JP4908804B2 - Toner for developing electrostatic image, manufacturing method thereof, image forming apparatus using the same, container thereof, process cartridge filled with the same - Google Patents

Description

  The present invention relates to a toner for developing an electrostatic image, a production method thereof, an image forming apparatus using the same, a container thereof, and a process cartridge filled with the same.

  Conventionally, a contact heating fixing method such as a heat roll fixing method has been widely adopted as a toner fixing method. A fixing device used for a heat roll fixing method includes a heating roll and a pressure roll, and passes a recording sheet carrying a toner image through a pressure contact portion (nip portion) between the heating roll and the pressure roll. As a result, the toner image is melted and fixed on the recording sheet.

  In the contact heating fixing method typified by the heat roll fixing method, the toner image on the recording sheet is fixed by bringing the surface of a heating member (for example, a heating roll) of the contact heating fixing device into contact with the toner image. It is necessary to prevent an offset phenomenon in which a part of the toner adheres to the next recording sheet and becomes dirty.

  In order to prevent the offset phenomenon, a technology for applying or impregnating fixing oil such as silicone oil to the heating roll or pressure roll of the fixing device is known, but fixing is performed from the viewpoint of downsizing and cost reduction of the fixing device. Oilless fixing devices that omit the oil application mechanism and fixing devices of a type that reduce the amount of fixing oil applied are employed. When such a fixing device is employed, a release agent is added to the toner as an anti-offset agent.

  In the case of the heat fixing method, the heating temperature is preferably as low as possible for energy saving. However, if the thermal properties of the binder resin constituting the toner are designed too low to achieve this, heat-resistant storage is possible. The property deteriorates and problems such as blocking occur. In order to achieve both, it is advantageous to use a polyester resin as the binder resin. Polyester resins have low viscosity and high elasticity compared to vinyl copolymer resins, so they have excellent low-temperature fixability and good heat-resistant storage properties.

  However, when a toner to which a sufficient amount of a release agent is added to prevent offset is produced by a conventional pulverization method, a large amount of the release agent is exposed on the surface of the toner, causing problems such as filming and blocking. . On the other hand, so-called polymerization methods are known, such as a suspension polymerization method in which a polymerization-reactive monomer is polymerized in an aqueous medium, and an emulsion aggregation method in which fine particles are prepared and aggregated in advance by emulsion polymerization. These polymerization methods can contain a larger amount of release agent as compared with the pulverization method. Furthermore, as for the suspension polymerization method, there is a description of a toner whose structure is controlled by adding a polymerizable monomer and polymerizing after completion of normal granulation (Patent Document 1). As for the emulsion aggregation method, there is a description of a toner whose structure is controlled by adding and aggregating emulsified fine particles after completion of granulation by normal aggregation (Patent Document 2). However, since these suspension polymerization methods and emulsion aggregation methods perform polymerization in an aqueous medium, vinyl copolymer resins are used, and it is difficult to use a polyester resin that is polymerized at a high temperature of about 200 ° C. .

  As a method for granulating toner using a polyester resin, a so-called dissolution suspension method is known in which a resin polymerized in advance is dissolved in an organic solvent and granulated in an aqueous medium. In this method, the molecular weight of the resin at the time of charging becomes the molecular weight of the toner as it is, and in order to adjust the thermal characteristics of the toner, it is common to use a mixture of a low molecular weight resin and a high molecular weight resin. If the resin is added, the viscosity of the solution becomes too high and the granulation property deteriorates, and a large amount of high molecular weight resin cannot be used. Therefore, the molecular weight of the low molecular weight resin must be increased, which is disadvantageous for low temperature fixing.

  In order to solve this, there is a method of adjusting the molecular weight by subjecting a modified polyester having a reactive group to elongation and / or crosslinking after granulation, instead of introducing a high molecular weight resin. When this method is used, it is possible to adjust the thermal characteristics of the toner, but the toner structure is not sufficiently controlled, and there is a tendency that a colorant, a release agent, etc. are exposed on the surface. However, there was a problem that soiling was caused by continuous use.

  As described above, low-temperature fixability and heat-resistant storage stability are compatible, offset resistance is excellent, toner structure can be controlled, and toner with good chargeability can be realized without contaminating the developing device. It wasn't.

Japanese Patent No. 3195362 JP 2002-116574 A

  The present invention has been made in view of the above-described problems, and is compatible with both low-temperature fixability and heat-resistant storage properties, excellent in offset resistance, can control the toner structure, and is sufficient without contaminating the developing device or the like. Non-magnetic toner for developing an electrostatic charge image, which maintains the chargeability and has little image deterioration such as scumming due to long-term use, and manufacturing method thereof, developer, toner container, process cartridge and An object is to provide an image forming apparatus.

As a result of intensive studies, the inventors have made it possible to increase the smoothness of the shell layer by a) making the resin of the shell part a specific molecular weight range, and maintain sufficient chargeability during the development process. It is possible to obtain a toner with little image deterioration such as scumming due to long-term use, and b) the polyester resin of the core portion is in a specific wave number by FTIR-ATR (total reflection absorption infrared spectroscopy) method. C) has both a low-temperature fixability and a heat-resistant storage property when the glass transition point Tg measured by a differential scanning calorimeter (DSC) of the resin in the shell portion is 45 ° C. or higher and 80 ° C. or lower, The inventors have found that a toner having excellent offset resistance can be obtained, and have reached the present invention.
That is, the present invention
[1] In the electrostatic charge developing toner having a core-shell structure composed of at least a colorant, a release material, and a core layer made of a polyester resin and a shell layer made of a resin obtained by vinyl polymerization, the following a), b) and c The resin having at least a polyester skeleton is a polyester resin, and the polyester resin includes a modified polyester resin and an unmodified polyester resin, and a weight ratio of the modified polyester resin to the unmodified polyester resin. (modified polyester resin / modified polyester resin not) 5/100 to 80/20 der toner for electrostatic charge development, wherein Rukoto.
a) The molecular weight of the shell layer resin satisfies 8000 <Mw <18000.
5000 <Mw <20000 Mw: Polystyrene resin in terms of polystyrene b obtained by immersing 20 mg of toner in 5 ml of THF for 1 minute and then measuring the dissolved matter in the filtrate by gel permeation chromatography (GPC). having a peak between 850 cm ^-1 and 783 cm ^-1 by FTIR-ATR (attenuated total reflectance infrared spectroscopy).
c) The glass transition point Tg measured by a differential scanning calorimeter (DSC) of the vinyl resin forming the shell is 45 ° C. or higher and 80 ° C. or lower.
[2] The resin obtained by vinyl polymerization of the shell layer is a binary or higher copolymer containing at least one monomer having two or more unsaturated bonds. [1] Toner for electrostatic charge development.
[3] The resin obtained by vinyl polymerization of the shell layer is —OH, —COOH, —CONR1R2, —NHCONR1R2 (wherein R1 and R2 are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, an aryl group) , An aralkyl group and an alicyclic group), a binary or higher copolymer containing at least one monomer having a linear alkyl group having 2 to 22 carbon atoms bonded to the terminal. The electrostatic charge developing toner according to [1] or [2], wherein
[4] The toner has a circularity of 0.95 or more and less than 0.99, a volume average particle diameter of 4.5 μm or more and less than 8 μm microns, and the ratio of the colorant in the core part to the core part (hereinafter referred to as RA (P ) And the ratio of the release agent in the core part (hereinafter referred to as RA (W)), the ratio of the colorant in the shell part to the shell part (hereinafter referred to as RB (P)). ) And the ratio of the release agent in the shell portion (hereinafter referred to as RB (P)) is a relational expression RA (P) × 0.5> RB (P) and RA (W) × 0.5> RB The electrostatic image developing toner according to any one of [1], [2], and [3], wherein (W) is satisfied.
[5] An oil phase obtained by dissolving or dispersing at least a colorant, a release material, and a polyester resin in an organic solvent having a Hansen solubility parameter of 19.5 or less is dispersed or emulsified in an aqueous medium. The method for producing an electrostatic charge developing toner according to any one of [1] to [4], wherein the toner is obtained.
[6] The aqueous medium is water or / and a water-soluble organic solvent, an organic solvent having a Hansen solubility parameter of 19.5 or less, a surfactant, a viscosity modifier, an emulsification / dispersion stabilized fine particle, a pH adjuster, or an inorganic [6] The method for producing a toner for developing an electrostatic charge image according to [5], comprising a combination selected from salts.
[7] After forming core particles in an aqueous medium, an aqueous dispersion in which at least vinyl copolymer resin fine particles are dispersed is added, and the fine particles are adhered to the core particles to form a shell layer to form a core-shell structure. The method for producing a toner for developing an electrostatic charge image according to [5] or [6].
[8] The electrostatic image development according to [7], wherein the organic solvent is removed before the fine particles are adhered, and then an aqueous dispersion in which resin fine particles are dispersed is added to adhere the fine particles. Of manufacturing toner.
[9] The method for producing a toner for developing an electrostatic charge image according to [7], wherein the organic solvent is removed after the fine particles are adhered.
[10] The method for producing a toner for developing an electrostatic charge image according to any one of [7] to [9], wherein the fine particles are adhered and then heated to fuse the fine particles.
[11] The toner according to any one of [5] to [11], wherein the toner is obtained by performing a cleaning process with a cleaning aqueous medium after forming toner particles in an aqueous medium, and then performing a drying process. A method for producing a toner for developing an electrostatic image.
[12] The electrostatic image developing toner according to any one of [1] to [4], wherein the polyester resin of the core layer is made of a polyester resin having a glass transition temperature of 40 ° C. or higher.
[13] The resin having at least a polyester skeleton is a polyester resin, and the polyester resin contains a polyester resin stretched by urethane or / and urea bonds, [1] to [4], or [ [12] The toner for developing an electrostatic image according to any one of [12].
[14] The resin having at least a polyester skeleton is a polyester resin, and the polyester resin contains a polyester resin component formed by a reaction between a modified polyester resin having an isocyanate group at a terminal and amines. The toner for developing an electrostatic charge image according to any one of [1] to [4], [12] or [13].
[15] The resin having at least a polyester skeleton is a polyester resin, and the polyester resin contains an unmodified polyester resin, [1] to [4], [12], [13] Or the electrostatic image developing toner according to any one of [14].
[ 16 ] The toner contains 3 to 30% by weight of one or more selected from paraffins, synthetic esters, polyolefins, carnauba wax, or rice wax as a release agent. The toner for developing an electrostatic charge image according to any one of [1] to [4] or [12] to [ 15 ].
[ 17 ] The toner for developing an electrostatic charge image according to any one of [1] to [4] or [12] to [ 16 ], wherein the toner contains a charge control agent.
[ 18 ] The electrostatic image developing toner according to any one of [1] to [4] or [12] to [ 17 ], wherein the toner is a nonmagnetic one-component developing toner.
[ 19 ] An image forming apparatus comprising a toner, wherein the nonmagnetic one-component developing toner described in [ 18 ] is used as the toner.
[ 20 ] The image forming apparatus according to [ 19 ], wherein the image forming apparatus is an apparatus for forming a multicolor image.
[ 21 ] The image forming apparatus according to [ 19 ] or [ 20 ], wherein the image forming apparatus has an endless intermediate transfer unit.
[ 22 ] The image forming apparatus according to any one of [ 19 ] to [ 21 ], wherein the image forming apparatus does not include a blade as a residual toner cleaning unit in the photoreceptor or / and the intermediate transfer unit.
[ 23 ] The image forming apparatus according to any one of [ 19 ] to [ 21 ], wherein the image forming apparatus includes a blade cleaning unit.
[ 24 ] The image forming apparatus according to any one of [ 19 ] to [ 23 ], wherein the image forming apparatus includes a fixing unit using a roller provided with a heating device.
[ 25 ] The image forming apparatus according to any one of [ 19 ] to [ 23 ], wherein the image forming apparatus includes a fixing unit using a belt provided with a heating device.
[ 26 ] The image forming apparatus according to any one of [ 19 ] to [ 25 ], wherein the image forming apparatus includes an oilless fixing unit that does not require oil application to the fixing member.
[ 27 ] A toner container filled with the electrostatic image developing toner according to any one of [1] to [4] or [12] to [ 16 ].
[ 28 ] A toner container filled with the nonmagnetic one-component developing toner described in [ 18 ].
[ 29 ] In a process cartridge which integrally supports a photosensitive member and at least one means selected from a charging means, a developing means, and a cleaning means, and is detachable from an image forming apparatus main body, the developing means comprises: A toner (developer) is held, and the toner (developer) is filled with the electrostatic charge developing toner according to any one of [1] to [4] or [12] to [ 18 ]. Process cartridge.
About.

