JP2008003360A - Toner for electrostatic image development - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a black toner which is good in bluing, excels in toner granulation property, offset property, charging property, and storage stability, and has good color developing property, and OHP transparency. <P>SOLUTION: The black toner for electrostatic image development is produced in an aqueous medium and includes at least a binder resin and a colorant, wherein the colorant is a mixed pigment of carbon black which is a black pigment and copper phthalocyanine which is a cyan pigment, and the colorant is used as a masterbatch prepared by kneading with a resin constituting part of the binder resin. The masterbatch is characterized in that mixing of part of the binder resin and carbon black and/or copper phthalocyanine is not carried out before mixing carbon black and copper phthalocyanine. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  This toner is used for developing an electrostatic latent image formed on a photoreceptor using toner, and particularly relates to a black toner. The present invention also relates to a developer for developing a one-component or two-component electrostatic latent image using the toner, and an image forming method and apparatus using the developer.

  Conventionally, in an electrophotographic apparatus, an electrostatic recording apparatus, or the like, an electric or magnetic latent image is visualized with toner. For example, in electrophotography, an electrostatic charge image (latent image) is formed on a photoreceptor, and then the latent image is developed with toner to form a toner image. The toner image is usually transferred onto a transfer material such as paper and then fixed by a method such as heating. Toner used for electrostatic image development is generally colored particles in which a binder, a colorant, a charge control agent, and other additives are contained in a binder resin. There is a suspension polymerization method. In the pulverization method, a colorant, a charge control agent, an offset preventing agent and the like are melt-mixed in a thermoplastic resin and uniformly dispersed, and the resulting composition is pulverized and classified to produce a toner. According to the pulverization method, a toner having some excellent characteristics can be produced, but there is a limitation in the selection of the toner material. For example, the composition obtained by melt mixing must be capable of being pulverized and classified by economically usable equipment.

  From this requirement, the melt-mixed composition must be made sufficiently brittle. For this reason, when the above composition is actually pulverized into particles, a wide range of particle size distribution is likely to be formed, and when attempting to obtain a copy image with good resolution and gradation, for example, a particle size of 5 μm The following fine powder and coarse powder of 20 μm or more must be removed by classification, which has the disadvantage that the yield becomes very low. Further, in the pulverization method, it is difficult to uniformly disperse the colorant, the charge control agent, and the like in the thermoplastic resin. In addition, since the colorant added to the toner is exposed on the surface of the obtained toner, there is a problem that the toner surface is not uniformly charged, the charge distribution of the toner is expanded, and the development characteristics are deteriorated. Therefore, because of these problems, the kneading and pulverizing method cannot sufficiently meet the demand for high performance.

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

Even those that can be polymerized using conventional materials may not be able to adequately control the particle size due to the influence of additives such as resins and colorants. There is a problem that is small. The problem in particular is that polyester resins that have exhibited excellent fixing performance and color suitability by conventional kneading and grinding methods cannot be used basically, and therefore they must be sufficiently compatible with miniaturization, high speed, and colorization. It is a point that cannot be done. For this reason, a method for obtaining irregularly shaped toner particles by associating resin fine particles obtained by an emulsion polymerization method is disclosed (see Patent Document 1).

  However, in the toner particles obtained by the emulsion polymerization method, a large amount of the surfactant remains not only on the surface but also inside the particles even after the water washing step, and the environmental stability of the toner charging is impaired. The amount distribution is widened, and the background stain of the obtained image becomes poor. Further, the remaining surfactant contaminates the photoreceptor, the charging roller, the developing roller, etc., and the original charging ability cannot be exhibited. In addition, even in the emulsion polymerization method in which the colorant component is hardly exposed on the toner surface, the colorant easily aggregates, so that it is difficult to add and disperse the colorant uniformly in the toner. Due to the difference, there is a problem that the non-uniformity of charging occurs and the stability when used for a long time is lowered.

In the case of color output, a slight deterioration in developability and transferability causes a problem in color balance and gradation. Furthermore, since the colorant in the toner is generally incompatible with the resin, the transmitted light is irregularly reflected at the interface, and the transparency of OHP or the like is hindered. Therefore, if the dispersion of the colorant is poor, there is also a problem that the transparency with OHP deteriorates.
However, in particular, color output machines do not require an oil supply device for the fixing device, and oilless toners in which a release agent that replaces oil is added to the toner are common sense. Further, since it cannot be atomized as much as the colorant, it is difficult to add and disperse more uniformly, and if the dispersion of the release agent is poor, there is a problem that charging property, developability, storage property and OHP permeability are inhibited.

  Patent Document 2 describes a toner obtained by dispersing an organic solvent liquid in a master batch of a colorant made of a resin material in which a colorant is dispersed in an aqueous medium, and Patent Document 3 describes , A melt-kneaded toner material consisting of a masterbatch of a colorant in which a colorant is dispersed in a resin, a resin that is the same as or different from the resin used in the masterbatch, and a release agent that may be included if necessary. A toner obtained by dispersing / dissolving the resin in an organic solvent in which the resin is dissolved, emulsifying and dispersing the resin in an aqueous medium, and then removing the organic solvent is disclosed. A toner obtained by using a master batch formed by kneading a master batch material made of resin at a temperature of Tg to (Tg + 40 ° C.) (Tg is the glass transition point of the resin) is described. Toner is -A master batch in which Bon Black and copper phthalocyanine are simultaneously kneaded is not used.

Further, when considering the hue of black, it is common to add cyan as a complementary color, but usually a method of mixing master batches separately kneaded in a subsequent step is employed. Although it is considered that there is no problem even if the conventional pulverized toner is mixed in the post-process, in the toner granulated in the liquid, the solubility of the master batch separately kneaded in the solvent is different. Phenomenon that inferior masterbatch remains is likely to occur. For this reason, the remaining master batch is present as a coarse powder toner, or the coloring power and hue are not as intended, thereby deteriorating the toner quality.
As described above, an electrophotographic black toner that can sufficiently meet the demand for high performance has not yet been obtained.

Japanese Patent No. 2537503 JP 2002-244348 A JP 2002-296839 A JP 2001-194427 A

  Accordingly, an object of the present invention is to provide a black toner having good bluishness, good coloring power and good toner granulation property as a black toner in an aqueous granulated toner, and responding to the demand for higher performance. It is desirable to provide a black toner having excellent storage stability, good color developability and OHP permeability.

  As a result of diligent study, the present inventors have determined that the colorant is a mixed pigment of carbon black as a black pigment and copper phthalocyanine as a cyan pigment, and is kneaded with a resin that forms part of the binder resin. The master batch is used for color reproducibility by preventing mixing of a part of the binder resin and carbon black and / or copper phthalocyanine at least before mixing of carbon black and copper phthalocyanine. As a result, a black toner excellent in coloring power and transparency has been completed.

That is, in the toner granulated in the liquid, since the solubility of the master batches kneaded separately in the solvent is different, a phenomenon that the master batch having poor solubility remains is likely to occur. For this reason, the remaining master batch remains as a coarse powder toner, which deteriorates the toner quality. If there is a large amount of remaining residue, the coloring power and the hue do not reach the target levels. The present inventors have used a master batch for simultaneously kneading a mixed pigment of carbon black as a black pigment and copper phthalocyanine as a cyan pigment as a colorant for a black toner in a polymerized toner. I found that there was no residue left.
In the present invention, 50 to 100% by weight of the binder resin of the toner is a polyester resin.

Further, the present inventors can express the excellent fixing performance and color suitability obtained by the conventional kneading and pulverization method by increasing the polyester resin to 50 to 100% by weight in the binder resin of the toner, and increase the speed. And found that it can sufficiently cope with colorization. Examples of the polyester resin include all polyester resins such as a modified polyester resin, a non-modified polyester resin, and a low molecular weight polyester resin, and the total of them is 50 to 100% by weight in the binder resin, more preferably 75 to 100% by weight. It is.
By applying the toner of the present invention to an electrophotographic developer, it is possible to form a black toner image excellent in coloring power, bluishness and light transmittance.
The configuration of the present invention made based on the above findings is as follows.

