with a low-temperature fixing system, has good offset resistance, and does not contaminate a fixing device and an image in view of the above-described problems of the prior art.
It is another object of the present invention to provide a toner capable of forming a visible image having a sharp charge amount distribution and good sharpness over a long period of time.

As a result of extensive studies by the present inventors, a toner composition comprising a modified polyester resin (i) capable of reacting with an active hydrogen group of a compound having an active hydrogen group or a toner binder resin material comprising a precursor thereof is obtained. Dissolve or disperse in an organic solvent, emulsify and disperse the disperse or disperse in an aqueous medium containing resin fine particles, and react with a cross-linking agent and / or an extender to remove the solvent from the resulting dispersion. In the method of obtaining toner particles, it is important that resin fine particles are unevenly distributed on the surface of the toner particles in order to control the particle size and shape, satisfy low temperature fixing, and have good offset resistance. In addition, in order to obtain a toner having good storage stability, the volume average particle diameter of the resin fine particles is 20 to 50 nm, and the coverage of the resin fine particles on the toner particle surface is 20 to 80%. It found that it is important, and have completed the present invention.
Specifically, unlike the conventional toner simply mixed with resin fine particles, the present invention emulsifies the organic solvent liquid of the toner composition in the form of oil droplets in the aqueous medium in the production of the toner. Sometimes, resin fine particles for controlling the toner particle size are present in an aqueous medium and adsorbed on oil droplets to control the particle size distribution of the emulsified oil droplets. The resin fine particles are not removed in the washing step and are present on the toner surface of the final product. Resin fine particles present on the toner surface cause fixing inhibition to the low-temperature fixing system depending on the particle size and the amount of adhesion.
Specifically, in order to achieve low-temperature fixing, it is important to reduce the resin particle size. As a result, the resin fine particles can suppress the adhesion inhibition between the binder resin component in the toner and the fixing paper.
In the present invention, the particle size of the resin fine particles is defined within the above range, and the presence state of the resin fine particles is defined as the coverage with respect to the toner surface area.
The volume average particle diameter of the resin fine particles specified in the present invention can be achieved by the material formulation used, as will be well understood from the detailed description including the examples and comparative examples shown later.

That is, the above-described problem is solved by (1) “a toner composition comprising a toner binder resin raw material comprising a modified polyester resin (i) capable of reacting with an active hydrogen group of a compound having an active hydrogen group or a precursor thereof. Is dissolved or dispersed in an organic solvent, the dissolved or dispersed material is emulsified and dispersed in an aqueous medium containing resin fine particles, and reacted with a crosslinking agent and / or an elongation agent, and the solvent is removed from the resulting dispersion. An electrostatic charge image, wherein the resin fine particles have a weight average particle diameter of 20 to 50 nm, and the coverage of the resin fine particles on the toner particle surface is 20 to 80%. Toner for development ",
(2) “Electrostatic image developing toner, wherein the toner has a BET specific surface area of 1.1 to 4.0 m ² / g”;
(3) “The toner binder resin contains an unmodified polyester resin (ii) together with the modified polyester resin (i), and a weight ratio of (i) and (ii) ((i) / ( ii)) is 5/95 to 75/25, and the electrostatic image developing toner according to item (1) or (2),
(4) The electrostatic image developing toner according to any one of (1) to (3), wherein the toner binder resin has an acid value of 0.5 to 40 mgKOH / g "
(5) The electrostatic image developing toner according to any one of (1) to (4) above, wherein the toner binder resin has a glass transition point (Tg) of 40 to 70 ° C. "
(6) Any one of the above items (1) to (5), wherein the resin fine particles are made of a vinyl resin, a polyurethane resin, an epoxy resin, a polyester resin and / or a mixture thereof. Toner for electrostatic image development according to
(7) “The residual ratio of the resin fine particles remaining on the toner particle surface to the toner particles is 0.5 to 5.0 wt% with respect to the toner particles as measured by a pyrolysis gas chromatograph (mass spectrometry) meter. The electrostatic image developing toner according to any one of items (1) to (6),
(8) The electrostatic image developing toner according to any one of (1) to (7) above, wherein the toner particles have a volume average particle diameter (Dv) of 4 to 8 μm. "
(9) The item (1), wherein the value (Dv / Dn) of the volume average particle diameter (Dv) of the toner particles to the number average particle diameter (Dn) is 1.25 or less. Thru | or the toner for electrostatic image development in any one of (8) term | claims,
(10) The electrostatic image developing toner according to any one of (1) to (9), wherein the toner particles have an average circularity of 0.97 to 0.90. "
(11) The method according to any one of (1) to (10), wherein the step of removing the solvent in the emulsified dispersion is performed at least under reduced pressure and / or heating conditions. The toner for developing an electrostatic image according to the description ",
(12) The electrostatic image developing toner according to any one of (1) to (11), wherein the step of removing the solvent in the emulsified dispersion is performed by filtration. Is achieved.
The above-mentioned object is achieved by (13) “Developer characterized in that it contains toner for developing electrostatic image according to any one of items (1) to (12)” of the present invention. Is done.

  As will be apparent from the following detailed and specific description, according to the present invention, it is possible to provide a toner that is compatible with a low-temperature fixing system, has good offset resistance, and does not contaminate the fixing device and the image. In addition, an extremely excellent effect that a toner capable of forming a visible image having a sharp charge amount distribution and a sharpness over a long period of time can be provided.

The present invention is described in detail below.
(Resin fine particles)
The resin fine particles in the toner of the present invention are added in a specific manufacturing process of the toner in order to control the toner shape (circularity, particle size distribution, etc.) described later, and the weight average particle diameter of the resin fine particles is 20 to 50 nm. It is important that the coverage of the resin fine particles on the toner particle surface is 20 to 80%. When the weight average particle size of the resin fine particles is less than 20 nm and the coverage of the resin fine particles on the toner particle surface is less than 20%, it is difficult to control the toner particle size stably, and the hot offset resistance and heat storage stability are low. Defects are seen.
Further, when the weight average particle diameter of the resin fine particles is larger than 50 nm and the coverage of the resin fine particles on the toner particle surface exceeds 80%, the resin fine particles cause the binder resin to ooze out and increase the minimum fixing temperature. Is seen. Further, the seepage of the wax is inhibited, and the effect of releasing the wax is not sufficiently obtained, and the occurrence of offset is observed.
The average particle diameter of the resin fine particles can be measured using a particle size distribution measuring apparatus LA-920 (manufactured by Horiba, Ltd.) using a laser light scattering method.
The coverage of the resin fine particles on the toner surface can be obtained by the following formula (1).