According to the present invention, the smoothness of the shell layer can be enhanced by making the range of Mw shown in the above a), and sufficient charging property can be maintained in the development process. A toner with little deterioration can be provided. Further, the above b) and c) can provide a toner having both low temperature fixability and heat resistant storage stability and excellent offset resistance and a method for producing the same.
In addition, an image forming apparatus, a toner container, and a process cartridge using the toner can be provided.

  The toner for developing an electrostatic charge image of the present invention comprises a core portion containing at least a colorant, a release agent and a binder resin (A), and a binder resin (B) covering the core portion. The binder resin (A) is mainly composed of a polyester resin, and the binder resin (B) is a vinyl copolymer resin, and the electrostatic charge image of the present invention. With this structure, the developing toner has both low-temperature fixability and heat-resistant storage stability, excellent offset resistance, control of the toner structure, and good chargeability without contaminating the developing device. Can improve dirt caused by durability.

The structure of the toner of the present invention is schematically shown in FIG.
As shown in FIG. 1, the toner 1 of the present invention includes a core portion 4 containing at least a colorant 2, a release agent 3, and a binder resin (A), and a binder resin (B The binder resin (A) is mainly composed of a polyester resin, and the binder resin (B) is a vinyl resin. That is, the core part that is the main component of the toner is a polyester resin that is advantageous for achieving both low-temperature fixability and heat-resistant storage stability as the characteristics of the resin itself, and is a surface part of the toner that greatly affects the chargeability of the toner. The shell portion is a vinyl resin that is advantageous for controlling the chargeability.

  The vinyl resin is preferably a vinyl copolymer resin from the viewpoint of chargeability control. The reason why the vinyl copolymer resin is advantageous in controlling the chargeability is as follows: (1) A plurality of types of monomers can be mixed and polymerized, and there is a high degree of freedom in selecting monomer types. For example, polar groups such as carboxylic acid sulfonic acid (2) For example, in emulsion polymerization and suspension polymerization, the structure of the polymer particles can be structured depending on the polarity of the monomers, and functional groups derived from the desired monomer species are efficiently applied to the particle surfaces. It can be unevenly distributed.

  Therefore, it is possible to obtain a toner having good fixing characteristics such as low-temperature fixability, and developability and transferability affected by charging properties. The weight ratio of the core portion to the shell portion is preferably 0.05 to 0.5, more preferably 0.07 to 0.4, and still more preferably 0.1 to 0.3. If the weight ratio of the core portion to the shell portion is less than 0.05, the effect of the binder resin (B) which is a vinyl copolymer resin cannot be sufficiently exhibited. The fixing resin (A) becomes too small, and the fixing characteristics are deteriorated. The volume average particle diameter of the toner is preferably 3 to 8 μm, and more preferably 4 to 7 μm. If the volume average particle diameter of the toner is smaller than 3 μm, the image forming process is hindered, and if it is larger than 8 μm, the resolution of the image is deteriorated.

In the toner of the present invention, in order to further enhance the effect of the core-shell structure, the ratio of the colorant in the core part (hereinafter referred to as RA (P)) and the ratio of the release agent in the core part (hereinafter referred to as “the core part”). RA (W).) Relative to the shell portion, the ratio of the colorant in the shell portion (hereinafter referred to as RB (P)) and the ratio of the release agent in the shell portion (hereinafter referred to as RB (P)). It is preferable that the following relationship is satisfied.
RA (P) × 0.5> RB (P) and RA (W) × 0.5> RB (W)
It is more preferable to satisfy the following relationship.
RA (P) × 0.2> RB (P) and RA (W) × 0.2> RB (W)
It is more preferable to satisfy the following relationship.
RA (P) × 0.01> RB (P) and RA (W) × 0.01> RB (W)

  That is, it is desirable that the colorant and the release agent are present in the vicinity of the toner surface and are not exposed on the toner surface. As a result, filming to the photoreceptor and the like by the release agent does not occur, and charging property with excellent environmental resistance is obtained. In full color toner, the difference in charging property due to the difference in colorant of each color is obtained. Can be kept to a minimum.

By designing the vinyl resin for forming the shell of the present invention to have an appropriate Tg and molecular weight range, soiling due to long-term use is improved, but Tg is 45 ° C to 80 ° C that can satisfy heat-resistant storage stability. It is preferably 50 to 70 ° C, and if it exceeds 80 ° C, the low-temperature fixability is deteriorated. On the other hand, after 20 mg of toner is immersed in 5 ml of THF for 1 minute, the dissolved matter in the filtrate is subjected to gel permeation chromatograph (GPC) measurement, and the molecular weight of the shell layer resin can be determined from the molecular weight in terms of polystyrene obtained. Mw <20000 is preferable, and 8000 ≦ Mw ≦ 18000 is particularly preferable. In addition, when Mw becomes lower than 5000, control of Tg and production of vinyl polymer resin particles become difficult, which is not suitable. On the other hand, when Mw is 20000 or more, uniform film formation is difficult to proceed, and it is difficult to sufficiently improve the smoothness.
By setting Mw to 5000 <Mw <20000, it is estimated that the smoothness of the shell layer can be improved. Sufficient chargeability is maintained in the development process, and image deterioration such as scumming due to long-term use is expected. A toner having a small amount can be obtained.

<Polyester resin>
The type of the polyester resin used in the core layer in the present invention is not particularly limited, and any resin having at least a polyester resin skeleton can be used. However, the polyester resin in the core layer is FTIR-ATR (all by reflection absorption infrared spectroscopy) preferably has a peak between 850 cm ^-1 and 783 cm ^-1. This peak is derived from the aromatic structure of the polyester resin, and the use of the polyester having this peak advantageously acts on the development of toner strength and negative chargeability.
Moreover, you may mix and use several types of polyester resins. Further, for example, a resin having both a polyester skeleton and a styrene-acryl skeleton may be used.
Examples of the polyester resin include polycondensates of the following polyol (1) and polycarboxylic acid (2).

(About polyol)
Examples of the polyol (1) include alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol, triethylene glycol, Ethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F, 4,4′-dihydroxybiphenyls such as bisphenol S, 3,3′-difluoro-4,4′-dihydroxybiphenyl, etc .; bis (3-fluoro-4-hydroxyphenyl) Nyl) methane, 1-phenyl-1,1-bis (3-fluoro-4-hydroxyphenyl) ethane, 2,2-bis (3-fluoro-4-hydroxyphenyl) propane, 2,2-bis (3 Bis (5-difluoro-4-hydroxyphenyl) propane (also known as: tetrafluorobisphenol A), 2,2-bis (3-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, etc. Hydroxyphenyl) alkanes; bis (4-hydroxyphenyl) ethers such as bis (3-fluoro-4-hydroxyphenyl) ether); alkylene oxides of the above alicyclic diols (ethylene oxide, propylene oxide, butylene oxide, etc.) Adducts; alkylene oxides of the above bisphenols (ethylene oxide) De, propylene oxide, and the like butylene oxide, 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.