(1) In a black toner produced in an aqueous medium and containing at least a binder resin and a colorant, the colorant is a mixed pigment of black pigment carbon black and cyan pigment copper phthalocyanine, and the binder Used in a masterbatch that is kneaded with a resin that forms part of the resin, the masterbatch comprising at least a part of the binder resin and carbon black and / or copper phthalocyanine at least prior to mixing of carbon black and copper phthalocyanine. A black toner for developing an electrostatic image, characterized in that no mixing is performed.
(2) In a black toner produced in an aqueous medium and containing at least a binder resin and a colorant, the colorant is a mixed pigment of black pigment carbon black and cyan pigment copper phthalocyanine; Electrostatic charge characterized in that it is used in a masterbatch kneaded with a resin that forms part of the resin, and the masterbatch is obtained by kneading carbon black and copper phthalocyanine at the same time as part of the binder resin. Black toner for image development.
(3) The black toner for developing electrostatic images according to (1) or (2) above, wherein the mixing ratio of the carbon black and copper phthalocyanine is 99: 1 to 70:30.
(4) The carbon black is C.I. I. Pigment Black 7, and the copper phthalocyanine is C.I. I. Pigment Blue 15: 3 and / or C.I. I. The black toner for developing an electrostatic charge image according to any one of the above (1) to (3), which is Pigment Blue 15: 4.
(5) The black toner for developing an electrostatic charge image according to any one of the above (1) to (4), wherein 50 to 100% by weight of the binder resin is a polyester resin.
(6) A toner material obtained by dissolving or dispersing a toner material containing at least an active hydrogen group-containing compound, a polymer having a site capable of reacting with an active hydrogen group, a colorant, and a release agent in an organic solvent. The organic solvent liquid is dispersed in an aqueous medium, and the organic solvent is removed and washed after or while reacting the active hydrogen group-containing compound and the polymer having a site capable of reacting with the active hydrogen group. The black toner for developing an electrostatic charge image according to any one of the above (1) to (5), which is obtained by a method including a drying step.
(7) The black toner is obtained by a method including a step of adding resin fine particles to the aqueous medium and attaching them to the toner particle surface of the toner. 6) The black toner for developing electrostatic images according to any one of 6).
(8) The black toner for developing an electrostatic charge image according to any one of the above (1) to (7), wherein the toner contains a release agent.
(9) The black toner for developing an electrostatic charge image according to any one of the above (6) to (8), wherein the releasing agent has a melting point of 160 ° C. or lower.
(10) The black toner for developing an electrostatic charge image according to any one of the above (7) to (9), wherein the resin fine particles have an average particle size of 5 to 500 nm.
(11) The polymer having a site capable of reacting with an active hydrogen group is a modified polyester resin and a non-modified polyester resin, and the weight ratio of the modified polyester resin to the non-modified polyester resin is 5/95 to 75. The electrostatic charge image developing black toner according to any one of the above (6) to (10), which is / 25.
(12) The black toner for developing an electrostatic charge image according to the above (11), wherein the acid value of the modified polyester resin and the non-modified polyester resin is 0 to 30 mg KOH / g.
(13) The electrostatic charge image as described in any one of (6) to (12) above, wherein the blending ratio of the colorant and the organic solvent is in the range of 5:95 to 50:50 by weight ratio. Black toner for development.
(14) The volume average particle diameter (Dv) of the toner particles of the black toner is 3.0 μm or more and 8.0 μm or less, and the ratio (Dv / Dv) of the volume average particle diameter (Dv) to the number average particle diameter (Dn). The black toner for developing an electrostatic charge image according to any one of (1) to (13) above, wherein Dn) is from 1.00 to 1.30.
(15) The black toner for developing electrostatic images according to any one of (1) to (14) above, wherein the toner particles of the black toner have an average circularity of 0.95 to 0.995.
(16) A one-component developer for developing an electrostatic latent image, comprising the black toner for developing an electrostatic image according to any one of (1) to (15).
(17) An electrostatic latent image developing two-component developer comprising the electrostatic charge image developing black toner according to any one of (1) to (15) and a carrier.
(18) A toner-containing container filled with the electrostatic charge image developing black toner according to any one of (1) to (15).
(19) The electrostatic charge according to any one of the above (1) to (15), which can be mounted on an image forming apparatus and an electrostatic latent image carrier and an electrostatic latent image formed on the electrostatic latent image carrier. A process cartridge comprising at least developing means for developing a visible image by developing with an image developing black toner.
(20) An electrostatic latent image forming unit that forms an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image according to at least any one of (1) to (15) above. At least development means for forming a visible image by developing with a developing black toner, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transferred image transferred to the recording medium An image forming apparatus including the image forming apparatus.

  According to the present invention, by using a master batch in which a mixed pigment of carbon black as a black pigment and copper phthalocyanine as a cyan pigment is simultaneously kneaded as a colorant, the toner has excellent granulation properties, coloring power, blue color A black toner having good taste, storage and transparency can be obtained. Therefore, by applying this toner to the developer, it is possible to form an image excellent in color development and light transmittance in OHP in an image forming method for forming a latent image.

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

(Binder resin)
The binder resin used in the toner of the present invention is made of the following constituent materials, for example.
Polymers of styrene such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene and 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, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer Coalesce, styrene-isoprene Styrene copolymers such as polymers, styrene-acrylonitrile-indene copolymers, styrene-maleic acid copolymers, styrene-maleic acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate , Polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin Chlorinated paraffin, paraffin wax and the like can be used, and these can be used alone or in combination. The resin used for preparing the masterbatch in the present invention (which is preferably a polyester-based resin as described later) forms part of these binder resins in the toner.

(Modified polyester resin)
The site (group) capable of reacting with the active hydrogen group can be used as long as it is known, and is preferably an isocyanate group, an epoxy group, a carboxylic acid, or an acid chloride group, more preferably an isocyanate group. Therefore, a particularly preferred resin used in the present invention is a polyester resin (RMPE) modified with a group capable of urea bonding. Examples thereof include a polyester prepolymer (A) having an isocyanate group. Examples of the prepolymer (A) include a polycondensate of a polyol (PO) and a polycarboxylic acid (PC) and a polyester having an active hydrogen group reacted with a polyisocyanate (PIC).
This prepolymer (A) can be produced by the method described below.
Polyol (PO) and polycarboxylic acid (PC) are heated to 150-280 ° C. in the presence of a known esterification catalyst such as tetrabutoxytitanate, dibutyltin oxide, etc., and the generated water is distilled off as necessary. Thus, a polyester having a hydroxyl group is obtained. Next, this is reacted with polyisocyanate (3) at 40 to 140 ° C. to obtain a prepolymer (A) having an isocyanate group.
Examples of the group containing active hydrogen of the polyester (polyester used for modification with a group capable of urea bonding) include hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups, and the like. Of these, alcoholic hydroxyl groups are preferred.

  Modified polyester (MPE) such as urea-modified polyester is easy to adjust the molecular weight of its polymer component, and is a dry toner, especially oil-less low-temperature fixing characteristics (extensive releasability without a mechanism for applying a release oil to a fixing heating medium) And fixing property). In particular, those obtained by modifying the end of the polyester prepolymer with urea can suppress adhesion to the heating medium for fixing while maintaining high fluidity and transparency in the fixing temperature range of the unmodified polyester resin itself.

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

  Examples of the polycarboxylic acid (PC) include dicarboxylic acid (DIC) and trivalent or higher polycarboxylic acid (TC), and DIC alone or a mixture of DIC and a small amount of TC is preferable. Dicarboxylic acids 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, etc.) ) And the like. Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Examples of the trivalent or higher valent polycarboxylic acid include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid). In addition, as polycarboxylic acid, you may make it react with a polyol using the acid anhydride or lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.) of the above-mentioned thing. The ratio of the polyol (PO) and the polycarboxylic acid (PC) is usually 2/1 to 1/1, as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH], preferably 1.5 / 1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.

  As polyisocyanate (PIC), aliphatic polyisocyanate (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanate (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); aromatic Diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; polyisocyanates such as phenol derivatives, oximes, caprolactam And a combination of two or more of these.

  The ratio of the polyisocyanate (PIC) is usually 5/1 to 2/1, 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. It is 1-2 / 1, more preferably 2.5 / 1-2.0 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. When the molar ratio of [NCO] is less than 1, in the case of a urea-modified polyester, the urea content in the polyester becomes low and the hot offset resistance deteriorates. The content of the polyisocyanate (PIC) component in the polyester 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. %. If it is less than 0.5% by weight, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. On the other hand, if it exceeds 40% by weight, the low-temperature fixability deteriorates. The number of isocyanate groups contained per molecule in the polyester prepolymer (A) having an isocyanate group is usually 2 or more, preferably 2 to 3 on average, and more preferably 2 to 2.5 on average. If it is less than 2 per molecule, the molecular weight of the modified polyester will be low, and the hot offset resistance will deteriorate.

  In the present invention, a urea-modified polyester that is preferably used as a toner binder can be obtained by a reaction between a polyester prepolymer (A) having an isocyanate group and an amine (B). As amines (B), diamine (B1), triamine or higher polyamine (B2), amino alcohol (B3), amino mercaptan (B4), amino acid (B5), and amino groups of (B1) to (B5) (B6) etc. that are blocked. Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, Isophorone diamine etc.); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine etc.) and the like. Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine. Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline. Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan. Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid. As (B6) which blocked the amino group of (B1) to (B5), ketimine compounds obtained from the amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) of (B1) to (B5), And oxazolyzone compounds. Among these amines (B), preferred are (B1) and a mixture of (B1) and a small amount of (B2).

  Furthermore, the molecular weight of a modified polyester such as urea-modified polyester can be adjusted using an elongation terminator. Examples of the elongation terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds). The ratio of amines (B) is the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B). The ratio is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. When [NCO] / [NHx] exceeds 2 or less than 1/2, the molecular weight of a modified polyester such as urea-modified polyester (UMPE) becomes low, and the hot offset resistance deteriorates. In the present invention, the polyester modified with urea bonds (UMPE) may contain urethane bonds as well as urea bonds. The molar ratio of the urea bond content to the urethane bond content is usually 100/0 to 10/90, preferably 80/20 to 20/80, and more preferably 60/40 to 30/70. When the molar ratio of the urea bond is less than 10%, the hot offset resistance is deteriorated.