前記式中、Ｄｃはキャリアの重量平均粒径（μｍ）、Ｄｔはトナーの重量平均粒径（μｍ）、Ｗｔはトナーの重量（ｇ）、Ｗｃはキャリアの重量（ｇ）、Ｐｔはトナー真密度（ｇ／ｃｍ^３）、Ｐｃはキャリア真密度（ｇ／ｃｍ^３）をそれぞれ表わす。

In the above formula, Dc is the weight average particle diameter (μm) of the carrier, Dt is the weight average particle diameter (μm) of the toner, Wt is the weight of the toner (g), Wc is the weight of the carrier (g), and Pt is the true toner The density (g / cm ³ ) and Pc represent the true carrier density (g / cm ³ ), respectively.

(BET specific surface area)
The BET specific surface area of the toner is preferably 1.1 to 4.0 m ² / g.
When the BET specific surface area of the toner is less than 1.1 m ² / g, the entire toner surface is densely covered, and the resin fine particles inhibit the adhesion between the binder resin component inside the toner and the fixing paper, and the minimum fixing temperature An increase is seen. In addition, the resin fine particles inhibit the exudation of the wax, the wax releasing effect cannot be obtained, and the occurrence of offset is observed.
When the BET specific surface area exceeds 4.0 m ² / g, the organic fine particles remaining on the toner surface largely protrude as convex portions, or the resin fine particles remain as a coarse multiple layer. The adhesiveness between the resin component and the fixing paper is hindered, and the minimum fixing temperature is increased. Further, the resin fine particles inhibit the exudation of the wax, and the effect of releasing the wax is not sufficiently obtained, and the occurrence of offset is observed. The specific surface area of the toner is likely to have an effect on image quality due to the surface of the additive and the surface irregularities. The specific surface area of the toner is determined according to the BET method by using a specific surface area measuring device Autosorb 1 (manufactured by Yuasa Ionics) with nitrogen gas on the sample surface. It can be adsorbed and measured using the BET multipoint method.

(Residual rate of resin fine particles)
The resin fine particles in the toner of the present invention are added in the toner production process in order to control the toner shape (circularity, particle size distribution, etc.), which will be described later, but the residual ratio with respect to the toner particles is 0.5 to 5.0 wt. % Is preferable. When the residual ratio is less than 0.5 wt%, the storage stability of the toner is deteriorated, and blocking occurs during storage and in the developing machine. When the residual amount exceeds 5.0 wt%, the resin fine particles Inhibits the exudation of the wax, the effect of releasing the wax is not obtained, and the occurrence of offset is observed.
The residual rate of the resin fine particles can be measured by analyzing a substance caused by the resin fine particles, not by the toner particles, using a pyrolysis gas chromatograph mass spectrometer, and calculating from the peak area.
The detector is preferably a mass spectrometer, but is not particularly limited.

(Circularity and circularity distribution)
The toner in the present invention preferably has a specific shape and shape distribution, and a toner having an average circularity of 0.97 to 0.90 is effective for forming a high-definition image having a reproducibility with an appropriate density. It turned out to be. More preferably, particles having an average circularity of 0.955 to 0.940 and a circularity of less than 0.94 are 15% or less. When the average circularity exceeds 0.97, in a system that employs blade cleaning or the like, a cleaning failure occurs on the photosensitive member and the transfer belt, causing stain on the image. For example, in development / transfer with a low image area ratio, there is little transfer residual toner, and cleaning defects do not become a problem. The image-formed toner may be generated as a transfer residual toner on the photosensitive member, and if accumulated, the image may be soiled. In addition, the charging roller that contacts and charges the photosensitive member is contaminated, and the original charging ability cannot be exhibited. In addition, with an irregularly shaped toner having an average circularity of less than 0.90 and too far from a spherical shape, satisfactory transferability and high-quality images without dust cannot be obtained.

  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. . This 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. This value was measured as an average circularity by a flow type particle image analyzer FPIA-2100 (manufactured by Toa Medical Electronics Co., Ltd.). A specific measurement method will be described later.

(Dv / Dn (ratio of volume average particle diameter / number average particle diameter))
The toner of the present invention preferably has a volume average particle diameter (Dv) of 4 to 8 μm, and a ratio (Dv / Dn) to the number average particle diameter (Dn) of 1.25 or less is more preferable. 1.10 to 1.25. With such a dry toner, the heat resistant storage stability, low temperature fixability, and hot offset resistance are all excellent, especially when used in a full-color copying machine, etc., and in a two-component developer, Even if the toner balance for a long period of time is performed, the fluctuation of the toner particle diameter in the developer is reduced, and good and stable developability can be obtained even with long-term stirring in the developing device. Even when the toner is used as a one-component developer, the toner particle size fluctuates even if the balance of toner (consumption of toner in the developer by image formation and replenishment of the consumed toner) is performed. (Conventionally, among toners having a particle size distribution, the consumption of large particle size toner is more rapid, and therefore the content of small particle size toner tends to increase after use for development) There is no filming of toner on the developing roller, and no toner fusion to a member such as a blade for thinning the toner, and good and stable developability even in long-term use (stirring) of the developing device. An image is obtained.

In general, it is said that the smaller the particle size of the toner, the more advantageous it is to obtain a high-resolution and high-quality image, but it is disadvantageous for transferability and cleaning properties. is there. Further, when the volume average particle size is smaller than the above range of the present invention, in the case of a two-component developer, the toner is fused to the surface of the carrier during a long period of stirring in the developing device, and the charging ability of the carrier is reduced. When used as a component developer, toner filming on the developing roller and toner fusion to a member such as a blade for thinning the toner are likely to occur.
Further, these phenomena are the same for the toner having a fine powder content higher than the above range of the present invention.
On the contrary, when the toner particle diameter is larger than the above range of the present invention, it becomes difficult to obtain a high-resolution and high-quality image, and the toner in the developer is balanced. In many cases, the fluctuation of the particle size of the particles becomes large.
It was also clarified that the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) is larger than 1.25. Further, when the volume average particle diameter / number average particle diameter (Dv / Dn) is smaller than 1.10, there are preferable aspects from the viewpoint of stabilizing the behavior of the toner and uniformizing the charge amount. It has become clear that there is a case where the toner cannot be charged or the cleaning property is deteriorated.