In addition, trihydric or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols (trisphenol PA, phenol novolac, cresol novolac, etc.) ); Alkylene oxide adducts of the above trihydric or higher polyphenols.
In addition, the said polyol can be used individually by 1 type or in combination of 2 or more types, It is not limited to the above.

(Polycarboxylic acid)
Examples of the polycarboxylic acid (2) include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, Naphthalenedicarboxylic acid, 3-fluoroisophthalic acid, 2-fluoroisophthalic acid, 2-fluoroterephthalic acid, 2,4,5,6-tetrafluoroisophthalic acid, 2,3,5,6-tetrafluoroterephthalic acid, 5- Trifluoromethylisophthalic acid, 2,2-bis (4-carboxyphenyl) hexafluoropropane, 2,2-bis (4-carboxyphenyl) hexafluoropropane, 2,2-bis (3-carboxyphenyl) hexafluoropropane 2,2′-bis (trifluoromethyl) -4,4′- Phenyldicarboxylic acid, 3,3′-bis (trifluoromethyl) -4,4′-biphenyldicarboxylic acid, 2,2′-bis (trifluoromethyl) -3,3′-biphenyldicarboxylic acid, hexafluoroisopropylidene Dendiphthalic anhydride, etc.).

Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Further, polycarboxylic acids having 3 or more valences include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.), and acid anhydrides or lower alkyl esters (methyl esters, ethyl esters) described above. , Isopropyl ester, etc.) may be used to react with polyol (1).
In addition, the said polycarboxylic acid can be used individually by 1 type or in combination of 2 or more types, It is not limited to the above.

(Ratio of polyol and polycarboxylic acid)
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.

(Molecular weight of polyester resin)
The peak molecular weight is usually 1000-30000, preferably 1500-10000, more preferably 2000-8000. If it is less than 1000, heat-resistant storage stability will deteriorate, and if it exceeds 30000, low-temperature fixability will deteriorate.

<Vinyl resin>
The vinyl resin used in the present invention is not particularly limited, and any vinyl resin can be used. However, the vinyl resin is preferably a vinyl copolymer resin. Further, several kinds of vinyl copolymer resins may be mixed and used.
The vinyl copolymer resin is a polymer obtained by copolymerizing a vinyl monomer. Examples of the vinyl monomer include the following (1) to (11).

(1) Vinyl hydrocarbons:
Aliphatic vinyl hydrocarbons: alkenes such as ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, α-olefins other than those mentioned above; alkadienes such as butadiene, isoprene, 1 , 4-pentadiene, 1,6-hexadiene, 1,7-octadiene.
Alicyclic vinyl hydrocarbons: mono- or di-cycloalkenes and alkadienes such as cyclohexene, (di) cyclopentadiene, vinylcyclohexene, ethylidenebicycloheptene and the like; terpenes such as pinene, limonene and indene.

  Aromatic vinyl hydrocarbons: styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl) substitutions such as α-methyl styrene, vinyl toluene, 2,4-dimethyl styrene, ethyl styrene, isopropyl styrene, Butyl styrene, phenyl styrene, cyclohexyl styrene, benzyl styrene, crotyl benzene, divinyl benzene, divinyl toluene, divinyl xylene, trivinyl benzene, etc .; and vinyl naphthalene.

(2) Carboxyl group-containing vinyl monomers and salts thereof:
C3-C30 unsaturated monocarboxylic acids, unsaturated dicarboxylic acids and anhydrides thereof and monoalkyl (C1-24) esters thereof such as (meth) acrylic acid, (anhydrous) maleic acid, monoalkyl maleate Carboxyl group-containing vinyl monomers such as esters, fumaric acid, fumaric acid monoalkyl esters, crotonic acid, itaconic acid, itaconic acid monoalkyl esters, itaconic acid glycol monoether, citraconic acid, citraconic acid monoalkyl esters, and cinnamic acid.

(3) Sulfonic group-containing vinyl monomers, vinyl sulfate monoesters and their salts:
Alkene sulfonic acids having 2 to 14 carbon atoms, such as vinyl sulfonic acid, (meth) allyl sulfonic acid, methyl vinyl sulfonic acid, styrene sulfonic acid; and alkyl derivatives thereof having 2 to 24 carbon atoms such as α-methyl styrene sulfonic acid Sulfo (hydroxy) alkyl- (meth) acrylate or (meth) acrylamide, such as sulfopropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloxypropylsulfonic acid, 2- (meth) acryloylamino- 2,2-dimethylethanesulfonic acid, 2- (meth) acryloyloxyethanesulfonic acid, 3- (meth) acryloyloxy-2-hydroxypropanesulfonic acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid, 3 -(Meth) acrylamide-2- Droxypropanesulfonic acid, alkyl (C3-18) allylsulfosuccinic acid, poly (n = 2-30) oxyalkylene (ethylene, propylene, butylene: single, random or block) sulfuric acid of mono (meth) acrylate Esters [poly (n = 5-15) oxypropylene monomethacrylate sulfate, etc.], polyoxyethylene polycyclic phenyl ether sulfate,

(4) Phosphoric acid group-containing vinyl monomers and salts thereof:
(Meth) acryloyloxyalkyl phosphoric acid monoesters such as 2-hydroxyethyl (meth) acryloyl phosphate, phenyl-2-acryloyloxyethyl phosphate, (meth) acryloyloxyalkyl (C1-24) phosphonic acids such as 2 -Acryloyloxyethylphosphonic acid; and salts thereof.
Examples of the salts (2) to (4) include alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (calcium salts, magnesium salts, etc.), ammonium salts, amine salts, or quaternary grades. An ammonium salt is mentioned.

(5) Hydroxyl group-containing vinyl monomer:
Hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, (meth) allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1- Buten-3-ol, 2-buten-1-ol, 2-butene-1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether, sucrose allyl ether, and the like.

(6) Nitrogen-containing vinyl monomer:
Amino group-containing vinyl monomers: aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl methacrylate, N-aminoethyl (meth) acrylamide, (meth) allylamine, Morpholinoethyl (meth) acrylate, 4-vinylpyridine, 2-vinylpyridine, crotylamine, N, N-dimethylaminostyrene, methyl-α-acetaminoacrylate, vinylimidazole, N-vinylpyrrole, N-vinylthiopyrrolidone, N-arylphenylenediamine, aminocarbazole, aminothiazole, aminoindole, aminopyrrole, aminoimidazole, aminomercaptothiazole, and salts thereof.

Amide group-containing vinyl monomers; (meth) acrylamide, N-methyl (meth) acrylamide, N-butyl acrylamide, diacetone acrylamide, N-methylol (meth) acrylamide, N, N-methylene-bis (meth) acrylamide, cinnamon Acid amide, N, N-dimethylacrylamide, N, N-dibenzylacrylamide, methacrylformamide, N-methyl-N-vinylacetamide, N-vinylpyrrolidone and the like.
Nitrile group-containing vinyl monomers: (meth) acrylonitrile, cyanostyrene, cyanoacrylate, and the like.

Quaternary ammonium cation group-containing vinyl monomers: tertiary amine group-containing vinyl monomers such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, diallylamine and the like Monomer quaternized product (quaternized with a quaternizing agent such as methyl chloride, dimethyl sulfate, benzyl chloride, dimethyl carbonate).
Nitro group-containing vinyl monomers: nitrostyrene and the like.

(7) Epoxy group-containing vinyl monomer:
Glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, p-vinylphenylphenyl oxide and the like.

(8) Vinyl esters, vinyl (thio) ethers, vinyl ketones, vinyl sulfones:
Vinyl esters such as vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl-4-vinylbenzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl (meth) acrylate, Vinyl methoxyacetate, vinyl benzoate, ethyl-α-ethoxyacrylate, alkyl (meth) acrylate having an alkyl group having 1 to 50 carbon atoms [methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl ( (Meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) ) Acrylate, eicosyl (meth) acrylate, etc.], dialkyl fumarate (two alkyl groups are straight, branched or alicyclic groups having 2 to 8 carbon atoms), dialkyl maleate (2 Each alkyl group is a linear, branched or alicyclic group having 2 to 8 carbon atoms), poly (meth) allyloxyalkanes [diallyloxyethane, triaryloxyethane, tetraaryl. Roxyethane, tetraallyloxypropane, tetraallyloxybutane, tetrametaallyloxyethane, etc.] vinyl monomers having a polyalkylene glycol chain [polyethylene glycol (molecular weight 300) mono (meth) acrylate, polypropylene glycol (molecular weight 500) Monoacrylate, methyl alcohol ethylene oxide 10 mol adduct (meth) ac Lilate, lauryl alcohol ethylene oxide 30-mole adduct (meth) acrylate, etc.], poly (meth) acrylates [poly (meth) acrylate of polyhydric alcohols: ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate , Neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, etc.]. Vinyl (thio) ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, hinyl butyl ether, vinyl-2-ethylhexyl ether, vinyl phenyl ether, vinyl-2-methoxyethyl ether, methoxybutadiene, vinyl-2-butoxy Ethyl ether, 3,4-dihumanro-1,2-pyran, 2-butoxy-2′-vinyloxydiethyl ether, vinyl-2-ethylmercaptoethyl ether, acetoxystyrene, phenoxystyrene. Vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone, vinyl phenyl ketone; vinyl sulfones such as divinyl sulfide, p-vinyl diphenyl sulfide, vinyl ethyl sulfide, vinyl ethyl sulfone, divinyl sulfone, divinyl sulfoxide and the like.

(9) Other vinyl monomers:
Isocyanate ethyl (meth) acrylate, m-isopropenyl-α, α-dimethylbenzyl isocyanate and the like.