As a crosslinking agent or an extender for the modified polyester used in the present invention, an active hydrogen compound capable of reacting with a reactive group such as an isocyanate group, preferably the amines (B) can be used.
The modified polyester such as urea-modified polyester (UMPE) used as a toner binder in the present invention is produced by a one-shot method or a prepolymer method. The weight average molecular weight of the modified polyester such as urea-modified polyester is usually 10,000 or more, preferably 20,000 to 1,000,000, and more preferably 30,000 to 1,000,000. If it is less than 10,000, the hot offset resistance deteriorates. The number average molecular weight of the modified polyester such as urea-modified polyester is not particularly limited when the unmodified polyester (PE) described later is used, and may be a number average molecular weight that can be easily obtained to obtain the weight average molecular weight. . In the case of the modified polyester alone, the number average molecular weight is usually 20000 or less, preferably 1000 to 10000, and more preferably 2000 to 8000. When it exceeds 20000, the low-temperature fixability and the glossiness when used in a full-color apparatus are deteriorated.

(Crosslinking agent and extender)
In the present invention, amines can be used as a crosslinking agent and / or an extender. As amines (B), diamine (B1), triamine or higher polyamine (B2), amino alcohol (B3), amino mercaptan (B4), amino acid (B5), and amino groups of (B1) to (B5) (B6) etc. that are blocked. Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, Isophorone diamine etc.); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine etc.) and the like. Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine. Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline. Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan. Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid. As (B6) which blocked the amino group of (B1) to (B5), ketimine compounds obtained from the amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) of (B1) to (B5), Examples include oxazoline compounds. Among these amines (B), preferred are (B1) and a mixture of (B1) and a small amount of (B2).
Furthermore, if necessary, the molecular weight of the modified polyester after completion of the reaction can be adjusted by using a terminator for crosslinking and / or elongation. Examples of the terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those blocked (ketimine compounds).

  The ratio of amines (B) is the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B). The ratio is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. When [NCO] / [NHx] 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.

(Non-modified polyester)
In the present invention, not only the modified polyester (A) is used alone, but also the unmodified polyester (C) having an acid value of 0.5 to 40 mgKOH / g is used together with the modified polyester (A). It can also be contained as. By using (C) in combination, the low-temperature fixability and the glossiness when used in a full-color apparatus are improved. Examples of (C) include the same polycondensates of polyol (1) and polycarboxylic acid (2) as in the polyester component (A), and preferred ones are also the same as (C). (C) is not limited to non-modified polyester, but may be modified with a chemical bond other than a urea bond, and may be modified with a urethane bond, for example.

  It is preferable that (A) and (C) are at least partially compatible with each other in terms of low-temperature fixability and hot offset resistance. Accordingly, the polyester component (A) and (C) preferably have similar compositions. When (A) is contained, the weight ratio of (A) to (C) is usually 5/95 to 75/25, preferably 10/90 to 25/75, more preferably 12/88 to 25/75, Especially preferably, it is 12 / 88-22 / 78. If the weight ratio of (A) is less than 5%, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.

The molecular weight distribution of the unmodified polyester (C) is measured by the following method. After about 1 g of non-modified polyester (C) is precisely weighed in an Erlenmeyer flask, 10 to 20 g of THF (tetrahydrofuran) is added to obtain a THF solution having a binder concentration of 5 to 10%. The column is stabilized in a heat chamber at 40 ° C., and THF as a solvent is allowed to flow through the column at this temperature at a flow rate of 1 ml / min, and 20 μl of the THF sample solution is injected.
The molecular weight of the sample is calculated from the relationship between the retention value and the logarithmic value of a calibration curve prepared from a monodisperse polystyrene standard sample. A calibration curve is created using a polystyrene standard sample. As a monodisperse polystyrene standard sample, the thing of the range of molecular weight 2.7 * 10 < ² > -6.2 * 10 < ⁶ > by Tosoh Corporation is used, for example. A refractive index (RI) detector is used as the detector. As the column, for example, TSKgel, G1000H, G2000H, G2500H, G3000H, G4000H, G5000H, G6000H, G7000H, GMH manufactured by Tosoh Corporation are used in combination.

  The main peak molecular weight is usually 1000 to 30000, preferably 1500 to 10000, more preferably 2000 to 8000. When the amount of the component having a molecular weight of less than 1000 is increased, the heat resistant storage stability tends to deteriorate and carrier contamination occurs. Therefore, the content is preferably 5.0% by weight or less. When the component increases from the molecular weight of 30000, the low-temperature fixability tends to decrease, but the decrease can be suppressed as much as possible by balance control. The content of the component having a molecular weight exceeding 30000 is 1% or more, and varies depending on the toner material, but is preferably 3 to 6%. If it is less than 1%, sufficient hot offset resistance cannot be obtained, and if it is 10% or more, the glossiness and transparency may be deteriorated.

  Mn is 2000 to 15000 and the value of Mw / Mn is preferably 5 or less. When it exceeds 5, sharp melt property is lacking and glossiness is impaired. Moreover, it leads to an improvement in hot offset by using a polyester resin containing 1 to 15% of THF insoluble matter. Insoluble in THF is effective for hot offset in color toners, but it is definitely negative in terms of gloss and transparency of OHP, but it is effective within 1 to 15% to widen the mold release width. There is also.

The hydroxyl value of (C) is preferably 5 or more, more preferably 10 to 120, and particularly preferably 20 to 80. If it is less than 5, it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.
The acid value of (C) is usually 0-30, preferably 5-25. By having an acid value, it tends to be negatively charged. In addition, those having an acid value and a hydroxyl value exceeding these ranges are easily affected by the environment under high temperature and high humidity and low temperature and low humidity, and are liable to cause image deterioration.
The THF-insoluble matter in the toner can be adjusted by controlling the elongation and / or crosslinking of the modified polyester by the acid value of the non-modified polyester.

The measurement method is shown below.
<Method for measuring THF-insoluble matter>
About 1.0 g (A) of resin or toner is weighed. To this, about 50 g of THF is added and left at 20 ° C. for 24 hours. This is first separated by centrifugation and filtered using JIS standard (P3801) type 5 C filter paper for quantification. The solvent content of this filtrate is vacuum-dried, and the residual amount (B) is measured only for the resin content.
This residual amount is the amount dissolved in THF.
The THF insoluble content (%) is obtained from the following formula.
THF insoluble matter (%) = (A−B) / A
In the case of toner, the THF-insoluble component amount (W1) and the THF-soluble component amount (W2) other than the resin are separately obtained by a known method, for example, a thermal loss method by the TG method, and obtained from the following formula.
THF insoluble matter (%) = (A−B−W2) / (A−W1−W2) × 100

(Toner and glass transition point of non-modified polyester)
In the present invention, a modified polyester and a non-modified polyester are included as a resin component of the toner. However, since a polymer obtained by extending and / or crosslinking the modified polyester has a high molecular weight, no clear glass transition behavior is observed. Therefore, there is no difference between the glass transition point (Tg) of the toner and the glass transition point (Tg) of the non-modified polyester, and the glass transition point (Tg) of the toner is adjusted by the glass transition point (Tg) of the non-modified polyester. The glass transition point of the toner is usually 40 to 70 ° C., preferably 45 to 55 ° C. If it is less than 40 ° C., the heat-resistant storage stability of the toner deteriorates, and if it exceeds 70 ° C., the low-temperature fixability becomes insufficient. Due to the coexistence of the crosslinked and / or elongated polyester resin, the dry toner of the present invention tends to have good heat-resistant storage stability even when the glass transition point is low, as compared with known polyester-based toners.

(Measuring method of glass transition point (Tg))
Here, the glass transition point (Tg) in the present invention is specifically determined by the following procedure. Using Shimadzu TA-60WS and DSC-60 as measuring devices, the measurement was performed under the following measurement conditions.

・ Measurement conditions Sample container: Aluminum sample pan (with lid)
Sample amount: 5mg
Reference: Aluminum sample pan (alumina 10mg)
Atmosphere: Nitrogen (flow rate 50 ml / min)
Temperature conditions Starting temperature: 20 ° C
Temperature increase rate: 10 ° C / min
End temperature: 150 ° C
Holding time: None Temperature drop: 10 ° C / min
End temperature: 20 ° C
Holding time: None Temperature increase rate: 10 ° C / min
End temperature: 150 ° C

  The measurement results were analyzed using the data analysis software (TA-60, version 1.52) manufactured by Shimadzu Corporation. The analysis method is to specify a range of ± 5 ° C centering on the point showing the maximum peak on the lowest temperature side of the DrDSC curve, which is the DSC differential curve of the second temperature rise, and use the peak analysis function of the analysis software to determine the peak temperature. Ask. Next, the maximum endothermic temperature of the DSC curve is determined using the peak analysis function of the analysis software in the range of the peak temperature + 5 ° C. and −5 ° C. in the DSC curve. The temperature shown here corresponds to the Tg of the toner.