  Examples of organic solvents that can be used in the present invention include aromatic solvents (toluene, xylene, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), esters (ethyl acetate, etc.), amides (dimethylformamide, dimethylacetamide). Etc.) and ethers (tetrahydrofuran etc.), for example, those which are inactive with respect to polyisocyanate (3) etc. described later.

(Modified polyester resin)
In the present invention, for example, a polyester prepolymer (A) having an isocyanate group can be used as the modified polyester resin (i) capable of reacting with the active hydrogen group of the compound having an active hydrogen group or a precursor thereof. Examples of the polyester prepolymer (A) having an isocyanate group include a polycondensate of a polyol (1) and a polycarboxylic acid (2) and a polyester having an active hydrogen group further reacted with a polyisocyanate (3). Can be mentioned. Examples of the active hydrogen group possessed by the polyester include hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups, and the like. Among these, alcoholic hydroxyl groups are preferred.

Examples of the polyol (1) include a diol (1-1) and a tri- or higher valent polyol (1-2). (1-1) alone or (1-1) and a small amount of (1-2) Mixtures are preferred.
Diol (1-1) 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, 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.
The trihydric or higher polyol (1-2) includes 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols (Trisphenol PA, phenol novolak, cresol novolak, etc.); and alkylene oxide adducts of the above trivalent or higher polyphenols.

Examples of the polycarboxylic acid (2) include dicarboxylic acid (2-1) and trivalent or higher polycarboxylic acid (2-2). (2-1) alone and (2-1) with a small amount of ( The mixture of 2-2) is preferred.
Dicarboxylic acid (2-1) includes alkylene dicarboxylic acid (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acid (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acid (phthalic acid, isophthalic acid, terephthalic acid) And naphthalenedicarboxylic acid). 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 (2-2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, and the like).
In addition, as polycarboxylic acid (2), you may make it react with polyol (1) using the acid anhydride or lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.) of the above-mentioned thing.

  The ratio of the polyol (1) to the polycarboxylic acid (2) 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 (3) 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; polyisocyanates such as phenol derivatives, oximes, caprolactams, etc. And a combination of two or more of these.

The ratio of the polyisocyanate (3) is usually 5/1 to 1/1, preferably 4 /, as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. If the molar ratio of [NCO] is less than 1, the urea content in the modified polyester will be low, and the hot offset resistance will deteriorate.
The content of the polyisocyanate (3) component in the prepolymer (A) having an isocyanate group at the terminal is usually 0.5 to 40 wt%, preferably 1 to 30 wt%, more preferably 2 to 20 wt%. If it is less than 0.5 wt%, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. On the other hand, if it exceeds 40 wt%, the low-temperature fixability deteriorates.

  The number of isocyanate groups contained per molecule in the prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2.5 on average. . When the number is less than 1 per molecule, the molecular weight of the modified polyester after the crosslinking and / or elongation reaction is lowered, and the hot offset resistance is deteriorated.

(Crosslinking agent and extender)
In the present invention, amines and the like can be used as the crosslinking agent and / or the extender (the compound having an active hydrogen group). As amines (B), diamine (B1), triamine or higher polyamine (B2), amino alcohol (B3), amino mercaptan (B4), amino acid (B5), and amino groups of (B1) to (B5) (B6) etc. that are blocked.
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.
As (B6) which blocked the amino group of (B1) to (B5), ketimine compounds obtained from the amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) of (B1) to (B5), Examples include oxazoline compounds. Among these amines (B), preferred are (B1) and a mixture of (B1) and a small amount of (B2).

  Furthermore, if necessary, the molecular weight of the modified polyester after completion of the reaction can be adjusted by using a terminator for crosslinking and / or elongation. Examples of the terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those blocked (ketimine compounds).

  The ratio of amines (B) is the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B). The ratio is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. When [NCO] / [NHx] exceeds 2 or less than 1/2, the molecular weight of the resulting urea-modified polyester (i) becomes low and the hot offset resistance deteriorates.

(Unmodified polyester)
In the present invention, not only the modified polyester resin (i) is used alone, but also the polyester resin (ii) which is not modified can be contained as a toner binder resin component together with the resin (i). By using the resin (ii) in combination, the low-temperature fixability and the glossiness when used in a full-color device are improved. Examples of the resin (ii) include the same polycondensates of polyol (1) and polycarboxylic acid (2) as those of the polyester component (i), and preferred ones are the same as those of the resin (i). The resin (ii) is not limited to unmodified polyester, but may be modified with a chemical bond other than a urea bond, and may be modified with a urethane bond, for example. It is preferable that (i) and (ii) are at least partially compatible with each other in terms of low-temperature fixability and hot offset resistance. Accordingly, the polyester component (i) and the polyester component (ii) preferably have similar compositions. In the case of containing (ii), the weight ratio of (i) to (ii) is usually 5/95 to 75/25, preferably 10/90 to 25/75, more preferably 12/88 to 25/75, Especially preferably, it is 12 / 88-22 / 78. When the weight ratio of (i) is less than 5%, the hot offset resistance is deteriorated, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.

  The peak molecular weight of the resin (ii) is usually 1000 to 30000, preferably 1500 to 10000, more preferably 2000 to 8000. If it is less than 1000, heat-resistant storage stability will deteriorate, and if it exceeds 30000, low-temperature fixability will deteriorate. The hydroxyl value of the resin (ii) is preferably 5 or more, more preferably 10 to 120, and particularly preferably 20 to 80. If it is less than 5, it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. The acid value of the resin (ii) is usually 0.5 to 40, preferably 5 to 35. By having an acid value, it tends to be negatively charged. Further, those having an acid value and a hydroxyl value exceeding these ranges are easily affected by the environment under high temperature and high humidity and low temperature and low humidity, and are liable to cause image deterioration.