(10) Fluorine-containing vinyl monomer:
4-fluorostyrene, 2,3,5,6-tetrafluorostyrene, pentafluorophenyl (meth) acrylate, pentafluorobenzyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, perfluorocyclohexylmethyl (meth) acrylate, 2, 2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 4H-hexafluorobutyl (meth) acrylate, 1H, 1H, 5H-octafluoro Pentyl (meth) acrylate, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, perfluorooctyl (meth) acrylate, 2-perfluorooctylethyl (meth) acrylate, heptadecafluorodecyl (Meth) acrylate, trihydroperfluoroundecyl (meth) acrylate, perfluoronorbornylmethyl (meth) acrylate, 1H-perfluoroisobornyl (meth) acrylate, 2- (N-butylperfluorooctanesulfonamido) ethyl (meth) acrylate 2- (N-ethylperfluorooctanesulfonamido) ethyl (meth) acrylate and the corresponding compounds derived from α-fluoroacrylic acid; bis-hexafluoroisopropyl itaconate, bis-hexafluoroisopropyl maleate, bis-perfluorooctyl Itaconate, bis-perfluorooctyl maleate, bis-trifluoroethyl itaconate and bis-trifluoroethyl maleate; vinyl heptafluoro Chireto, vinyl perfluoro heptanoate, vinyl perfluoro nonanoate and vinyl perfluoro octanoate, and the like.

(11) Polar monomer capable of providing a toner having excellent image resistance Among the vinyl monomers described above, the toner having excellent image resistance of the present invention can be provided. As the vinyl monomers in the above paragraphs 0031 to 004, A functional group represented by —OH, —COOH, —CONR1R2, —NHCONR1R2 (R1, R2: a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, an aryl group, an aralkyl group, an alicyclic group); A monomer having a linear alkyl group having 2 to 22 carbon atoms bonded to a terminal, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 12-hydroxydodecyl acrylate, 6- (P-carboxyphenoxy) hexyl methacrylate, acryloyloxy (3-carboxy Propane), 17-allyloxystearic acid amide, 18- (vinylphenoxy) stearyl urea, 21-allyloxybehenic acid (N-methyl) amide, and the like may be used alone or in combination with two or more monomers.
By using a monomer having these functional groups, the adhesion between the toner and paper can be enhanced.

(Vinyl copolymer)
Examples of the vinyl monomer copolymer include a polymer obtained by copolymerizing any of the above monomers (1) to (11) in two or more in an arbitrary ratio, for example, styrene. -(Meth) acrylic acid ester copolymer, styrene-butadiene copolymer, (meth) acrylic acid-acrylic acid ester copolymer, styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- ( A meth) acrylic acid copolymer, a styrene- (meth) acrylic acid, a divinylbenzene copolymer, a styrene-styrenesulfonic acid- (meth) acrylic acid ester copolymer, and the like.

<Vinyl copolymer resin fine particles>
It is more preferable to use vinyl copolymer resin fine particles dispersed in an aqueous medium as the vinyl copolymer resin used in toner production. Vinyl copolymer resin fine particles can be easily produced by general emulsion polymerization. Further, the binder resin (B) in the toner of the present invention is more preferably one in which fine particles made of a vinyl copolymer resin are aggregated and / or fused. By using a material in which fine particles are aggregated as the shell portion, the core portion can be coated without any gap, and if it is fused, the core surface can be coated without any gap, and the toner surface becomes smooth and uniform. In addition, effects such as stable charge amount distribution and improved transferability can be obtained.

<Modified polyester resin>
The binder resin (A) used in the present invention may contain a modified polyester resin having a urethane or / and urea group in order to adjust viscoelasticity for the purpose of preventing offset. In the binder resin (A), the content of the modified polyester resin having urethane or / and urea groups is preferably 20% or less, more preferably 15% or less, and still more preferably 10% or less. When the content ratio exceeds 20%, the low-temperature fixability is deteriorated. The modified polyester resin having a urethane or / and urea group may be directly mixed with the binder resin (A), but from the viewpoint of productivity, a relatively low molecular weight modified polyester having an isocyanate group at the terminal. A resin (hereinafter sometimes referred to as a prepolymer) and an amine that reacts with the resin are mixed with the binder resin (A), and during the granulation / after granulation, chain elongation or / and a crosslinking reaction are carried out to produce the urethane. Alternatively, it is preferable to become a modified polyester resin having a urea group. By doing so, it becomes easy to contain a relatively high molecular weight modified polyester resin for adjusting the viscoelasticity in the core portion.

(Prepolymer)
Examples of the prepolymer having an isocyanate group include a polycondensate of the polyol (1) and the polycarboxylic acid (2) and a polyester having an active hydrogen group that is further reacted with a polyisocyanate (3). . 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.

(Polyisocyanate)
Examples of the polyisocyanate (3) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); 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.

(Ratio of isocyanate group to hydroxyl group)
The ratio of the polyisocyanate (3) is usually 5/1 to 1/1, preferably 4 /, as the 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 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% by weight, preferably 1 to 30% by weight, more preferably 2 to 20% by weight. It is. If it is less than 0.5% by weight, the offset resistance deteriorates. On the other hand, if it exceeds 40% by weight, the low-temperature fixability deteriorates.

(Number of isocyanate groups in the prepolymer)
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. It is. When the number is less than 1 per molecule, the molecular weight of the modified polyester after chain extension and / or crosslinking becomes low, and offset resistance deteriorates.

(Chain extension and / or cross-linking agent)
In the present invention, amines can be used as chain extenders and / or crosslinkers. As amines (B), diamine (B1), trivalent or higher polyamine (B2), aminoalcohol (B3), aminomercaptan (B4), amino acid (B5), and amino acids B1-B5 blocked (B6) etc. are mentioned.

Examples of the diamine (B1) include the following.
Aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, tetrafluoro-p-xylylenediamine, tetrafluoro-p-phenylenediamine, etc.);
Alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, isophoronediamine, etc.);
And aliphatic diamines (ethylenediamine, tetramethylenediamine, hexamethylenediamine, dodecafluorohexylenediamine, tetracosafluorododecylenediamine, etc.)

Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine.
Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline.
Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.

Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.
Examples of the B1 to B5 amino group blocked (B6) include ketimine compounds and oxazoline compounds obtained from the B1 to B5 amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.).

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

(Ratio of amino group to isocyanate group)
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] is greater than 2 or less than 1/2, the molecular weight of the urea-modified polyester (i) becomes low and the hot offset resistance deteriorates.

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

<Colorant masterbatch>
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 masterbatch or the masterbatch, in addition to the modified and unmodified polyester resins mentioned above, styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, 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

<Master batch production method>
This master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under a high shear force to obtain a master batch. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. Also, a so-called flushing method called watering paste containing water of colorant is mixed and kneaded with resin and 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, as the mold release agent used in the present invention, known ones can be used, for example, polyolefin wax (polyethylene wax, polypropylene wax, etc.); long chain hydrocarbon (paraffin wax, sazol wax, etc.); carbonyl group-containing wax. Etc. 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 (ethylenediamine 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. In the present invention,

  It is more preferable that the wax content in the toner is 5 to 15% by weight with respect to 100% by weight of the resin component. If the amount of wax with respect to the total amount of toner is less than 5%, the releasing effect by the wax may be lost, and the margin for preventing offset may be lost. On the other hand, if it exceeds 15%, the wax melts at a low temperature, so it is easily affected by thermal energy and mechanical energy, and the wax oozes out from the inside of the toner during stirring in the developing unit, and becomes a toner regulating member or photoreceptor. It may adhere and cause image noise. Further, the endothermic peak at the time of temperature rise measured by a differential scanning calorimeter (DSC) of the wax can fix the toner at a low temperature of 65 to 115 ° C., but if the melting point is less than 65 ° C., the fluidity becomes poor. When the temperature is higher than 115 ° C., the fixability tends to deteriorate.

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

<External additive>
(Inorganic fine particles)
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 nm to 2 μm, and particularly preferably 5 nm to 500 nm. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The proportion of the inorganic fine particles used is preferably 0.01 to 5% by weight of the toner, and particularly preferably 0.01 to 2.0% by weight. Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth. Soil, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, complex oxides such as silicon oxide / magnesium oxide and silicon oxide / aluminum oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, nitriding Silicon etc. can be mentioned.

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

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

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

<Toner production method>
The production method of the toner of the present invention is not limited to this, but is preferably produced by the following production method.
In the toner production method of the present invention, at least a polyester resin, a colorant, and a release agent are dissolved or dispersed in an organic solvent, and then the dissolved or dispersed material is dispersed in an aqueous medium to granulate core particles. And at least a step of adding an aqueous dispersion in which at least vinyl resin fine particles are dispersed and attaching the fine particles to the core particles.
More specifically, it is as follows.

<Granulation of core particles>
(Organic solvent)
As the organic solvent for dissolving or dispersing the polyester resin, the colorant and the release agent, those having a Hansen solubility parameter of 19.5 or less described in Volume 2, Section VII of “POLYMER HANDBOOK” 4th Edition, WILEY-INTERSCIENCE are preferable. It is preferable that the boiling point is volatile with a temperature of less than 100 ° C. from the viewpoint of easy subsequent solvent removal. Examples of such organic solvents 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. Particularly preferred are ester solvents such as methyl acetate and ethyl acetate, aromatic solvents such as toluene and xylene, and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform and carbon tetrachloride. The polyester resin, the colorant and the release agent may be dissolved or dispersed at the same time. Usually, each of them is dissolved or dispersed alone, and the organic solvents used at that time may be different or the same. The same is preferable considering the above.