(Coloring agent)
The pigment used as the colorant of the present invention is a mixed pigment of black pigment carbon black and cyan pigment copper phthalocyanine.
The mixing ratio of carbon black and copper phthalocyanine is preferably 99: 1 to 70:30, and more preferably 95: 5 to 85:15. When the mixing ratio of copper phthalocyanine is 1% or less, the function as a complementary color is low, and it is not preferable in that it becomes a grayish color. Further, when the mixing ratio of copper phthalocyanine is 30% or more, the complementary color is too strong, and it is not preferable in that it is far from the hue of black.

As carbon black of the black pigment, C.I. I. Pigment Black 6, C.I. I. Pigment Black 7, C.I. I. Pigment Black 8, C.I. I. Pigment Black 9 or the like can be used, but a particularly preferred black pigment carbon black is C.I. I. Pigment Black 7.
Examples of copper phthalocyanine as a cyan pigment include C.I. I. Pigment Blue 15: 1, C.I. I. Pigment Blue 15: 2, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4 or the like can be used, but a preferable cyan pigment, copper phthalocyanine, is C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4.
C. I. Pigment Black 7 is “NIPex70 manufactured by Degussa”, C.I. I. Pigment Blue 15: 3 is “HOSTAPERM BLUE B2G manufactured by Clariant”, C.I. I. As the Pigment Blue 15: 4, a commercially available product such as “4937 manufactured by Dainichi Seika Co., Ltd.” can be used.

  In addition, C.I. I. Pigment Black 7 and C.I. I. Pigment Blue 15: 3 or C.I. I. The content of the mixed pigment of Pigment Blue 15: 4 is preferably 1 to 25 parts by weight and more preferably 2.5 to 15.0 parts by weight with respect to 100 parts by weight of the binder resin. When the ratio of the colorant is less than 1.0 part with respect to 100 parts by mass of the resin, it is not preferable in that a sufficient color density cannot be obtained. When the ratio of the colorant exceeds 25 parts by mass with respect to 100 parts by mass of the binder resin, it is not preferable in that the color saturation is impaired and the influence on the fixing characteristics and charging characteristics appears.

The colorant used in the present invention may be subjected to a surface treatment, and any conventional treatment method can be adopted as a method for treating the colorant with a rosin resin. For example, rosin is dissolved in a solvent, A method in which a colorant is dispersed and rosin is adsorbed on the colorant, and then the colorant and rosin liquid are filtered and the colorant is dried, or JP-A-7-188575 or the like, The method of depositing is mentioned.
In addition, the rosin used in this case can be a general rosin and known ones. There are rosins mainly composed of abietic acid and dextropimaric acid, for example, natural rosins such as wood rosin and gum rosin. Furthermore, there can be mentioned modified rosins polymerized, hydrogenated or oxidized, rosin derivatives such as rosin alkyd adducts, rosin alkylene oxide adducts, rosin modified phenols, and the like.

  In performing the rosin resin treatment, the amount of rosin to be adsorbed on the colorant is preferably 0.1 to 10% by mass with respect to 100% by mass of the present colorant. Although the action of rosin itself is not well understood, the color of the present colorant becomes clear when the rosin resin treatment is performed. Further, the dispersibility with the resin is improved, and there is a dispersant effect. Moreover, even a small amount is effective. However, if the amount of rosin is too large, the binding property with the binder resin may be weakened, and unevenness may occur in the finally obtained toner chargeability.

The colorant used in the present invention is 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 non-modified 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-malein 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

  In this master batch, a master batch is obtained by mixing and kneading a resin for a master batch and a colorant under a high shear force. At this time, an organic solvent or water can be used to enhance the interaction between the colorant and the resin. In addition, 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. Can be used as it is, and is preferably used without being dried. For mixing and kneading, a high shear dispersion device such as a two-roll mill or a pressure kneader is preferably used. Moreover, you may use an additive in order to improve the dispersibility at the time of kneading | mixing. Examples of the additive to be used include polyethylene wax, polypropylene wax, amide wax, and montan wax that are generally used in plastic processing.

It is preferable that the blending ratio of the colorant and the organic solvent in the dispersion liquid of the color component is in the range of 5:95 to 50:50 by weight ratio. If the blending ratio of the colorant is less than this, the amount of the dispersion is increased at the time of toner preparation, and the efficiency of toner preparation tends to be reduced. If the blending ratio of the colorant is larger than this, the dispersion of the colorant tends to be insufficient.
The particle size of the colorant in the dispersion after dispersing the colorant is desirably 1 μm or less. When the particle size is larger than 1 μm, the particle size of the colorant is increased when the toner is formed, and the image quality is likely to be deteriorated. In particular, the light transmittance of OHP is likely to be decreased. The particle size of the colorant can be determined with a laser Doppler type distribution measuring device “UPA-150” (manufactured by Nikkiso Co., Ltd.).

<Measurement method of particle size of colorant>
(I) For sample preparation, 0.5 g of the master batch is dispersed in a solution containing 10 g of ethyl acetate and 0.35 g of an optional pigment dispersant (20% solution).
(Ii) Measuring conditions of measuring instrument Distribution display: Volume Number of channels: 52
Measurement time: 30 sec
Particle refractive index: 1.81
Temperature: 25 ° C
Particle shape: non-spherical viscosity (CP): 0.8750
Solvent refractive index: 1.37
Solvent name: ethyl acetate (iii) The sample diluent to be measured is added using a dropper or a syringe or the like so as to be within (1-100) while watching the sample loading of the measuring instrument.

(Dispersant)
The colorant used in the present invention may use a dispersant when dispersing the colorant. As the dispersant, those having an acid value of 30 mgKOH / g or less and an amine value of 1 or more and 100 or less are preferable. More preferred is a dispersant having an acid value of 20 mgKOH / g or less and an amine value of 10 or more and 50 or less. When the acid value exceeds 30 mgKOH / g, the chargeability under high humidity is lowered and the dispersibility of the colorant becomes insufficient. Also, when the amine value is less than 1 and when the amine value exceeds 100, the colorant dispersibility becomes insufficient. The acid value can be measured by the method described in JIS K0070, and the amine value can be measured by the method described in JIS K7237. The dispersant is preferably highly compatible with the binder resin in terms of dispersibility of the colorant.

  Specific examples of the dispersant having such requirements include “Azisper PB711”, “Azisper PB821”, “Azisper PB822”, “Azisper PB824” (manufactured by Ajinomoto Fine Techno Co., Ltd.), “Disperbyk-112”, "Disperbyk-116", "Disperbyk-161", "Disperbyk-162", "Disperbyk-163", "Disperbyk-164", "Disperbyk-166", "Disperbyk-167", "Disperbyk-168", "Disperbyk-168" -2000 "," Disperbyk-2001 "," Disperbyk-2050 "," Disperbyk-2070 "," Disperbyk-2150 "," Disperbyk-9 " 77 "(manufactured by Big Chemie)," EFKA-4008 "," EFKA-4009 "," EFKA-4010 "," EFKA-4046 "," EFKA-4047 "," EFKA-4520 "," EFKA-4015 ", “EFKA-4020”, “EFKA-4050”, “EFKA-4055”, “EFKA-4060”, “EFKA-4080”, “EFKA-4300”, “EFKA-4330”, “EFKA-4400”, “EFKA” -4401 "," EFKA-4402 "," EFKA-4403 "," EFKA-4406 "," EFKA-4510 "(manufactured by EFKA) and the like. The dispersant is preferably blended in the toner at a ratio of 0.1 wt% to 10 wt% with respect to the colorant. When the amount is less than 0.1% by weight, the colorant dispersibility is insufficient, and when the amount is more than 10% by weight, the chargeability under high humidity may be lowered. The weight average molecular weight of the dispersant is the maximum molecular weight of the main peak in terms of styrene in gel permeation chromatography, preferably 2000 or more, and more preferably 3000 or more in terms of colorant dispersibility. In particular, about 5000 to 50000 is preferable, and 5000 to 30000 is more preferable. When the molecular weight is less than 2000, the polarity increases and the dispersibility of the colorant tends to decrease, and when the molecular weight exceeds 50000, the affinity with the solvent increases and the dispersibility of the colorant tends to decrease.

  The added amount of the dispersant is preferably 1 part by weight or more and 50 parts by weight or less, more preferably 5 parts by weight or more and 30 parts by weight or less with respect to 100 parts by weight of the colorant. This is because if the amount is less than 1 part by weight, the dispersibility is lowered, and if it exceeds 50 parts by weight, the chargeability tends to decrease. These dispersants may be used alone or in combination with other dispersants. Examples of other dispersants that can be used include polyester dispersants, acrylic acid, methacrylic acid and / or ester polymers thereof, and colorant derivatives.