(Coloring agent)
As the colorant of the toner of the present invention, 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 oxidation Iron, 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, Faisa Red, Parachlor Rutonitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carnmin BS, 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, pyrazo Red, 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, indance Ren 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 , 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 wt%, preferably 3 to 10 wt%, 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 to be kneaded together with the production of the master batch or the master batch, in addition to the above-mentioned modified and unmodified polyester resins, styrene such as polystyrene, poly p-chlorostyrene, and polyvinyl toluene, and polymers of substituted products thereof; 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, Tylene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid Styrene copolymers such as acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, poly Acrylic resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, etc. The

  The masterbatch can be obtained by mixing and kneading a resin for a masterbatch and a colorant with a high shearing force to obtain a masterbatch. In this case, an organic solvent can be used in order 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.

(Release agent)
Further, the toner of the present invention may contain a wax together with a toner binder resin and a colorant. Known waxes can be used, and examples thereof include polyolefin waxes (polyethylene wax, polypropylene wax, etc.); long-chain hydrocarbons (paraffin wax, sazol wax, etc.); carbonyl group-containing waxes, and the like. 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 -Octadecanediol 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 wt%, preferably 3 to 30 wt%.

(Charge control agent)
The toner of the present invention may contain a charge control agent as necessary. 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 4 Secondary ammonium salts or compounds, tungsten simple substances or compounds, fluorine 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 Co., Ltd.), quaternary ammonium Copy charge PSYVP 2038 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, quinacridone, Examples thereof include azo pigments and other polymer 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 uniquely by the type of binder resin, the presence or absence of additives used as necessary, and the toner production method including 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. More preferably, the range of 0.2 to 5 parts by weight is good. 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. May be.

(Resin fine particles)
The resin fine particles to be contained in the toner of the present invention may be any resin as long as it is a resin that can form an aqueous dispersion, and may be a thermoplastic resin or a thermosetting resin. For example, vinyl resins, polyurethane resins, epoxy resins, polyesters Examples thereof include resins, polyamide resins, polyimide resins, silicon resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, and polycarbonate resins. As the resin fine particles, two or more of the above resins may be used in combination. Of these, vinyl resins, polyurethane resins, epoxy resins, polyester resins, and combinations thereof are preferred because an aqueous dispersion of fine spherical resin particles is easily obtained.
Vinyl resins are polymers obtained by homopolymerization or copolymerization of vinyl monomers, such as styrene- (meth) acrylic acid ester copolymers, styrene-butadiene copolymers, (meth) acrylic acid-acrylic acid ester copolymers. Examples thereof include a polymer, a styrene-acrylonitrile copolymer, a styrene-maleic anhydride copolymer, and a styrene- (meth) acrylic acid copolymer.
The resin fine particles preferably have a weight average particle diameter of 20 to 50 nm. Further, the coverage of the resin fine particles on the surface of the toner particles is preferably 20 to 80% when determined by the above formula (1) by the measurement method.

(External additive)
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 use ratio of the inorganic fine particles is preferably 0.01 to 5 wt% of the toner, and particularly preferably 0.01 to 2.0 wt%.
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, silica 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.
In addition, 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, thermosetting resin And polymer particles.

  Such an external additive such as a fluidizing agent can be subjected to surface treatment to increase hydrophobicity and prevent deterioration of fluidity 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. .

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

(Production method)
The modified polyester resin (i) capable of reacting with the active hydrogen of the toner binder resin can be produced by the following method.
The polyol (1) and the polycarboxylic acid (2) are heated to 150 to 280 ° C. in the presence of a known esterification catalyst such as tetrabutoxytitanate or dibutyltin oxide, and the generated water is distilled off as necessary. Thus, a polyester having a hydroxyl group is obtained. Subsequently, at 40-140 degreeC, this is made to react with polyisocyanate (3), and the polyester prepolymer (A) which has an isocyanate group is obtained. Furthermore, when using amines as a crosslinking agent and an extending | stretching agent, for example, amines (B) are made to react with this polyester prepolymer (A) at 0-140 degreeC, and the polyester modified | denatured by the urea bond is obtained. When (3) is reacted and (A) and (B) are reacted, a solvent can be used as necessary. Solvents that can be used include aromatic solvents (toluene, xylene, etc.): ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.): esters (ethyl acetate, etc.): amides (dimethylformamide, dimethylacetamide, etc.) and ethers And those inert to the isocyanate (3), such as tetrahydrofuran (such as tetrahydrofuran).
Moreover, when using together polyester-type resin (ii) which is not modified | denatured, it manufactures by the method similar to polyester which has a hydroxyl group, this is melt | dissolved and mixed in the solution after completion of reaction of said (i).

The dry toner of the present invention can be produced by the following method, but is not limited thereto.
(Toner production method in aqueous medium)
In the present invention, the aqueous medium used for the production of the toner may be water alone, or a solvent miscible with water may be used in combination. Examples of miscible solvents include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.), and the like.
The toner particles are obtained by forming a dispersion made of, for example, a polyester prepolymer (A) having an isocyanate group by reacting with an amine (B) or the like in an aqueous medium. As a method for stably forming a dispersion comprising a polyester prepolymer (A) in an aqueous medium, a composition of a toner raw material comprising a polyester prepolymer (A) is added to an aqueous medium and dispersed by shearing force. The method etc. are mentioned. A colorant, a colorant masterbatch, a release agent, a charge control agent, an unmodified polyester resin (ii), etc., which are polyester prepolymer (A) and other toner compositions (hereinafter referred to as toner raw materials), Mixing may be performed when the dispersion is formed in the aqueous medium, but it is more preferable to mix the toner raw material in advance and then add and disperse the mixture in the aqueous medium. In the present invention, other toner materials such as a colorant, a release agent, and a charge control agent do not necessarily have to be mixed when forming particles in an aqueous medium, but after the particles are formed. , May be added. For example, after forming particles containing no colorant, the colorant can be added by a known dyeing method.

  Although it does not specifically limit as a dispersion method, Well-known facilities, such as a low-speed shearing type, a high-speed shearing type, a friction type, a high pressure jet type, and an ultrasonic wave, are applicable. In order to make the particle size of the dispersion 2 to 20 μm, a high-speed shearing type is preferable. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 40 to 98 ° C. Higher temperatures are preferred in that the dispersion of the polyester prepolymer (A) has a low viscosity and is easy to disperse.