(Dissolution or dispersion of polyester resin)
The dissolved or dispersed polyester resin preferably has a resin concentration of about 40% to 80%. If the concentration is too high, it will be difficult to dissolve or disperse, and the viscosity will be too high to handle. On the other hand, if the density is too low, the amount of toner produced decreases. When mixing a polyester resin with a modified polyester resin having an isocyanate group at the terminal, it may be mixed in the same solution or dispersion, or separately dissolved or dispersed, but the respective solubility and Considering the viscosity, it is preferable to prepare separate solutions or dispersions.

(Dissolution or dispersion of colorant)
The colorant may be dissolved or dispersed alone, or may be mixed in the solution or dispersion of the polyester resin. If necessary, a dispersion aid or a polyester resin may be added, or the master batch may be used.

(Dissolution or dispersion of release agent)
When the wax is dissolved or dispersed as a release agent, if an organic solvent in which the wax does not dissolve is used, it is used as a dispersion, but the dispersion is prepared by a general method. That is, an organic solvent and wax may be mixed and dispersed with a disperser such as a bead mill. Further, after mixing the organic solvent and the wax, it is sometimes possible to shorten the dispersion time by once heating to the melting point of the wax, cooling with stirring and then dispersing with a disperser such as a bead mill. In addition, a plurality of waxes may be mixed and used, or a dispersion aid or a polyester resin may be added.

(Aqueous medium)
As an aqueous medium to be used, water alone may be used, but a solvent miscible with water may be used in combination. Furthermore, an organic solvent having a Hansen solubility parameter of 19.5 or less used in the oil phase may be mixed, and preferably the addition amount in the vicinity of the saturation amount with respect to water increases the emulsification or dispersion stability of the oil phase. it can. Examples of the miscible solvent include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methylcellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.) and the like. The amount of the aqueous medium used relative to 100 parts by weight of the toner composition 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. Moreover, it is not economical when it exceeds 2000 weight part.

(Inorganic dispersant and organic resin fine particles)
When the dissolved or dispersed toner composition is dispersed in the aqueous medium, by dispersing the inorganic dispersant or the organic resin fine particles in the aqueous medium in advance, the particle size distribution is sharpened and the dispersion is reduced. It is preferable in terms of stability. As the inorganic dispersant, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite and the like are used. As the resin for forming the organic resin fine particles, any resin that can form an aqueous dispersion can be used, and it may be a thermoplastic resin or a thermosetting resin. Includes vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate resin and the like. These resins may be used in combination of two or more. Of these, vinyl resins, polyurethane resins, epoxy resins, polyester resins, and combinations thereof are preferable from the viewpoint that an aqueous dispersion of fine spherical resin particles is easily obtained.

(Method for dispersing organic resin fine particles in water)
The method of making the resin into an aqueous dispersion of fine organic resin particles is not particularly limited, and examples thereof include the following (a) to (h).
(A) In the case of a vinyl resin, a method of directly producing an aqueous dispersion of resin fine particles by a polymerization reaction such as a suspension polymerization method, an emulsion polymerization method, a seed polymerization method or a dispersion polymerization method using a monomer as a starting material .
(B) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., a precursor (monomer, oligomer, etc.) or a solvent solution thereof is dispersed in an aqueous medium in the presence of a suitable dispersant, A method of producing an aqueous dispersion of resin fine particles by heating and then adding a curing agent to cure.
(C) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, and epoxy resin, a precursor (monomer, oligomer, etc.) or a solvent solution thereof (preferably liquid) may be liquefied by heating. .) A method in which a suitable emulsifier is dissolved therein, and then water is added to perform phase inversion emulsification.

(D) A resin prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) can be used as a mechanical rotary type or jet type resin. A method in which resin fine particles are obtained by pulverization using a fine pulverizer and then classification, and then dispersed in water in the presence of an appropriate dispersant.
(E) A resin solution obtained by dissolving a resin prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent, A method in which resin fine particles are obtained by spraying in the form of a mist and then dispersed in water in the presence of an appropriate dispersant.
(F) A solvent is added to a resin solution obtained by dissolving a resin prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent. The resin fine particles are precipitated by cooling the resin solution previously dissolved in a solvent by heating, and then the solvent is removed to obtain resin fine particles, which are then dispersed in water in the presence of a suitable dispersant. Method.

(G) A resin solution obtained by dissolving a resin prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent, A method of dispersing in an aqueous medium in the presence of an appropriate dispersant and removing the solvent by heating or decompression.
(H) In a resin solution in which a resin prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is dissolved in a solvent. A method of phase inversion emulsification by adding water after dissolving an appropriate emulsifier.

(Surfactant)
Further, a surfactant or the like can be used as necessary in order to emulsify and disperse the oily phase containing the toner composition in the aqueous medium. As surfactants, anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, Quaternary ammonium salt type cationic surfactants such as alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride, fatty acid amide derivative, polyhydric alcohol Nonionic surfactants such as derivatives, for example, amphoteric surfactants such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine. It is.

  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- [ω-fluoroalkyl (C6 -C11) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [ω-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) ) Carboxylic acid and metal salt, perfluoroalkyl carboxylic acid (C7 to C13) and its metal salt, perfluoroalkyl (C4 to C12) sulfonic acid and its metal salt, perfluorooctane sulfonic acid diethanolamide, N-propyl-N -(2-hydroxyethyl) par Fluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Can be mentioned. In addition, examples of the cationic surfactant include aliphatic quaternary ammonium salts such as aliphatic primary, secondary or secondary amine acids having a fluoroalkyl group, and perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts. Benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt and the like.

(Protective colloid)
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 -Of methyl alcohol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, or compounds containing vinyl alcohol and carboxyl group Esters 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 , Homopolymers or copolymers such as those having a nitrogen atom such as ethyleneimine or its heterocyclic ring, polyoxyethylene, polyoxypropylene, Oxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonylphenyl Polyoxyethylenes such as esters, 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 washing with water. To do. It can also be removed by operations such as enzymatic degradation. When a dispersant is used, the dispersant can remain on the surface of the toner particles, but it is preferable to remove it by washing from the charged surface of the toner.

(Distribution method)
The dispersion method is not particularly limited, and known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. 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 temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 20 to 80 ° C.

(Desolation)
In order to remove the organic solvent from the obtained emulsified dispersion, a known method can be used. For example, a method can be employed in which the entire system is gradually heated under normal pressure or reduced pressure to completely evaporate and remove the organic solvent in the droplets.

<Particle adhesion process>
A process for attaching fine particles made of vinyl resin to core particles mainly made of polyester resin will be described. In this step, it is preferable to use an aqueous dispersion in which at least vinyl resin fine particles are dispersed. This dispersion can be easily produced by a usual emulsion polymerization method and may be used as it is in the adhesion step. In order to stabilize the dispersion of the core particles and fine particles to some extent, for example, a surfactant or the like may be added. The timing of introducing the fine particles is preferably after the organic solvent is removed.

  In the step of attaching, the pH may be adjusted with sodium hydroxide or hydrochloric acid in order to make the attachment more efficient. Further, a monovalent to trivalent metal salt may be added as a flocculant. Examples of the monovalent metal constituting the salt include lithium, potassium, and sodium. Examples of the divalent metal include calcium and magnesium. Examples of the trivalent metal include aluminum. Examples of the anion constituting the salt include chloride ion, bromide ion, iodide ion, carbonate ion and sulfate ion. Further, the adhesion may be promoted by heating, but the adhesion may be performed at a temperature lower than the glass transition temperature of the fine particles, or may be performed at a temperature higher than the glass transition temperature. However, when adhered at a temperature near or below the glass transition temperature, aggregation or / and fusion between the fine particles may hardly proceed, so that the aggregation or / and It is preferable to promote fusion, promote the coating of the core particles, and make the surface of the shell portion uniform. However, the heating temperature and the heating time are appropriately adjusted from the viewpoint of adjusting the degree of surface uniformity and adjusting the sphericity of the toner particles.

<Extension or / and cross-linking reaction>
For the purpose of introducing a modified polyester resin having a urethane or / and urea group, when a modified polyester resin having an isocyanate group at the terminal and an amine capable of reacting with the polyester resin are added, the toner composition is placed in an aqueous medium. Before dispersion, amines may be mixed in the oil phase, or amines may be added to the aqueous medium. The time required for the above reaction is selected depending on the reactivity between the isocyanate group structure of the polyester prepolymer and the added amines, but is usually 1 minute to 40 hours, preferably 1 to 24 hours. The reaction temperature is usually 0 to 150 ° C., preferably 20 to 98 ° C. This reaction may be performed before the fine particle adhesion step, or may be performed simultaneously during the fine particle adhesion step. Further, it may be after the fine particle adhesion step is completed. Moreover, a well-known catalyst can be used as needed.

<Washing and drying process>
A known technique is used for washing and drying the toner particles dispersed in the aqueous medium.
That is, after solid-liquid separation with a centrifuge, a filter press, etc., the obtained toner cake is redispersed in ion exchange water at about room temperature to about 40 ° C., and after adjusting the pH with acid or alkali as necessary, After removing the impurities and surfactants by repeating the process of solid-liquid separation again and again, the toner powder is obtained by drying with an air dryer, circulating dryer, vacuum dryer, vibration fluid dryer, etc. . At this time, the fine particle component of the toner may be removed by centrifugation or the like, and a desired particle size distribution can be obtained using a known classifier after drying, if necessary.

<External processing>
The obtained dried toner powder is mixed with different kinds of particles such as charge control fine particles and fluidizing agent fine particles, or fixed and fused on the surface by applying a mechanical impact force to the mixed powder. It is possible to prevent the dissociation 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 lower the pulverization air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), kryptron System (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar, etc.