  In the present invention, when an acid treatment is performed on the surface of the colorant, the dispersant amine is used on the surface of the acid colorant by using the colorant dispersant having the acid value and the amine value within a certain range. When the sites are adsorbed, the amount of the dispersant polymer having an amine value that tends to be positively charged is not present on the toner surface, and the amount of acid sites in the dispersant is increased on the toner surface side. Further, even when the dispersant has no acid value, the amine sites of the dispersant are efficiently adsorbed on the acid sites on the surface of the colorant, so that deterioration of charging property can be minimized. There is no hindrance to chargeability.

  Furthermore, in the present invention, a pigment derivative having high affinity for the colorant may be added in order to enhance the interaction between the colorant and the dispersant and to stabilize the colorant in dispersion. Specific examples of pigment derivatives include dimethylaminoethylquinacridone, dihydroquinacridone, carboxylic acid derivatives of anthraquinone, sulfonic acid derivatives of anthraquinone, “Solsperse 22000” (manufactured by Avicia), “EKKA-6750” (manufactured by EFKA Chemicals) ) And the like. The addition amount of the pigment derivative is preferably 0.1 to 100% by weight, more preferably 0.1 to 10% by weight with respect to the colorant.

By using the pigment derivative as described above in combination, the amine site of the dispersant is adsorbed on the surface of the pigment derivative via the pigment derivative, and the acidic group of the dispersant is directed to the outside of the toner particle, so that it is produced in the aqueous phase. The disposition of the colorant in the toner can be controlled by the amount of the dispersant used for granulation, and the adverse effect of the dispersant having an amine value that tends to be positively charged is eliminated.
Moreover, it is preferable that the mixture ratio of the coloring agent and the organic solvent in the dispersion liquid of the coloring component is in the range of 5:95 to 50:50. If the blending ratio of the colorant is less than this, the amount of the dispersion is increased at the time of toner preparation, and the efficiency of toner preparation tends to be reduced. If the blending ratio of the colorant is larger than this, the dispersion of the pigment tends to be insufficient.

(Release agent)
Further, a wax can be contained together with the binder resin and the colorant. Known waxes can be used as the wax of the present invention, and examples thereof include polyolefin waxes (polyethylene wax, polypropylene wax, etc.); long-chain hydrocarbons (paraffin wax, sazol wax, etc.); carbonyl group-containing waxes. Of these, carbonyl group-containing waxes are preferred. Examples of the carbonyl group-containing wax include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18. -Octadecanediol distearate, etc.); polyalkanol esters (tristearyl trimellitic acid, distearyl maleate, etc.); polyalkanoic acid amides (ethylene diamine dibehenyl amide, etc.); polyalkylamides (trimellitic acid tristearyl amide, etc.) And dialkyl ketones (such as distearyl ketone). Among these carbonyl group-containing waxes, polyalkanoic acid esters are preferred.

The melting point of the wax of the present invention is usually 40 to 160 ° C, preferably 50 to 120 ° C, more preferably 60 to 90 ° C. A wax having a melting point of less than 40 ° C. has an adverse effect on heat resistant storage stability, and a wax having a melting point of more than 160 ° C. tends to cause a cold offset when fixing at a low temperature. Further, the melt viscosity of the wax is preferably 5 to 1000 cps, more preferably 10 to 100 cps as a measured value at a temperature 20 ° C. higher than the melting point. Waxes exceeding 1000 cps have poor effects for improving hot offset resistance and low-temperature fixability. The content of the wax in the toner is usually 0 to 40% by weight, preferably 3 to 30% by weight.
The softening point (Tm) of the release agent in the present invention is determined by the peak top indicating the maximum endotherm of the DSC curve in differential scanning calorimetry (DSC). The measurement was performed under the following measurement conditions using TA-60WS and DSC-60 manufactured by Shimadzu Corporation.

<Measurement conditions>
Sample container: Aluminum sample pan (with lid)
Sample amount: 5mg
Reference: Aluminum sample pan (alumina 10mg)
Atmosphere: Nitrogen (flow rate 50 ml / min)
Temperature conditions Starting temperature: 20 ° C
Temperature increase rate: 10 ° C / min
End temperature: 150 ° C
Holding time: None Temperature drop: 10 ° C / min
End temperature: 20 ° C
Holding time: None Temperature increase rate: 10 ° C / min
End temperature: 150 ° C

  The measurement results were analyzed using the data analysis software (TA-60, version 1.52) manufactured by Shimadzu Corporation. The analysis method specifies a range of ± 5 ° C. around the point showing the maximum peak of the DrDSC curve which is the DSC differential curve of the second temperature rise, and obtains the peak temperature using the peak analysis function of the analysis software. Next, the maximum endothermic temperature of the DSC curve is determined using the peak analysis function of the analysis software in the range of the peak temperature + 5 ° C. and −5 ° C. in the DSC curve. The temperature indicated here corresponds to the Tm of the wax.

(Charge control agent)
The toner of the present invention may contain a charge control agent as necessary. Known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified 4 Secondary ammonium salts or compounds, tungsten simple substances or compounds, fluorine activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives.

  Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of a phenol-based condensate (manufactured by Orient Chemical Industry Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP-415 (manufactured by Hodogaya Chemical Industry Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit), copper phthalocyanine, perylene, quinaclide And azo pigments, and other high molecular compounds having a functional group such as a sulfonic acid group, a carboxyl group, and a quaternary ammonium salt.

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

(Resin fine particles)
The resin fine particles used in the present invention are added in the production process in order to control the toner shape (circularity, particle size distribution, etc.), and have a glass transition point (Tg) of 30 to 70 ° C. and a weight average. If the molecular weight is from 8000 to 400,000, the glass transition point (Tg) is less than 30 ° C. and / or the weight average molecular weight is less than 8000, the storability of the toner deteriorates, and storage and development Blocking occurs in the plane. When the glass transition point (Tg) exceeds 70 ° C. and / or the weight average molecular weight exceeds 400,000, the resin fine particles inhibit the adhesion to the fixing paper, and the minimum fixing temperature increases.

It is important that the residual ratio with respect to the toner particles is 0.5 to 5.0 wt%. When the residual ratio is less than 0.5 wt%, the storage stability of the toner is deteriorated, and blocking occurs during storage and in the developing machine. When the residual amount exceeds 5.0 wt%, the resin fine particles Inhibits the exudation of the wax, the effect of releasing the wax is not obtained, and the occurrence of offset is observed.
The residual rate of the resin fine particles can be measured by analyzing a substance caused by the resin fine particles, not by the toner particles, using a pyrolysis gas chromatograph mass spectrometer, and calculating from the peak area. The detector is preferably a mass spectrometer, but is not particularly limited.

  The resin fine particles may be known resins as long as they can form an aqueous dispersion, and may be thermoplastic resins or thermosetting resins. For example, vinyl resins, polyurethane resins, epoxy resins, polyester resins, polyamide resins, Examples include polyimide resins, silicon resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, and polycarbonate resins. As the resin fine particles, two or more of the above resins may be used in combination. Of these, vinyl resins, polyurethane resins, epoxy resins, polyester resins, and combinations thereof are preferred because an aqueous dispersion of fine spherical resin particles is easily obtained.

  The particle size of the resin fine particles is preferably 5 to 500 nm. When the average particle size of the resin fine particles is less than 5 nm, the resin fine particles remaining on the toner surface become a film or cover the entire toner surface, and the release agent fine particles are formed between the binder resin component in the toner and the fixing paper. Adhesion is hindered, the minimum fixing temperature is increased, and the particle size and shape are also difficult to control. Also, if the particle size of the resin fine particles is larger than 500 nm, the resin fine particles remaining on the toner surface largely protrude as convex portions, or the resin fine particles remain as a multilayered layer in a rough state. Desorption of mold fine particles is observed. The particle diameter of the resin fine particles can be measured as a volume average diameter by a laser diffraction / scattering particle size distribution analyzer LA-920 (manufactured by Horiba, Ltd.).

  The vinyl resin is a polymer obtained by homopolymerization or copolymerization of a vinyl monomer, such as a styrene- (meth) acrylate resin, a styrene-butadiene copolymer, a (meth) acrylic acid-acrylate polymer, Examples include styrene-acrylonitrile copolymers, styrene-maleic anhydride copolymers, styrene- (meth) acrylic acid copolymers, and the like.

(Inorganic fine particles)
In order to assist the heat resistant storage stability and chargeability of the toner of the present invention, inorganic fine particles can be used. The primary particle diameter of the inorganic fine particles is preferably 0.5 nm to 200 nm, and particularly preferably 0.5 nm to 50 nm. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The use ratio of the inorganic fine particles is preferably 0.01 to 5 wt% of the toner, and particularly preferably 0.01 to 2.0 wt%.
Specific examples of inorganic fine particles include, for example, tricalcium phosphate, colloidal silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica. And wollastonite, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride, and hydroxyapatite.

(BET specific surface area)
The toner of the present invention preferably has a BET specific surface area of 0.5 to 6.0 (m ² / g), and if the BET specific surface area is less than 0.5 (m ² / g), the presence or addition of coarse particles When the amount exceeds 6.0 (m ² / g), the image quality is likely to be affected by the presence of fine particles, the presence of additives, and surface irregularities.
The BET specific surface area of the toner of the present invention can be obtained by measuring using a device compatible with JIS standards (Z8830 and R1626) such as Tristar 3000 manufactured by Shimadzu Corporation.