The amount of the aqueous medium used relative to 100 parts by weight of the toner composition containing the polyester prepolymer (A) is usually 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight. If the amount is less than 50 parts by weight, the dispersion state of the toner composition is poor, and toner particles having a predetermined particle diameter cannot be obtained.
If it exceeds 20000 parts by weight, it is not economical. Moreover, a dispersing agent can also be used as needed. It is preferable to use a dispersant because the particle size distribution becomes sharp and the dispersion is stable.

  Anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates and phosphates, alkylamines as dispersants for emulsifying and dispersing the oily phase in which the toner composition is dispersed in a liquid containing water Amine salts such as salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazolines, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride, etc. Nonionic surfactants such as quaternary ammonium salt type cationic surfactants, fatty acid amide derivatives, polyhydric alcohol derivatives, such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl N, amphoteric surfactants such as N- dimethyl ammonium betaine and the like.

  Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount. Examples of the anionic surfactant having a fluoroalkyl group preferably used include fluoroalkylcarboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [omega-fluoroalkyl (C6- C11) sodium oxy] -1-alkyl (C3-C4) sulfonate, sodium 3- [omega-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonate, fluoroalkyl (C11-C20) Carboxylic acid and metal salt thereof, perfluoroalkyl (C7 to C13) carboxylic acid and metal salt thereof, perfluoroalkyl (C4 to C12) sulfonic acid and metal salt thereof, perfluorooctanesulfonic acid diethanolamide, N-propyl-N -(2 hydroxyethyl ) Perfluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate Etc.

  Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (Daikin Kogyo Co., Ltd.), MegaFuck F-110, F-120, F-113, F-191, F-812, F-833 (Dainippon Ink Co., Ltd.), Xtop EF-102 , 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fgentent F-100, F150 (manufactured by Neos).

  Cationic surfactants include aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, aliphatic quaternary ammonium salts such as perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts, benzaza Luconium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, trade names include Surflon S-121 (Asahi Glass), Florard FC-135 (Sumitomo 3M), Unidyne DS-202 (Daikin Industries) Megafac F-150, F-824 (manufactured by Dainippon Ink, Inc.), Xtop EF-132 (manufactured by Tochem Products), and Footgent F-300 (manufactured by Neos).

  Further, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite and the like can be used as an inorganic compound dispersant which is hardly soluble in water.

  Further, the dispersed droplets may be stabilized by a polymer protective colloid. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Bodies such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-acrylate Chloro-2-hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N -Methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, etc., or esters of compounds containing vinyl alcohol and carboxyl groups, such as Vinyl acetate, vinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethylene imine, etc. Homopolymers or copolymers such as those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylene, polyoxypropylene, Oxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonyl phenyl ester Polyoxyethylenes such as, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

In addition, when an acid such as calcium phosphate salt or an alkali-soluble substance is used as the dispersion stabilizer, the calcium phosphate salt is removed from the fine particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and then washing with water. To do. It can also be removed by operations such as enzymatic degradation.
When a dispersant is used, the dispersant may remain on the surface of the toner particles, but it is preferable from the charged surface of the toner that the dispersant is washed and removed after the elongation and / or crosslinking reaction.

Furthermore, in order to lower the viscosity of the toner composition, a solvent in which the urea-modified polyester or the polyester prepolymer (A) is soluble can be used. The use of a solvent is preferable in that the particle size distribution becomes sharp. The solvent is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal. Examples of the solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, Methyl ethyl ketone, methyl isobutyl ketone and the like can be used alone or in combination of two or more. In particular, aromatic solvents such as toluene and xylene and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform and carbon tetrachloride are preferred.
The amount of the solvent used is usually 0 to 300 parts by weight, preferably 0 to 100 parts by weight, and more preferably 25 to 70 parts by weight with respect to 100 parts by weight of the modified polyester resin (i) such as polyester prepolymer (A). . When a solvent is used, it is removed by heating under normal pressure or reduced pressure after elongation and / or crosslinking reaction.

  The elongation and / or cross-linking reaction time is selected depending on the reactivity depending on the combination of the isocyanate group structure of the polyester prepolymer (A) and the amines (B), but is usually 10 minutes to 40 hours, preferably 2 to 24. It's time. The reaction temperature is usually 0 to 150 ° C., preferably 40 to 98 ° C. Moreover, a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate.

  In order to remove the organic solvent from the obtained emulsified dispersion, a method in which the temperature of the entire system is gradually raised to completely evaporate and remove the organic solvent in the droplets can be employed. Alternatively, the emulsified dispersion can be sprayed into a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner fine particles, and the aqueous dispersant can be removed by evaporation together. . As a dry atmosphere in which the emulsified dispersion is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, or the like, in particular, various air currents heated to a temperature equal to or higher than the boiling point of the highest boiling solvent used is generally used. Sufficient quality can be obtained with a short treatment such as spray dryer, belt dryer or rotary kiln.

When the particle size distribution at the time of emulsification dispersion is wide and washing and drying processes are performed while maintaining the particle size distribution, the particle size distribution can be adjusted by classifying into a desired particle size distribution.
In the classification operation, the fine particle portion can be removed in the liquid by a cyclone, a decanter, centrifugation, or the like. Of course, the classification operation may be performed after obtaining the powder as a powder after drying. The unnecessary fine particles or coarse particles obtained can be returned to the kneading step and used for the formation of particles. At that time, fine particles or coarse particles may be wet.
The dispersant used is preferably removed from the obtained dispersion as much as possible, but it is preferable to carry out it simultaneously with the classification operation described above.

By mixing the resulting dried toner powder with dissimilar particles such as release agent fine particles, charge control fine particles, fluidizing agent fine particles, and colorant fine particles, or by giving mechanical impact force to the mixed powder By immobilizing and fusing on the surface, it is possible to prevent detachment of the foreign particles from the surface of the resulting composite particle.
Specific means include a method of applying an impact force to the mixture by blades rotating at high speed, a method of injecting and accelerating the mixture in a high-speed air stream, and causing particles or composite particles to collide with an appropriate collision plate, etc. is there. As equipment, Ong mill (manufactured by Hosokawa Micron Co., Ltd.), I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) has been modified to reduce the pulverization air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), kryptron Examples include a system (manufactured by Kawasaki Heavy Industries, Ltd.) and an automatic mortar.