<Process cartridge>
The developer of the present invention can be used in, for example, an image forming apparatus provided with a process cartridge as shown in FIG.
In the present invention, a plurality of constituent elements such as the above-mentioned photosensitive member, charging means, developing means, and cleaning means are integrally combined as a process cartridge, and this process cartridge is formed. It is configured to be detachable from the image forming apparatus main body such as a copying machine or a printer.

  The process cartridge shown in FIG. 2 includes a photoreceptor, a charging unit, a developing unit, and a cleaning unit. Explaining the operation, the photosensitive member is rotationally driven at a predetermined peripheral speed. In the rotation process, the photosensitive member is uniformly charged with a predetermined positive or negative potential on its peripheral surface by the charging unit, and then image exposure light from an image exposing unit such as slit exposure or laser beam scanning exposure. In this way, an electrostatic latent image is sequentially formed on the circumferential surface of the photosensitive member, and the formed electrostatic latent image is then toner developed by the developing means, and the developed toner image is exposed from the paper feeding unit. The transfer unit sequentially transfers the image to the transfer material fed in synchronization with the rotation of the photosensitive member between the transfer unit and the transfer unit. The transfer material that has received the image transfer is separated from the surface of the photosensitive member, introduced into the image fixing means, and the image is fixed, and printed out as a copy (copy) or print (print). The surface of the photoconductor after the image transfer is cleaned by removing the transfer residual toner by a cleaning means, and after being further discharged, it is repeatedly used for image formation.

Toner analysis and evaluation were performed as follows. Although the following was evaluated as a one-component developer, the toner of the present invention can also be used as a two-component developer by using a suitable external addition process and a suitable carrier.
<Measurement method>
(Particle size)
Next, a method for measuring the particle size distribution of toner particles will be described.
Examples of the measuring 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 the measurement sample is further added as a solid content. 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 measurement 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 volume average particle diameter (Dv) and the number average particle diameter (Dp) of the toner can be obtained.

  As a channel, for example, less than 2.00 to 2.52 μm; less than 2.52 to 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; Less than .40 μm; 25.40 to less than 32.00 μm; 13 channels of 32.00 to less than 40.30 μm are used, and particles having a particle size of 2.00 μm to less than 40.30 μm can be targeted.

(Average circularity)
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. The average circularity 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 is a value measured as an average circularity by a flow type particle image analyzer FPIA-2000. 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 for about 1 to 3 minutes with an ultrasonic disperser and measuring the shape and distribution of the toner with the above apparatus at a dispersion concentration of 3000 to 10,000 / μl. .

(Molecular weight)
The molecular weights of the polyester resin and vinyl copolymer resin used were measured under the following conditions by ordinary GPC (gel permeation chromatography).
・ Device: HLC-8220GPC (manufactured by Tosoh Corporation)
Column: TSKgel SuperHZM-M x 3
・ Temperature: 40 ℃
・ Solvent: THF (tetrahydrofuran)
・ Flow rate: 0.35 ml / min ・ Sample: 0.01 ml injection of a sample having a concentration of 0.05 to 0.6% A molecular weight calibration curve prepared by a monodisperse polystyrene standard sample from the molecular weight distribution of the toner resin measured under the above conditions Was used to calculate the weight average molecular weight Mw. As the monodisperse polystyrene standard sample, 10 samples in the range of 5.8 × 100 to 7.5 × 1000000 were used.

(Glass transition point)
For measuring the glass transition point of the polyester resin or vinyl copolymer resin to be used, for example, using a differential scanning calorimeter (for example, DSC-6220R: Seiko Instruments Inc.) After heating to 150 ° C. for 10 minutes, leave the sample at 150 ° C. for 10 minutes, cool the sample to room temperature, leave it for 10 minutes, heat it again to 150 ° C. at a heating rate of 10 ° C./min, The height of the baseline above the glass transition point can be obtained from a curved portion corresponding to ½.

(Particle size)
The particle size of the vinyl copolymer resin fine particles used can be measured as a dispersion using a measuring device such as LA-920 (Horiba Seisakusho) or UPA-EX150 (Nikkiso).

<Evaluation method>
(Fixed separation evaluation)
Using an externally added toner (developer) with Ricoh's ipsio CX2500, an unfixed image in which a solid belt image (adhesion amount 9 g / m ² ) having a width of 36 mm is printed on the tip 3 mm with A4 longitudinal paper. did. This unfixed image was fixed at a fixing temperature of 10 ° C. in the range of 130 ° C. to 190 ° C. using the following fixing device, and a separable / non-offset temperature range was obtained. The temperature range refers to a fixing temperature range in which the paper is satisfactorily separated from the heating roller, no offset phenomenon occurs, and image peeling does not easily occur. The paper used and the paper passing direction were 45 g / m ² of Y-long vertical paper that is disadvantageous in separability. The peripheral speed of the fixing device was 120 mm / sec.

  The fixing device is of a soft roller type having a fluorine surface layer composition as shown in FIG. Specifically, the heating roller 11 has an outer diameter of 40 mm, an aluminum core 13 and a 1.5 mm-thick elastic body layer 14 made of silicone rubber, and a PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer) surface layer. 15 and a heater 16 is provided inside the aluminum cored bar. The pressure roller 12 has an outer diameter of 40 mm, and has an elastic body layer 18 made of silicone rubber and a PFA surface layer 19 made of silicone rubber on an aluminum core bar 17. The paper 21 on which the unfixed image 20 is printed is passed as shown in the figure.

○: Separable / non-offset temperature range was 50 ° C. or higher;
Δ: Separable / non-offset temperature range was 30 ° C or higher and lower than 50 ° C;
X: The separable / non-offset temperature range was less than 30 ° C.

(Filming evaluation)
The toner (developer) subjected to the external addition treatment was continuously printed in a N / N environment (23 ° C., 45%) with a predetermined print pattern having a B / W ratio of 6% using Ricoh's ipsio CX2500. After continuous printing (after endurance) in an N / N environment, the photosensitive member and the intermediate transfer belt were visually observed and evaluated. Judgment criteria are as follows.
○: There was no filming on the photosensitive member and the intermediate transfer member, and there was no problem at all;
Δ: Filming was observed on one of the photosensitive member and the intermediate transfer member, but it was not visible on the copied image, and there was no practical problem;
X: Filming occurred on the photoreceptor and / or the intermediate transfer member, which could be confirmed on the image, and there was a problem in practical use.

(Stress resistance evaluation and background contamination evaluation)
The toner (developer) subjected to the external addition treatment was continuously printed in a N / N environment (23 ° C., 45%) with a predetermined print pattern having a B / W ratio of 6% using Ricoh's ipsio CX2500. After continuous printing of 50 and 2000 sheets in N / N environment (after endurance), the toner on the developing roller during blank pattern printing is sucked and the amount of charge is measured with an electrometer. After 50 and 2000 sheets The difference in charge amount was evaluated. In addition, for the evaluation of the background stain on the photoreceptor, a colorless transparent tape was applied to the uncleaned portion after development, the toner on the photoreceptor was peeled off, and the density after the blank paper was attached was visually evaluated (evaluation level: None, △ Slightly soiled but not worrisome, × stained).

Stress resistance evaluation ○: Absolute value of charge amount difference is 10 μC / g or less Δ: Absolute value of charge amount difference is within a range of 10 μC / g to 15 μC / g ×: Absolute value of charge amount difference is 15 μC / g or more

(Heat resistant storage stability)
The toner was stored at 50 ° C. for 8 hours, and then sieved with a 42 mesh sieve for 2 minutes. The residual rate on the wire mesh was used as an index for heat resistant storage stability. The heat resistant storage stability was evaluated in the following four stages.

×: 30% or more △: 20-30%
○: 10 to 20%
A: Less than 10%

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. “Parts” means all parts by mass.

<Synthesis of polyester>
(Polyester 1) In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 553 parts of bisphenol A ethylene oxide 2-mole adduct, 196 parts of bisphenol A propylene oxide 2-mole adduct, 220 parts of terephthalic acid, adipic acid 45 parts and 2 parts of dibutyltin oxide were added, reacted for 8 hours at 230 ° C. under normal pressure, and further reacted for 5 hours under reduced pressure of 10 to 15 mmHg. Then, 26 parts of trimellitic anhydride was added to the reaction vessel, and 180 ° C. Reaction was performed at normal pressure for 2 hours to obtain [Polyester 1]. [Polyester 1] had a number average molecular weight of 2200, a weight average molecular weight of 5600, a Tg of 43 ° C., and an acid value of 13.

<Synthesis of vinyl resin fine particles>
(Vinyl resin fine particles V-1) 1.6 parts of sodium dodecyl sulfate and 492 parts of ion-exchanged water were placed in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introducing tube, heated to 80 ° C., and then polymerized. As an initiator, 2.5 parts of KPS (potassium persulfate) dissolved in 100 parts of ion-exchanged water was added, and 15 minutes later, 152 parts of styrene monomer, 38 parts of butyl acrylate, 10 parts of methacrylic acid, molecular weight adjustment A mixed solution of 3.5 parts of NOM (n-octyl mercaptan) as an agent was added dropwise over 90 minutes, and then kept at 80 ° C. for 60 minutes. Thereafter, the mixture was cooled to obtain a dispersion of [Vinyl resin fine particles V-1]. The average particle diameter of the fine particles was 50 nm. The dispersion was taken up in a small petri dish, and the solid obtained by evaporating the dispersion medium was measured. The number average molecular weight was 11,000, the weight average molecular weight was 18000, and Tg was 65 ° C.
(Vinyl Copolymer Resin Fine Particles V-2 to V-7) As described in the list of production resins in Table 1, the monomer composition, molecular weight regulator and polymerization polymerization initiator were changed, and the above (vinyl resin fine particles The same procedure as in the synthesis of V-1) was performed.
The monomer composition and physical properties of the vinyl resin fine particles V-1 to V-7 are summarized in the production resin list in Table 1.