(External additive)
In order to assist the fluidity and developability of the colored particles obtained in the present invention, polymer fine particles such as soap-free emulsion polymerization, suspension polymerization, dispersion polymerization, polystyrene, methacrylate ester and acrylate ester copolymer Polymer particles such as a polymer, a polycondensation system such as silicone, benzoguanamine, and nylon, or a thermosetting resin can be externally added as a fluidizing agent.
Such a fluidizing agent performs surface treatment to increase hydrophobicity, and can prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. .

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

(Volume average particle diameter, number average particle diameter of toner)
Further, the toner of the present invention has a volume average particle diameter (Dv) of 3.0 μm or more and 8.0 μm or less, and a ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn). Is preferably 1.00 or more and 1.30 or less. By using a toner having such a particle size and particle size distribution, it is excellent in heat-resistant storage stability, low-temperature fixability, and hot offset resistance, and particularly when used in a full-color copying machine, etc. Sex is obtained. In general, it is said that the smaller the particle size of the toner, the more advantageous it is to obtain a high-resolution and high-quality image, but it is disadvantageous for transferability and cleaning properties. is there. In addition, when the volume average particle size is smaller than the range of the present invention, in the case of a two-component developer, the toner is fused to the surface of the magnetic carrier during a long period of stirring in the developing device, and the charging ability of the magnetic carrier is reduced. When used as a developer, toner filming on the developing roller and toner fusion to a member such as a blade for thinning the toner are likely to occur. On the contrary, when the volume average particle diameter of the toner is larger than the range of the present invention, it becomes difficult to obtain a high-resolution and high-quality image, and when the balance of the toner in the developer is performed. In many cases, the variation in toner particle size becomes large. On the other hand, if Dv / Dn exceeds 1.30, the charge amount distribution becomes wide and the resolving power decreases, which is not preferable.

  The volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner of the present invention are measured with a particle size measuring device (“Multisizer III”, manufactured by Beckman Coulter, Inc.) at an aperture diameter of 100 μm, and analysis software ( Analysis was performed with a Beckman Coulter Multisizer 3 Version 3.51). Specifically, 0.5 ml of 10 wt% surfactant (alkylbenzene sulfonate Neogen SC-A; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is added to a 100 ml glass beaker, 0.5 g of each toner is added, and the mixture is stirred with a micropartel. Subsequently, 80 ml of ion-exchanged water was added. The obtained dispersion was subjected to a dispersion treatment for 10 minutes with an ultrasonic disperser (W-113MK-II, manufactured by Honda Electronics Co., Ltd.). The dispersion was measured using the Multisizer III and Isoton III (manufactured by Beckman Coulter) as the measurement solution. In the measurement, the toner sample dispersion was dropped so that the concentration indicated by the apparatus was 8 ± 2%. In this measurement method, it is important that the concentration is 8 ± 2% from the viewpoint of the reproducibility of the particle size. Within this concentration range, no error occurs in the particle size.

The toner of the present invention can be produced by the following method, but is not limited thereto.
(Toner production method in aqueous medium)
The toner of the present invention can also be produced in the following manner as a base particle composed of at least a binder resin and a colorant produced in an aqueous medium. That is, a method in which a resin in which a colorant is dispersed in a resin is heated or dispersed in a toner particle size in an air stream or an aqueous medium by using a solvent (dissolution suspension method), polymerizability Resin particles can be produced by a so-called suspension polymerization method in which a monomer in which a colorant or the like is dispersed is dispersed in an aqueous medium and polymerized (see Japanese Patent No. 3631468).

  The aqueous phase used in the present invention is used by adding organic fine particles in advance. The water used for the aqueous phase may be water alone, or a solvent miscible with water may be used in combination. 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.

  In the case of the dissolution suspension method, in order to add a polymer having a urea bond to toner particles, a dispersion composed of a polyester prepolymer (A) having an isocyanate group is reacted with amines (B) in an aqueous medium. The urea-modified polyester (i) produced in advance may be used. As a method for stably forming a dispersion comprising a urea-modified polyester (i) or a polyester prepolymer (A) in an aqueous medium, the urea-modified polyester (i) or the polyester prepolymer (A) is formed in an aqueous medium. Examples thereof include a method of adding a toner raw material composition and dispersing it by shearing force.

  The polyester prepolymer (A) and other toner compositions such as a colorant, a release agent, and a non-modified polyester resin (hereinafter referred to as toner raw material) may be mixed when forming a dispersion in an aqueous medium. However, it is more preferable to mix the toner raw materials in advance and then add and disperse the mixture in the aqueous medium. Further, in the present invention, other toner raw materials such as a colorant and a release agent are not necessarily mixed when forming particles in an aqueous medium, and are added after the particles are formed. May be. For example, after forming particles containing no colorant, the colorant can be added by a known dyeing 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 8 μm, a high-speed shearing type is preferable. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 40 to 98 ° C. Higher temperatures are preferable in that the dispersion of the urea-modified polyester (i) or the polyester prepolymer (A) has a low viscosity and is easily dispersed.

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

  The amount of the aqueous phase to be used with respect to 100 parts by weight of the toner composition containing the polyester prepolymer (A) is usually 50 to 20000 parts by weight, preferably 100 to 10,000 parts by weight. If the amount is less than 50 parts by weight, the dispersion state of the toner composition is poor, and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 20000 parts by weight, it is not economical. Moreover, a dispersing agent can also be used as needed. It is preferable to use a dispersant because the particle size distribution becomes sharp and the dispersion is stable.

  Anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamine salts, amino acids as dispersants for emulsifying and dispersing the oily phase in which the toner composition is dispersed in the aqueous phase Amine salt types such as alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline, and quaternary ammonium such as alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride Nonionic surfactants such as salt-type cationic surfactants, fatty acid amide derivatives, polyhydric alcohol derivatives, such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N − Amphoteric surfactants such as ammonium betaine.

  Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount. Preferred anionic surfactants having a fluoroalkyl group include fluoroalkyl carboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [omega-fluoroalkyl (C6-C11 ) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [omega-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carboxylic acid And metal salts, perfluoroalkyl carboxylic acids (C7 to C13) and metal salts thereof, perfluoroalkyl (C4 to C12) sulfonic acids and metal salts thereof, perfluorooctane sulfonic acid diethanolamide, N-propyl-N- (2 Hydroxyethyl) -Fluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Can be mentioned,

  Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (Daikin Kogyo Co., Ltd.), MegaFuck F-l10, F-l20, F-113, F-191, F-812, F-833 (Dainippon Ink Co., Ltd.), Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products Co., Ltd.), and Fgentent F-100, F150 (manufactured by Neos).

  Examples of cationic surfactants include aliphatic primary, secondary or secondary amine acids having a fluoroalkyl group, aliphatic quaternary ammonium salts such as perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, benza Luconium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, trade names include Surflon S-121 (manufactured by Asahi Glass), Florard FC-135 (manufactured by Sumitomo 3M), Unidyne DS-202 (manufactured by Daikin Industries) , Megafac F-150, F-824 (Dainippon Ink Co., Ltd.), Xtop EF-132 (Tochem Products Co., Ltd.), Footgent F-1300 (Neos Co., Ltd.), and the like.

Further, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite and the like can be used as an inorganic compound dispersant that is hardly soluble in water.
Further, the dispersed droplets may be stabilized by a polymer protective colloid. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-chloroacrylate 2-hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N -Methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, etc., or esters of compounds containing vinyl alcohol and carboxyl groups, such as Vinyl acetate, vinyl propionate, vinyl butyrate, etc., acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethyleneimine, etc. Homopolymers or copolymers such as those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylene, polyoxypropylene, Oxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonyl phenyl ester Polyoxyethylenes such as, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

In addition, when an acid such as calcium phosphate salt or an alkali-soluble one is used as the dispersion stabilizer, the calcium phosphate salt is removed from the fine particles by a method such as washing with water after dissolving the calcium phosphate salt with an acid such as hydrochloric acid. To do. It can also be removed by operations such as enzymatic degradation.
When a dispersant is used, the dispersant may remain on the surface of the toner particles, but it is preferable from the charged surface of the toner that the dispersant is washed and removed after the elongation and / or crosslinking reaction.
The elongation and / or cross-linking reaction time is selected depending on the reactivity of the isocyanate group structure of the prepolymer (A) and the amines (B), but is usually 10 minutes to 40 hours, preferably 2 to 24 hours. is there. The reaction temperature is generally 0 to 150 ° C, preferably 40 to 98 ° C. Moreover, a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate.