(Carrier for two-component developer)
When the toner of the present invention is used for a two-component developer, it may be used by mixing with a magnetic carrier, and the content ratio of the carrier and the toner in the developer is 1 to 10 wt. Part is preferred. As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier having a particle diameter of about 20 to 200 μm can be used.
Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and styrene acrylic copolymer resins, Halogenated olefin resins such as vinyl, polyester resins such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resins, polyethylene resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polytrifluoroethylene resins, polyhexafluoro Propylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride And fluoro such as terpolymers of non-fluoride monomers including, and silicone resins.
Moreover, you may contain electrically conductive powder etc. in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. These conductive powders preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control electric resistance.

  The toner of the present invention can also be used as a one-component magnetic toner that does not use a carrier or a non-magnetic toner.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this. Moreover, a part shows a weight part.

[Example 1]
(1)-Synthesis of organic fine particle emulsion 1-
In a reaction vessel in which a stir bar and a thermometer were set, 683 parts of water, 14 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 weight average particle diameter of the [resin fine particle dispersion 1] measured by LA-920 was 41 nm. A portion of [resin fine particle dispersion 1] was dried to isolate the resin component.

(2)-Adjustment of aqueous phase-
990 parts of water, 70 parts of [resin fine particle dispersion 1], 37 parts of a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries) and 90 parts of ethyl acetate are mixed and stirred. A milky white liquid was obtained. This is designated as [Aqueous Phase 1].

(3)-Synthesis of low molecular weight polyester 1-
In a reaction vessel equipped with a condenser, stirrer and nitrogen inlet tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 3-mole adduct, 208 parts terephthalic acid, 46 parts adipic acid and dibutyl Add 2 parts of tin oxide, react for 8 hours at 230 ° C. under normal pressure, and further react for 5 hours under reduced pressure of 10 to 15 mmHg. The mixture was reacted for 2 hours to obtain [Low molecular polyester 1]. [Low molecular polyester 1] had a number average molecular weight of 2500, a weight average molecular weight of 6700, a Tg of 43 ° C., and an acid value of 25.

(4) Synthesis of intermediate polyester and prepolymer
In a reaction vessel equipped with a condenser, stirrer and nitrogen inlet tube, 682 parts bisphenol A ethylene oxide 2-mole adduct, 81 parts bisphenol A propylene oxide 2-mole adduct, 283 parts terephthalic acid, 22 parts trimellitic anhydride and 2 parts of dibutyltin oxide was added, reacted at 230 ° C. at normal pressure for 8 hours, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester 1]. [Intermediate Polyester 1] had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, Tg of 55 ° C., an acid value of 0.5, and a hydroxyl value of 51.
Next, 410 parts of [Intermediate Polyester 1], 89 parts of isophorone diisocyanate and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Polymer 1] was obtained. [Prepolymer 1] had a free isocyanate weight% of 1.53%.

(5)-Synthesis of ketimine-
In a reaction vessel equipped with a stirrer and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to obtain [ketimine compound 1]. The amine value of [ketimine compound 1] was 418.

(6)-Synthesis of master batch-
1200 parts of water, 540 parts of carbon black (made by Printex 35 Dexa) [DBP oil absorption = 42 ml / 100 mg, pH = 9.5] and 1200 parts of polyester resin are added and mixed with a Henschel mixer (made by Mitsui Mining Co., Ltd.). After kneading at 150 ° C. for 30 minutes using two rolls, rolling and cooling and pulverizing with a pulverizer, [Masterbatch 1] was obtained.

(7)-Creation of oil phase-
In a container equipped with a stirrer and a thermometer, 378 parts of [Low molecular weight polyester 1], 110 parts of Carnauba WAX, 22 parts of CCA (salicylic acid metal complex E-84: Orient Chemical Industry), and 947 parts of ethyl acetate were charged with stirring. The temperature was raised to 0 ° C., kept at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 1].
[Raw material solution 1] 1324 parts were transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads were 80% by volume. Carbon black and WAX were dispersed under conditions of filling and 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] was added, followed by one pass with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 1]. The solid content concentration of [Pigment / WAX Dispersion 1] (130 ° C., 30 minutes) was 50%.
Using the above materials, [Toner 1] was obtained by the following operation means.

(8)-Emulsification => Solvent removal-
[Pigment / WAX Dispersion 1] 749 parts, [Prepolymer 1] 115 parts, [Ketimine Compound 1] 2.9 parts in a container, and TK homomixer (manufactured by Tokushu Kika) at 5,000 rpm for 1 minute After mixing, 1200 parts of [Aqueous phase 1] was added to the container, and mixed with a TK homomixer at 13,000 rpm for 20 minutes to obtain [Emulsion slurry 1].
[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 4 hours to obtain [Dispersion slurry 1]. [Dispersion Slurry 1] had a volume average particle size of 5.99 μm and a number average particle size of 5.70 μm (measured with Multisizer II).

(9) ~ Cleaning ⇒ Drying ~
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure,
1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
2) 100 parts of 10% hydrochloric acid was added to the filter cake of 1), mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
3): 300 parts of 25 ° C. ion-exchanged water was added to the filter cake of 2), mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered twice to obtain [Filter cake 1]. It was.
[Filtration cake 1] was dried at 45 ° C. for 48 hours in a circulating drier, and sieved with an opening of 75 μm mesh to obtain [Toner 1]. [Toner 1] had a resin fine particle coverage of 57%.

[Example 2]
(1)-Synthesis of organic fine particle emulsion 2-
In a reaction vessel equipped with a stir bar and a thermometer, 683 parts of water, 16 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, 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 2] was obtained. The weight average particle diameter of the [resin fine particle dispersion 2] measured by LA-920 was 23 nm. A portion of [resin fine particle dispersion 2] was dried to isolate the resin component.
(2)-Adjustment of aqueous phase 2-
990 parts of water, 20 parts of [resin fine particle dispersion 1], 37 parts of a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries) and 90 parts of ethyl acetate are mixed and stirred. A milky white liquid was obtained. This is designated as [Aqueous Phase 2].
(3) Example 1 except that [resin fine particle dispersion 2] was used instead of [resin fine particle dispersion 1] in Example 1, and [aqueous phase 2] was used instead of [aqueous phase 1]. [Toner 2] was obtained in the same manner as above. [Toner 2] had a resin fine particle coverage of 26%.