<Synthesis of prepolymer>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction pipe, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, 22 parts of trimellitic anhydride Then, 2 parts of dibutyltin oxide was added, reacted at 230 ° C. under normal pressure for 8 hours, and further reacted at reduced pressure of 10 to 15 mmHg for 5 hours 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 49.
Next, 411 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 tube, a stirrer and a nitrogen introduction tube, and reacted at 100 ° C. for 5 hours. Polymer 1] was obtained. [Prepolymer 1] had a free isocyanate weight% of 1.53%.

<Synthesis of master batch>
Carbon black (Cabot Co., Ltd. Regal 400R): 40 parts, Binder resin: Polyester resin (Sanyo Kasei RS-801 Acid value 10, Mw 20000, Tg 64 ° C.): 60 parts, Water: 30 parts are mixed in a Henschel mixer, A mixture in which water was soaked into the pigment aggregate was obtained. This was kneaded for 45 minutes with two rolls set at a roll surface temperature of 130 ° C. and pulverized to a size of 1 mmφ with a pulverizer to obtain [Masterbatch 1].

Example 1
<Preparation of pigment / WAX dispersion (oil phase)>
In a container equipped with a stir bar and a thermometer, 543.5 parts of [Polyester 1], 181 parts of carnauba wax, and 1450 parts of ethyl acetate were charged, heated to 80 ° C. with stirring, and maintained at 80 ° C. for 5 hours. Thereafter, it was cooled to 30 ° C. in 1 hour. Next, 500 parts of [Masterbatch 1] and 100 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 1].
[Raw material solution 1] 1500 parts are transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feed speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads are 80% by volume. Carbon black and WAX were dispersed under conditions of filling and 3 passes. Next, 655 parts of a 65% ethyl acetate solution of [Polyester 1] was added, followed by one pass with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 1]. It was adjusted by adding ethyl acetate so that the solid content concentration of [Pigment / WAX Dispersion 1] (130 ° C., 30 minutes) was 50%.

<Preparation of aqueous phase>
968 parts of ion-exchanged water, 40 parts of a 25 wt% aqueous dispersion of organic resin fine particles for dispersion stabilization (styrene copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate), dodecyl diphenyl ether 150 parts of a 48.5% aqueous solution of sodium disulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries) and 98 parts of ethyl acetate were mixed and stirred to obtain a milky white liquid. This is designated [Aqueous Phase 1].

<Emulsification process>
[Pigment / WAX Dispersion 1] 976 parts, 2.6 parts of isophorone diamine as amines, TK homomixer (manufactured by Special Machine) for 1 minute at 5,000 rpm, 88 parts of [Prepolymer 1] In addition, after mixing for 1 minute at 5,000 rpm with a TK homomixer (manufactured by Tokushu Kika), add 1200 parts of [Aqueous Phase 1], while adjusting with a TK homomixer at a rotational speed of 8,000 to 13,000 rpm. The mixture was mixed for 20 minutes to obtain [Emulsion slurry 1].

<Desolvent>
[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 8 hours to obtain [Dispersion slurry 1].

<Particle adhesion process>
A dispersion of [Vinyl resin fine particles V-1] was added to [Dispersion slurry 1] so that the solid content ratio was 1: 0.15, and the mixture was heated to 73 ° C. over 30 minutes. A solution obtained by dissolving 100 parts of magnesium chloride hexahydrate in 100 parts of ion-exchanged water was added little by little, kept at 73 ° C., and after 4 hours, an aqueous hydrochloric acid solution was added to adjust the pH to 5, followed by heating to 80 ° C. After cooling for 2 hours, [Dispersion Slurry 1-2] was obtained.

<Washing->Drying>
[Dispersion Slurry 1-2] 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 (10 minutes at 12,000 rpm), and then filtered.
(2): 900 parts of ion-exchanged water was added to the filter cake of (1), ultrasonic vibration was applied, and the mixture was mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure. This operation was repeated so that the electric conductivity of the reslurry liquid was 10 μC / cm or less.
(3): 10% hydrochloric acid was added so that the reslurry solution of (2) had a pH of 4, and the mixture was directly filtered with a three-one motor for 30 minutes.
(4): 100 parts of ion-exchanged water was added to the filter cake of (3), mixed with a TK homomixer (10 minutes at 12,000 rpm) and then filtered. This operation was repeated so that the reslurry liquid had an electric conductivity of 10 μC / cm or less to obtain [Filter Cake 1].

  [Filtration cake 1] was dried at 45 ° C. for 48 hours in a circulating drier and sieved with a mesh of 75 μm to obtain [Toner base 1]. The volume average particle diameter (Dv) was 5.8 μm, the number average particle diameter (Dp) was 5.2 μm, Dv / Dp was 1.12 and the average circularity was 0.973. Subsequently, 100 parts of the base toner was mixed with 0.5 part of hydrophobic silica and 0.5 part of hydrophobic titanium oxide using a Henschel mixer to obtain [Developer 1] of the present invention.

(Examples 2 to 7)
As shown in the toner evaluation results in Table 2, the same procedure as in Example 1 was carried out except that the vinyl resin fine particles used in the fine particle adhesion step in Example 1 were changed. Obtained.

(Example 8)
<Preparation of pigment / WAX dispersion (oil phase)>
In a container equipped with a stir bar and a thermometer, 543.5 parts of [Polyester 1], 181 parts of carnauba wax, and 1450 parts of ethyl acetate were charged, heated to 80 ° C. with stirring, and maintained at 80 ° C. for 5 hours. Thereafter, it was cooled to 30 ° C. in 1 hour. Next, 500 parts of [Masterbatch 1] and 10 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 2].
[Raw material solution 2] 1500 parts are transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by IMEX), liquid feeding speed is 1 kg / hr, disk peripheral speed is 6 m / sec, and 0.5 mm zirconia beads are 80% by volume. Carbon black and WAX were dispersed under conditions of filling and 3 passes. Next, 538 parts of a 65% ethyl acetate solution of [Polyester 1] was added, and one pass was performed with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 2]. Ethyl acetate was added to adjust the solid content concentration of [Pigment / WAX Dispersion 2] (130 ° C., 30 minutes) to 50%.
<Emulsification process>
[Pigment / WAX Dispersion 2] 976 parts were mixed with TK homomixer (manufactured by Tokushu Kika) at 5,000 rpm for 1 minute, and then [Water Phase 1] 1200 parts were added. The mixture was mixed for 20 minutes while adjusting at 1,000 to 13,000 rpm to obtain [Emulsion slurry 2].
<Desolvent>
[Dispersion slurry 2] was obtained in the same procedure as in Example 1.
<Particle adhesion process>
A dispersion of [Vinyl resin fine particles V-4] was added to [Dispersion slurry 8] so that the solid content ratio was 1: 0.2, and the mixture was heated to 73 ° C. over 30 minutes. A solution prepared by dissolving 150 parts of magnesium chloride hexahydrate in 150 parts of ion-exchanged water was added little by little and kept at 73 ° C. After 6 hours, the aqueous solution was adjusted to pH 5 by adding aqueous hydrochloric acid, and then heated to 80 ° C. After cooling for 2 hours, [Dispersed Slurry-8-2] was obtained.
Thereafter, [Developer 8] was obtained in the same procedure as in Example 1.
(Examples 9 to 10)
As shown in the toner evaluation results in Table 2, the same procedure as in Example 8 was performed except that the vinyl resin fine particles used in the fine particle adhesion step in Example 8 were changed. Obtained.

(Comparative Examples 1-2)
As shown in the toner evaluation results in Table 2, the developer of Comparative Examples 1 and 2 was used in the same manner as in Example 1 except that the vinyl resin fine particles used in the fine particle adhesion step of Example 1 were changed. Obtained.

(Comparative Examples 3 and 4)
As shown in the toner evaluation results in Table 2, the same procedure as in Examples 1 and 8 was performed except that the particle adhesion step in Examples 1 and 8 was omitted. Obtained.

(Comparative Example 5)
<Colorant dispersion>
50 parts of carbon black (Regal 400R manufactured by Cabot), 33 parts of a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate, and 587 parts of ion-exchanged water are placed in a container and dispersed using a TK homomixer. R5] was obtained.
<Releasing agent dispersion>
A bead mill using 50 parts of carnauba wax, 25 parts of a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate and 275 parts of ion-exchanged water, dispersed using a TK homomixer, and further using 0.5 mm zirconia beads To obtain [Releasing Agent Dispersion Liquid R5].
<Aggregation process>
1600 parts of [Vinyl resin fine particles V-3], 474 parts of [colorant dispersion R5], 225 parts of [release agent dispersion R5] and 2300 parts of ion-exchanged water are placed in a container, and sodium hydroxide is stirred. The pH was adjusted to 6 with an aqueous solution. Thereafter, the mixture was heated and maintained at 45 ° C. to 50 ° C., and an aqueous sodium hydroxide solution was added little by little while observing the aggregation state. When the average particle size reached about 5.0 μm, 40 parts of a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate was added, and the pH was adjusted to 5 to obtain [Dispersion Slurry R5]. <Washing->Drying>
[Dispersion Slurry R5] 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 (10 minutes at 12,000 rpm), and then filtered.
(2): 900 parts of ion-exchanged water was added to the filter cake of (1), ultrasonic vibration was applied, and the mixture was mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure. This operation was repeated so that the electric conductivity of the reslurry liquid was 10 μC / cm or less.
(3): 10% hydrochloric acid was added so that the reslurry solution of (2) had a pH of 4, and the mixture was directly filtered with a three-one motor for 30 minutes.
(4): 100 parts of ion-exchanged water was added to the filter cake of (3), mixed with a TK homomixer (10 minutes at 12,000 rpm) and then filtered. This operation was repeated so that the reslurry liquid had an electric conductivity of 10 μC / cm or less to obtain [Filter Cake 1].