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

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

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

(Carrier for two components)
When the toner of the present invention is used for a two-component developer, it may be used by mixing with a magnetic carrier. The carrier to toner content ratio in the developer is 1 to 10 weights of toner with respect to 100 parts by weight of carrier. Part is preferred. As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier having a particle diameter of about 20 to 200 μm can be used. Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and styrene acrylic copolymer resins, Halogenated olefin resins such as vinyl, polyester resins such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resins, polyethylene resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polytrifluoroethylene resins, polyhexafluoro Propylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride And fluoro such as terpolymers of non-fluoride monomers including, and silicone resins. Moreover, you may contain electrically conductive powder etc. in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. These conductive powders preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control electric resistance. The toner of the present invention can also be used as a one-component magnetic toner that does not use a carrier or a non-magnetic toner.

(Toner container)
The toner-containing container of the present invention contains the black toner or the developer of the present invention in a container.
There is no restriction | limiting in particular as said container, It can select suitably from well-known things, For example, what has a toner container main body and a cap etc. are mentioned suitably.
The size, shape, structure, material and the like of the toner container body are not particularly limited and can be appropriately selected according to the purpose. For example, the shape is preferably a cylindrical shape, A spiral unevenness is formed on the surface, the toner as the contents can be transferred to the discharge port side by rotating, and a part or all of the spiral part has a bellows function, etc. Particularly preferred.
The material of the toner container main body is not particularly limited, and those having good dimensional accuracy are preferable. For example, a resin is preferable. Among them, for example, polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, polychlorinated resin Preferred examples include vinyl resin, polyacrylic acid, polycarbonate resin, ABS resin, polyacetal resin, and the like.
The toner-containing container of the present invention is easy to store and transport, has excellent handleability, and is preferably used for replenishing toner by being detachably attached to the process cartridge and image forming apparatus of the present invention described later. Can do.

(Process cartridge)
The process cartridge of the present invention can be mounted on an image liquid apparatus, and includes an electrostatic latent image carrier that carries an electrostatic latent image, and an electrostatic latent image carried on the electrostatic latent image carrier. A developing unit that develops with a developer to form a visible image, and further selected appropriately according to need, a charging unit, an exposure unit, a developing unit, a transfer unit, a cleaning unit, a static elimination unit. It has other means such as means.
The developing means includes a developer container that contains the toner or developer of the present invention, and an electrostatic latent image carrier that carries and transports the toner or developer contained in the developer container. And a layer thickness regulating member for regulating the thickness of the toner layer to be carried.
The process cartridge of the present invention can be detachably provided in various electrophotographic apparatuses, facsimiles, and printers, and is preferably provided detachably in an image forming apparatus described later.

Here, for example, as shown in FIG. 1, the process cartridge includes a photosensitive member (101), and further includes a charging means (102), a developing means (104), and a cleaning means (107), and is further necessary. Depending on the case, it has other members. The process cartridge example of FIG. 1 has a transfer means (108) for transferring the toner image on the developed photoreceptor (101) to the image receiving paper (105).
As the photoconductor (101), those described above can be used.
A light source capable of writing with high resolution is used for the exposure means (103).
An arbitrary charging member is used for the charging means (102).

(Image forming apparatus and image forming method)
The image forming apparatus of the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing unit, and further appropriately selected as necessary. It has other means, for example, static elimination means, cleaning means, recycling means, control means and the like.
The image forming method of the present invention includes at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step, and other steps appropriately selected as necessary, for example, a static elimination step, a cleaning step. , Including recycling process, control process, etc.

  The image forming method of the present invention can be preferably implemented by the image forming apparatus, the electrostatic latent image forming step can be performed by the electrostatic latent image forming unit, and the developing step can be performed by the developing unit. The transfer step can be performed by the transfer unit, the fixing step can be performed by the fixing unit, and the other steps can be performed by the other unit.

(Development process and development means)
The developing step is a step of developing the electrostatic latent image using the toner or the developer of the present invention to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image using at least the toner or the developer of the present invention, and can be performed by the developing unit.
The developing unit is not particularly limited as long as it can be developed using at least the toner or the developer of the present invention, and can be appropriately selected from known ones. Preferably, the toner container includes at least a developing device that accommodates toner or developer and can apply the toner or developer to the electrostatic latent image in a contact or non-contact manner. A developing device provided is more preferable.

  The developing unit may be a dry developing type, a wet developing type, a single color developing unit, or a multi-color developing unit. For example, a toner having a stirrer for charging the toner or the developer by frictional stirring and a rotatable magnet roller is preferable.

In the developing device, for example, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier (photoconductor), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted. It moves to the surface of the electrostatic latent image carrier (photoconductor) by force. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier (photoconductor).
The developer accommodated in the developing device is a developer containing the toner of the present invention, but the developer may be a one-component developer or a two-component developer. The toner contained in the developer is the toner of the present invention.

  Next, an aspect in which the image forming method of the present invention is performed by the image forming apparatus will be described with reference to FIG. An image forming apparatus (100) shown in FIG. 2 includes a photosensitive drum (10) as the electrostatic latent image carrier (hereinafter referred to as “photosensitive member (10)”) and a charging roller (20) as the charging means. An exposure device (30) as the exposure means, a developing device (40) as the development means, an intermediate transfer member (50), and a cleaning device (60) as the cleaning means having a cleaning blade, A neutralizing lamp (70) as the neutralizing means.

  The intermediate transfer member (50) is an endless belt, and is designed to be movable in the direction of the arrow by three rollers (51) that are arranged on the inner side and stretch the belt. A part of the three rollers (51) also functions as a transfer bias roller capable of applying a predetermined transfer bias (primary transfer bias) to the intermediate transfer member (50). A cleaning device (90) having a cleaning blade is disposed in the vicinity of the intermediate transfer member (50), and a developed image (toner image) is transferred to a transfer sheet (95) as a final recording medium (two). A transfer roller (80) as the transfer means capable of applying a transfer bias for the next transfer) is disposed to face the transfer roller. Around the intermediate transfer member (50), a corona charger (50a) for applying a charge to the toner image on the intermediate transfer member (50) is arranged in the rotational direction of the intermediate transfer member (50). (10) and the intermediate transfer member (50) and the contact portion between the intermediate transfer member (50) and the transfer paper (95).

  The developing device (40) includes a developing belt (41) as the developer carrying member, a black developing unit (45K), a yellow developing unit (45Y), and a magenta developing unit (45M) provided around the developing belt (41). ) And a cyan developing unit (45C). The black developing unit (45K) includes a developer accommodating portion (42K), a developer supply roller (43K), and a developing roller (44K). The yellow developing unit (45Y) includes a developer accommodating portion ( 42Y), a developer supply roller (43Y), and a development roller (44Y). The magenta development unit (45M) includes a developer container (42M), a developer supply roller (43M), and a development roller (44M). The cyan developing unit (45C) includes a developer container (42C), a developer supply roller (43C), and a developing roller (44C). Further, the developing belt (41) is an endless belt, is rotatably stretched around a plurality of belt rollers, and a part thereof is in contact with the photoreceptor (10). Of the black developing unit (45K), yellow developing unit (45Y), magenta developing unit (45M) and cyan developing unit (45C), the black developing unit (45K) uses the black toner of the present invention.

  In the image forming apparatus (100) shown in FIG. 2, for example, the charging roller (20) uniformly charges the photosensitive drum (10). An exposure device (30) performs imagewise exposure on the photosensitive drum (10) to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum (10) is developed by supplying toner from the developing device (40) to form a toner image. The toner image is transferred (primary transfer) onto the intermediate transfer member (50) by the voltage applied from the roller (51), and further transferred (secondary transfer) onto the transfer paper (95). As a result, a transfer image is formed on the transfer paper (95). The residual toner on the photoconductor (10) is removed by the cleaning device (60), and the charge on the photoconductor (10) is once removed by the charge eliminating lamp (70).

  Another mode for carrying out the image forming method of the present invention by the image forming apparatus will be described with reference to FIG. The image forming apparatus (100) shown in FIG. 3 does not include the developing belt (41) in the image forming apparatus (100) shown in FIG. 2, and a black developing unit (45K), Except that the yellow developing unit (45Y), the magenta developing unit (45M), and the cyan developing unit (45C) are directly opposed to each other, the image forming apparatus (100) shown in FIG. 2 has the same configuration. The same effect is exhibited. In FIG. 3, the same components as those in FIG. 2 are denoted by the same reference numerals.

  In the tandem type electrophotographic apparatus (T) in which the image forming method of the present invention is carried out by the image forming apparatus, as shown in FIG. 4, the image on each photoreceptor (1) is transferred to the sheet by the transfer apparatus (2). As shown in FIG. 5, an image on each photoconductor (1) is temporarily intermediated by a primary transfer device (2) as shown in FIG. There is an indirect transfer type in which the image on the intermediate transfer body (4) is transferred onto the transfer body (4) and then transferred onto the sheet (s) by the secondary transfer device (5). The transfer device (5) is a transfer conveyance belt, but there are also roller shapes and methods. 4 and 5, reference numeral (7) indicates a fixing means (device).

  Comparing the direct transfer type with the indirect transfer type, the former is the upstream side of the tandem type image forming apparatus (T) in which the photoconductors (1) are arranged, and the downstream side. Therefore, the fixing device (7) must be arranged on the sheet, and there is a disadvantage that the fixing device (7) is enlarged in the sheet conveying direction. On the other hand, the latter can set the secondary transfer position relatively freely. The sheet feeding device (6) and the fixing device (7) can be arranged so as to overlap the tandem type image forming device (T), and there is an advantage that downsizing is possible.