Example 3
(1)-Synthesis of organic fine particle emulsion 3-
In a reaction vessel equipped with a stirring bar and a thermometer, 683 parts of water, 12 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 2] was obtained. The weight average particle diameter of the [resin fine particle dispersion 3] measured by LA-920 was 48 nm. A portion of [resin fine particle dispersion 3] was dried to isolate the resin component.
(2)-Adjustment of aqueous phase 3-
990 parts of water, 75 parts of [resin fine particle dispersion 1], 37 parts of a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries) and 90 parts of ethyl acetate are mixed and stirred. A milky white liquid was obtained. This is designated as [Aqueous Phase 3].
(3) Example 1 except that [Resin fine particle dispersion 3] was used instead of [Resin fine particle dispersion 1] in Example 1, and [Aqueous phase 3] was used instead of [Water phase 1]. In the same manner, [Toner 3] was obtained. [Toner 3] had a resin fine particle coverage of 74%.

Example 4
(1)-Synthesis of organic fine particle emulsion 4-
In a reaction vessel in which a stir bar and a thermometer were set, 683 parts of water, 15 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 2] was obtained. The weight average particle diameter of the [resin fine particle dispersion 4] measured by LA-920 was 30 nm. A portion of [resin fine particle dispersion 4] was dried to isolate the resin component.
(2)-Adjustment of aqueous phase 4-
990 parts of water, 40 parts of [resin fine particle dispersion 1], 37 parts of a 48.5% aqueous solution of dodecyl diphenyl ether disulfonate (Eleminol MON-7: Sanyo Chemical Industries) and 90 parts of ethyl acetate are mixed and stirred. A milky white liquid was obtained. This is designated as [Aqueous Phase 4].
(3) Example 1 except that [resin fine particle dispersion 4] was used instead of [resin fine particle dispersion 1] in Example 1, and [aqueous phase 4] was used instead of [aqueous phase 1]. [Toner 4] was obtained in the same manner as above. [Toner 4] had a resin fine particle coverage of 79%.

Example 5
(1)-Synthesis of organic fine particle emulsion 5-
In a reaction vessel in which a stir bar and a thermometer were set, 683 parts of water, 13 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 2] was obtained. The weight average particle diameter of [resin fine particle dispersion 5] measured by LA-920 was 44 nm. A portion of [resin fine particle dispersion 5] was dried to isolate the resin component.
(2)-Adjustment of aqueous phase 5-
990 parts of water, 40 parts of [resin fine particle dispersion 1], 37 parts of a 48.5% aqueous solution of dodecyl diphenyl ether disulfonate (Eleminol MON-7: Sanyo Chemical Industries) and 90 parts of ethyl acetate are mixed and stirred. A milky white liquid was obtained. This is designated as [Aqueous Phase 5].
(3) Example 1 except that [Resin fine particle dispersion 5] was used instead of [Resin fine particle dispersion 1] in Example 1, and [Aqueous phase 5] was used instead of [Water phase 1]. [Toner 5] was obtained in the same manner as described above. [Toner 5] had a resin fine particle coverage of 34%.

[Comparative Example 1]
(1)-Synthesis of organic fine particle emulsion 6-
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 2] was obtained. The weight average particle diameter of the [resin fine particle dispersion 6] measured by LA-920 was 55 nm. A portion of [resin fine particle dispersion 6] was dried to isolate the resin component.
(2)-Adjustment of aqueous phase 6-
990 parts of water, 80 parts of [resin fine particle dispersion 1], 37 parts of a 48.5% aqueous solution of dodecyl diphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries) and 90 parts of ethyl acetate are mixed and stirred. A milky white liquid was obtained. This is designated as [Aqueous Phase 6].
(3) Example 1 except that [Resin fine particle dispersion 6] was used instead of [Resin fine particle dispersion 1] in Example 1, and [Aqueous phase 6] was used instead of [Water phase 1]. [Toner 6] was obtained in the same manner as above. [Toner 6] had a resin fine particle coverage of 59%.

[Comparative Example 2]
(1)-Synthesis of organic fine particle emulsion 7-
In a reaction vessel in which a stir bar and a thermometer were set, 683 parts of water, 20 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 2] was obtained. The weight average particle diameter of the [resin fine particle dispersion 7] measured by LA-920 was 16 nm. A portion of [resin fine particle dispersion 7] was dried to isolate the resin component.
(2)-Adjustment of aqueous phase 7-
990 parts of water, 20 parts of [resin fine particle dispersion 1], 37 parts of a 48.5% aqueous solution of sodium dodecyldiphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries) and 90 parts of ethyl acetate are mixed and stirred. A milky white liquid was obtained. This is designated as [Aqueous Phase 7].
(3) Example 1 except that [Resin fine particle dispersion 7] was used instead of [Resin fine particle dispersion 1] in Example 1, and [Aqueous phase 7] was used instead of [Water phase 1]. [Toner 7] was obtained in the same manner as above. [Toner 7] had a resin fine particle coverage of 58%.

[Comparative Example 3]
(1)-Synthesis of organic fine particle emulsion 8-
In a reaction vessel in which a stir bar and a thermometer were set, 683 parts of water, 14 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 2] was obtained. The weight average particle diameter of the [resin fine particle dispersion 8] measured by LA-920 was 38 nm. A portion of [resin fine particle dispersion 8] was dried to isolate the resin component.
(2)-Adjustment of aqueous phase 8-
990 parts of water, 85 parts of [resin fine particle dispersion 1], 37 parts of a 48.5% aqueous solution of dodecyl diphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries) and 90 parts of ethyl acetate are mixed and stirred. A milky white liquid was obtained. This is designated as [Aqueous Phase 8].
(3) Example 1 except that [resin fine particle dispersion 8] is used instead of [resin fine particle dispersion 1] in Example 1, and [aqueous phase 8] is used instead of [aqueous phase 1]. [Toner 8] was obtained in the same manner as above. [Toner 8] had a resin fine particle coverage of 98%.