  [Filtration cake 1] was dried at 45 ° C. for 48 hours in a circulating drier and sieved with a mesh of 75 μm to obtain [Toner base 1]. The volume average particle diameter (Dv) was 5.8 μm, the number average particle diameter (Dp) was 5.2 μm, Dv / Dp was 1.12 and the average circularity was 0.973. Subsequently, 100 parts of the base toner was mixed with 0.5 part of hydrophobic silica and 0.5 part of hydrophobic titanium oxide using a Henschel mixer to obtain a developer of Comparative Example 5.

(Comparative Example 6)
A developer of Comparative Example 6 was obtained in the same manner as Comparative Example 5 except that the following fine particle adhesion step was added after the aggregation step of Comparative Example 5.
<Particle adhesion process>
To the obtained [Dispersion Slurry R6], a dispersion of [Vinyl Resin Fine Particle V-4] was added at a solid content ratio of 1: 0.2 and heated to 73 ° C. over 30 minutes. A solution obtained by dissolving 100 parts of magnesium chloride hexahydrate in 100 parts of ion-exchanged water was added little by little and kept at 73 ° C. After 5 hours, an aqueous hydrochloric acid solution was added to adjust to pH 5 and then heated to 80 ° C. After 2 hours, the mixture was cooled to obtain [Dispersion Slurry R6-2].

The resin physical properties of the vinyl resin fine particles V-1 to V-7 produced as described above are listed in the production resin list of Table 1, and the characteristics and evaluation of the developers produced in Examples 1 to 10 and Comparative Examples 1 to 6 are as follows. The results are summarized in the toner evaluation results shown in Table 2.

  According to the evaluation results, the toner of the example which is the toner of the present invention has obtained very good results in the electrophotographic process in general. However, the toners of Comparative Examples 1 and 2 having a shell structure made of a resin not having a preferred molecular weight or Tg of the present invention are deteriorated in the background stain after durability or inferior in heat-resistant storage stability. Further, the toners of Comparative Examples 3 to 5 having no shell are particularly poor in soiling and inferior in filming and fixing properties. Furthermore, the toners of Comparative Examples 5 and 6 that did not contain a polyester resin in the core layer were not satisfactory in terms of both fixability (low temperature fixing) and heat resistant storage stability (blocking).

  The toner of the present invention has both low-temperature fixability and heat-resistant storage stability, is excellent in offset resistance, can control the toner structure, and has good charging properties without contaminating the developing device. And can be suitably used as a toner for image formation in an electrostatic recording apparatus or the like.

It is a figure which shows the structure of the toner of this invention. FIG. 3 is a diagram illustrating an example of a process cartridge used in the image forming apparatus of the present invention. 1 is a diagram illustrating an example of a fixing device used in an image forming apparatus of the present invention.

Claims (29)

In the electrostatic charge developing toner having a core-shell structure composed of at least a colorant, a release material, and a core layer composed of a resin having at least a polyester skeleton and a shell layer composed of a resin obtained by vinyl polymerization, a), b) and The resin defined in c) and having at least the polyester skeleton is a polyester resin, and the polyester resin includes a modified polyester resin and an unmodified polyester resin, and the weight of the modified polyester resin and the unmodified polyester resin. the ratio (modified polyester resin / modified polyester resin not) 5/100 to 80/20 der toner for electrostatic charge development, wherein Rukoto.
a) The molecular weight of the shell layer resin satisfies 8000 <Mw <18000.
Mw: 20 mg of toner was immersed in 5 ml of THF for 1 minute, and the dissolved resin in the filtrate was measured by gel permeation chromatography (GPC). having a peak between 850 cm ^-1 and 783 cm ^-1 by reflection absorption infrared spectroscopy).
c) The glass transition point Tg measured by a differential scanning calorimeter (DSC) of the vinyl resin forming the shell is 45 ° C. or higher and 80 ° C. or lower. 2. The electrostatic charge according to claim 1, wherein the resin obtained by vinyl polymerization of the shell layer is a binary or higher copolymer containing at least one monomer having two or more unsaturated bonds. Development toner. The resin obtained by vinyl polymerization of the shell layer is —OH, —COOH, —CONR1R2, —NHCONR1R2 (wherein R1 and R2 are hydrogen atoms, substituted or unsubstituted alkyl groups having 1 to 8 carbon atoms, aryl groups, and aralkyl groups. , Which represents an alicyclic group), and is a binary or higher copolymer containing at least one monomer having a linear alkyl group having 2 to 22 carbon atoms bonded to the end of the functional group. The electrostatic charge developing toner according to claim 1, wherein the toner is an electrostatic charge developing toner. The toner has a circularity of 0.95 or more and less than 0.99 and a volume average particle diameter of 4.5 μm or more and less than 8 μm, and the ratio of the colorant in the core portion to the core portion (hereinafter referred to as RA (P)). ) And the ratio of the release agent in the core part (hereinafter referred to as RA (W)) and the ratio of the colorant in the shell part to the shell part (hereinafter referred to as RB (P)) and the shell. The ratio of the release agent in the part (hereinafter referred to as RB (P)) is such that the relation RA (P) × 0.5> RB (P) and RA (W) × 0.5> RB (W). The electrostatic image developing toner according to claim 1, wherein the electrostatic image developing toner is satisfied. The core particles to be the core layer are obtained by dispersing or emulsifying in an aqueous medium an oil phase in which at least a colorant, a release material, and a polyester resin are dissolved or dispersed in an organic solvent having a Hansen solubility parameter of 19.5 or less. The method for producing a toner for electrostatic charge development according to any one of claims 1 to 4. The above aqueous medium is selected from water or / and water-soluble organic solvent, organic solvent having Hansen solubility parameter of 19.5 or less, surfactant, viscosity modifier, emulsification / dispersion stabilized fine particles, pH adjuster or inorganic salt 6. The method for producing a toner for developing an electrostatic charge image according to claim 5, wherein the toner comprises a combination thereof. After forming core particles in an aqueous medium, an aqueous dispersion in which at least vinyl copolymer resin fine particles are dispersed is added, and the fine particles are adhered to the core particles to form a shell layer to form a core-shell structure. The method for producing a toner for developing an electrostatic image according to claim 5. 8. The electrostatic image developing toner according to claim 7, wherein the organic solvent is removed before the fine particles are adhered, and then an aqueous dispersion in which resin fine particles are dispersed is added to adhere the fine particles. Production method. 8. The method for producing a toner for developing an electrostatic charge image according to claim 7, wherein the organic solvent is removed after the fine particles are adhered. 10. The method for producing a toner for developing an electrostatic charge image according to claim 7, wherein the fine particles are adhered and then heated to fuse the fine particles. 11. The electrostatic charge image developing device according to claim 5, wherein the toner is obtained by subjecting the toner particles to a washing treatment with an aqueous washing medium after the toner particles are formed in an aqueous medium, followed by a drying treatment. Toner manufacturing method. The electrostatic charge image developing toner according to claim 1, wherein the polyester resin of the core layer is made of a polyester resin having a glass transition temperature of 40 ° C. or higher. 13. The resin having at least a polyester skeleton is a polyester resin, and the polyester resin contains a polyester resin stretched by urethane or / and urea bonds. Toner for developing electrostatic images. The resin having at least a polyester skeleton is a polyester resin, and the polyester resin contains a polyester resin component formed by a reaction between a modified polyester resin having an isocyanate group at a terminal and amines. 14. The toner for developing an electrostatic charge image according to any one of 4, 12 and 13. 15. The static electricity according to claim 1, wherein the resin having at least a polyester skeleton is a polyester resin, and the polyester resin contains an unmodified polyester resin. Toner for charge image development. 2. The toner according to claim 1, wherein the toner contains 3 to 30% by weight of one or more selected from paraffins, synthetic esters, polyolefins, carnauba wax, or rice wax as a release agent. The toner for developing an electrostatic charge image according to any one of 4 and 12 to 15 . The toner according to any one of claims 1 to 4 or 12 to 16, characterized in that the toner contains a charge control agent. The toner according to any one of claims 1 to 4 or 12 to 17, characterized in that said toner is a non-magnetic one-component developing toner. 19. An image forming apparatus comprising a toner, wherein the non-magnetic one-component developing toner according to claim 18 is used as the toner. 20. The image forming apparatus according to claim 19 , wherein the image forming apparatus forms a multicolor image. The image forming apparatus an image forming apparatus according to claim 19 or 20 further characterized in that an intermediate transfer means endless type. The image forming apparatus according to any one of claims 19 to 21 , wherein the image forming apparatus does not include a blade as a residual toner cleaning unit in the photoreceptor or / and the intermediate transfer unit. The image forming apparatus according to any one of claims 19 to 21 , wherein the image forming apparatus includes a blade cleaning unit. The image forming apparatus according to any one of claims 19 to 23 , wherein the image forming apparatus includes a fixing unit using a roller provided with a heating device. The image forming apparatus according to any one of claims 19 to 23 , wherein the image forming apparatus includes a fixing unit using a belt provided with a heating device. The image forming apparatus according to any one of 25 claims 19, characterized in that it comprises an oil-less fixing unit by the image forming apparatus does not need oil application to a fixing member. A toner container filled with the electrostatic image developing toner according to any one of claims 1 to 4 or 12 to 16 . A toner container filled with the nonmagnetic one-component developing toner according to claim 18 . In a process cartridge that integrally supports at least one member selected from a photosensitive member, a charging unit, a developing unit, and a cleaning unit and is detachable from the main body of the image forming apparatus, the developing unit includes toner (developing). A process cartridge in which the toner (developer) is filled with the electrostatic charge developing toner according to any one of claims 1 to 4 or 12 to 18 .

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