[Comparative Example 4]
(1)-Synthesis of organic fine particle emulsion 9-
In a reaction vessel in which a stir bar and a thermometer were set, 683 parts of water, 14 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 2] was obtained. The weight average particle diameter of the [resin fine particle dispersion 9] measured by LA-920 was 40 nm. A portion of [resin fine particle dispersion 9] was dried to isolate the resin component.
(2)-Adjustment of aqueous phase 9-
990 parts of water, 20 parts of [resin fine particle dispersion 1], 37 parts of a 48.5% aqueous solution of sodium dodecyldiphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries) and 90 parts of ethyl acetate are mixed and stirred. A milky white liquid was obtained. This is designated as [Aqueous Phase 9].
(3) Example 1 except that [resin fine particle dispersion 9] was used instead of [resin fine particle dispersion 1] in Example 1, and [aqueous phase 9] was used instead of [aqueous phase 1]. [Toner 9] was obtained in the same manner as above. [Toner 9] had a resin fine particle coverage of 18%.

As described above, 0.7 part of hydrophobic silica and 0.3 part of hydrophobized titanium oxide were mixed with 100 parts of the toner obtained in each of Examples and Comparative Examples using a Henschel mixer. The obtained toner physical properties (BET specific surface area, Dv value, Dv / Dn value) are shown in Table 1.
Ricoh's 5 wt% external additive-treated toner and 95 wt% copper-zinc ferrite carrier with an average particle size of 40 μm coated with a silicone resin are prepared, and Ricoh can print 45 sheets of A4 size paper per minute Using imagioNeo 450, continuous printing was performed and the following criteria were evaluated.

(Evaluation item)
(A) Particle size Examples of the measurement device for the particle size distribution of toner particles by the Coulter counter method include Coulter Counter TA-II and Coulter Multisizer II (both manufactured by Coulter). The measurement method is described below.
First, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of an aqueous electrolytic solution. Here, the electrolytic solution is a solution prepared by preparing a 1% NaCl aqueous solution using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the measuring device is used to measure the volume and number of toner particles or toner using a 100 μm aperture as an aperture. Volume distribution and number distribution are calculated. From the obtained distribution, the weight average particle diameter (D4) and the number average particle diameter of the toner can be obtained.
As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 .35 to less than 8.00 μm; 8.00 to less than 10.08 μm; 10.08 to less than 12.70 μm; 12.70 to less than 16.00 μm; 16.00 to less than 20.20 μm; Uses 13 channels of less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm, and targets particles having a particle size of 2.00 μm to less than 40.30 μm.

(B) Fixability
Using Ricoh's imgio Neo 450, solid images and thick paper transfer paper (Ricoh Type 6200 and NBS Ricoh's copy printing paper <135>) are developed with 1.0 ± 0.1 mg / cm2 of toner in a solid image. The temperature of the fixing belt was adjusted to be variable, and the temperature at which no offset occurred on plain paper and the lower limit of fixing temperature on thick paper were measured.
The lower limit fixing temperature was determined as the fixing lower limit temperature at the fixing roll temperature at which the residual ratio of the image density after rubbing the obtained fixed image with a pad was 70% or more.

(C) Circularity It measured as average circularity with the flow type particle image analyzer FPIA-2100 (made 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. .
(D) Measuring method of resin fine particle residual ratio
Using a styrene monomer, which is a thermal decomposition product of styrene-acrylic resin fine particles in the toner, as a fingerprint component, 0.01 wt%, 0.10 wt%, 1.00 wt% of styrene-acrylic resin fine particles are added to the toner particles under the following conditions. Using the standard addition method of adding 3.00 wt% and 10.0 wt%, the resin fine particles remaining in the toner were calculated and measured by the peak area of the styrene monomer.
Analytical instrument: Pyrolysis gas chromatograph mass spectrometer
Equipment: Shimadzu Corporation QR-5000
Japan Analytical Industry JHP-3S
Thermal decomposition temperature: 590 ° C x 12 seconds
Column; DB-1 L = 30 m
I. D = 0.25mm
Film = 0.25 μm
Column temperature: 40 ° C. (holding 2 minutes) to (10 ° C./minute temperature increase) 300 ° C.
Vaporization chamber temperature: 300 ° C

Claims (13)

A toner composition containing a toner binder resin raw material composed of a modified polyester resin (i) or a precursor thereof that can react with an active hydrogen group of a compound having an active hydrogen group is dissolved or dispersed in an organic solvent. A toner obtained by emulsifying and dispersing a dispersion in an aqueous medium containing resin fine particles and reacting with a crosslinking agent and / or an extender, and removing the solvent from the obtained dispersion, A toner for developing an electrostatic charge image, wherein the weight average particle size of the toner particles is 20 to 50 nm, and the coverage of the resin fine particles on the toner particle surface is 20 to 80%. A toner for developing an electrostatic image, wherein the toner has a BET specific surface area of 1.1 to 4.0 m ² / g. The toner binder resin contains an unmodified polyester resin (ii) together with the modified polyester resin (i), and the weight ratio ((i) / (ii)) of (i) and (ii) is The electrostatic charge image developing toner according to claim 1, wherein the toner is 5/95 to 75/25. 4. The electrostatic image developing toner according to claim 1, wherein the toner binder resin has an acid value of 0.5 to 40 mg KOH / g. The electrostatic image developing toner according to any one of claims 1 to 4, wherein the toner binder resin has a glass transition point (Tg) of 40 to 70 ° C. 6. The electrostatic image developing toner according to claim 1, wherein the resin fine particles are made of a vinyl resin, a polyurethane resin, an epoxy resin, a polyester resin, and / or a mixture thereof. . The residual ratio of the resin fine particles remaining on the toner particle surface to the toner particles is 0.5 to 5.0 wt% with respect to the toner particles as measured by a pyrolysis gas chromatograph (mass spectrometry) meter. The toner for developing an electrostatic charge image according to any one of claims 1 to 6. 8. The electrostatic image developing toner according to claim 1, wherein the toner particles have a volume average particle diameter (Dv) of 4 to 8 [mu] m. The value (Dv / Dn) of the ratio of the volume average particle diameter (Dv) to the number average particle diameter (Dn) of the toner particles is 1.25 or less. Toner for developing electrostatic images. 10. The electrostatic image developing toner according to claim 1, wherein the toner particles have an average circularity of 0.97 to 0.90. 11. The toner for developing an electrostatic charge image according to claim 1, wherein the step of removing the solvent in the emulsified dispersion is performed at least under reduced pressure and / or heating conditions. The electrostatic image developing toner according to claim 1, wherein the step of removing the solvent in the emulsified dispersion is performed by filtration. A developer comprising the electrostatic image developing toner according to claim 1.