  In the former, in order not to increase the size in the sheet conveying direction, the fixing device (7) is disposed close to the tandem type image forming apparatus (T). Therefore, the fixing device (7) cannot be disposed with a sufficient margin that the sheet (s) can bend, and an impact (particularly thick sheet) when the leading edge of the sheet (s) enters the fixing device (7). The fixing device (7) affects the upstream side image formation due to the difference in speed between the sheet conveyance speed when passing through the fixing device (7) and the sheet conveyance speed by the transfer conveyance belt. There are easy drawbacks. On the other hand, in the latter case, the fixing device (7) can be disposed with a sufficient margin that the sheet (s) can be bent, so that the fixing device (7) hardly affects the image formation. Can do.

In view of the above, recently, an indirect transfer type of tandem type electrophotographic apparatus has attracted attention.
In this type of color electrophotographic apparatus, as shown in FIG. 5, the transfer residual toner remaining on the photoconductor (1) after the primary transfer is removed by the photoconductor cleaning device (8) to remove the photoconductor 1. The surface was cleaned and prepared for another image formation. Further, the transfer residual toner remaining on the intermediate transfer member (4) after the secondary transfer is removed by the intermediate transfer member cleaning device (9) to clean the surface of the intermediate transfer member (4), so as to prepare for image formation again. It was.

A tandem image forming apparatus (100) shown in FIG. 6 is a tandem color image forming apparatus. The tandem image forming apparatus (120) includes a copying apparatus main body (150), a paper feed table (200), a scanner (300), and an automatic document feeder (ADF) (400).
The copying machine main body (150) is provided with an endless belt-like intermediate transfer member (50) at the center. The intermediate transfer member (50) is stretched around the support rollers (14), (15) and (16), and can be rotated clockwise in FIG. An intermediate transfer body cleaning device (17) for removing residual toner on the intermediate transfer body (50) is disposed in the vicinity of the support roller (15). The intermediate transfer member (50) stretched between the support roller (14) and the support roller (15) has four image forming units (18) of yellow, cyan, magenta, and black along the conveyance direction. A tandem developing device (120) arranged opposite to each other is arranged. An exposure device (21) is disposed in the vicinity of the tandem developing device (120). A secondary transfer device (22) is disposed on the side of the intermediate transfer member (50) opposite to the side on which the tandem developing device (120) is disposed. In the secondary transfer device (22), a secondary transfer belt (24), which is an endless belt, is stretched between a pair of rollers (23), and a transfer sheet conveyed on the secondary transfer belt (24); The intermediate transfer member (50) can contact each other. A fixing device (25) is disposed in the vicinity of the secondary transfer device (22).
In the tandem image forming apparatus (100), in the vicinity of the secondary transfer device (22) and the fixing device (25), sheet reversal is performed for reversing the transfer paper in order to form an image on both sides of the transfer paper. A device (28) is arranged.

  Next, full color image formation (color copying) using the tandem developing device (120) will be described. That is, first, a document is set on the document table (130) of the automatic document feeder (ADF) (400) or the automatic document feeder (400) is opened and the contact glass (32) of the scanner (300) is opened. A document is set on the document and the automatic document feeder (400) is closed.

  When a start switch (not shown) is pressed, when a document is set on the automatic document feeder (400), the document is transported and moved onto the contact glass (32). ) Immediately after the document is set on the scanner (300), the first traveling body (33) and the second traveling body (34) travel. At this time, light from the light source is irradiated by the first traveling body (33) and reflected light from the document surface is reflected by the mirror in the second traveling body (34), and is read through the imaging lens (35). The color original (color image) is read at (36), and is read as black, yellow, magenta and cyan image information.

  Each image information of black, yellow, magenta and cyan is stored in each image forming means (18) (black image forming means, yellow image forming means, magenta image forming means and cyan in the tandem developing device (120). Image forming means), and each toner image of black, yellow, magenta and cyan is formed in each image forming means. That is, each image forming means (18) (black image forming means, yellow image forming means, magenta image forming means and cyan image forming means) in the tandem developing device (120) is as shown in FIG. The photosensitive member (10) (the black photosensitive member (10K), the yellow photosensitive member (10Y), the magenta photosensitive member (10M), and the cyan photosensitive member (10C)) and the photosensitive member uniformly. The charging member (20a) to be charged and the photosensitive member are exposed (L in FIG. 7) like an image corresponding to each color image based on each color image information, and corresponding to each color image on the photosensitive member. An exposure device for forming an electrostatic latent image, and developing the electrostatic latent image with each color toner (black toner, magenta toner, cyan toner, and yellow toner of the present invention) A developing device (61) for forming the toner image, a transfer charger (62) for transferring the toner image onto the intermediate transfer member (50), a photoconductor cleaning device (63), and a static eliminator (64). It is possible to form each monochrome image (black image, yellow image, magenta image, and cyan image) based on the image information of each color. The black image, the yellow image, the magenta image, and the cyan image formed in this way are respectively transferred onto the intermediate transfer member (50) that is rotationally moved by the support rollers (14), (15), and (16). Black image formed on the photoconductor (10K), yellow image formed on the yellow photoconductor (10Y), magenta image formed on the magenta photoconductor (10M), and cyan photoconductor (10C). ) The cyan image formed thereon is sequentially transferred (primary transfer). Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member (50) to form a composite color image (color transfer image).

  On the other hand, in the paper feed table (200), one of the paper feed rollers (142) is selectively rotated so that the sheet (recording paper) is fed from one of the paper feed cassettes (144) provided in the paper bank (143). ), Separated one by one by the separation roller (145), sent to the paper feed path (146), and conveyed by the conveyance roller (147) to the paper feed path (148) in the copier body (150). Guide and stop against the registration roller (49). Alternatively, the sheet feed roller (150) is rotated to feed out the sheets (recording paper) on the manual feed tray (53a) and separated one by one by the separation roller (52) into the manual feed path (53). Stop against the registration roller (49). The registration roller (49) is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet.

  Then, the registration roller (49) is rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member (50), and the intermediate transfer member (50), the secondary transfer device (22), The sheet (recording paper) is fed between the sheets, and the composite color image (color transfer image) is transferred (secondary transfer) onto the sheet (recording paper) by the secondary transfer device (22). A color image is transferred and formed on (recording paper). The residual toner on the intermediate transfer member (50) after the image transfer is cleaned by the intermediate transfer member cleaning device (17).

  The sheet (recording paper) on which the color image formed using the black toner of the present invention has been transferred is conveyed by the secondary transfer device (22), sent to the fixing device (25), and fixed. In the apparatus (25), the composite color image (color transfer image) is fixed on the sheet (recording paper) by heat and pressure. Thereafter, the sheet (recording paper) is switched by the switching claw (55) and discharged by the discharge roller (56) and stacked on the discharge tray (57), or switched by the switching claw (55) and the sheet is reversed. The image is reversed by the device (28) and guided again to the transfer position, and an image is recorded also on the back surface. Then, the image is discharged by the discharge roller (56) and stacked on the discharge tray (57).

Below, an Example and a comparative example are given and the structure and effect of this invention are demonstrated in detail.
First, the manufacture example of the material used by the Example and the comparative example is described. In the following description, “part” means “part by weight” and “%” means “% by weight”.

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

<Adjustment of aqueous phase>
(Production Example 2)
990 parts of water, 83 parts of [resin fine particle dispersion 1], 37 parts of 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries) and 90 parts of ethyl acetate were mixed and stirred. A liquid was obtained. This is designated as [Aqueous Phase 1].

<Synthesis of low molecular weight polyester>
(Production Example 3)
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 3-mole adduct, 208 parts terephthalic acid, 46 parts adipic acid and dibutyl 2 parts of tin oxide was added, reacted at 230 ° C. for 8 hours at normal pressure, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg. Then, 44 parts of trimellitic anhydride was added to the reaction vessel, and 2 parts at 180 ° C. and normal pressure. The reaction was performed for a while to obtain [Low molecular weight polyester 1]. [Low molecular polyester 1] had a number average molecular weight of 2500, a weight average molecular weight of 6700, a Tg of 43 ° C., and an acid value of 25.

<Synthesis of intermediate polyester>
(Production Example 4)
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 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. for 8 hours at normal pressure, and further [intermediate polyester 1] reacted for 5 hours at a reduced pressure of 10 to 15 mmHg. [Intermediate Polyester 1] had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, Tg of 55 ° C., an acid value of 0.5, and a hydroxyl value of 51.
Next, 410 parts of [Intermediate Polyester 1], 89 parts of isophorone diisocyanate and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Polymer 1] was obtained. [Prepolymer 1] had a free isocyanate weight% of 1.53%.

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

<Synthesis of MB>
(Production Example 6)
260 parts of water, C.I. I. Pigment Black 7 (NIPex70 manufactured by Degussa) and C.I. I. Pigment Blue 15: 3 (Clearant's HOSTAPERM BLUE B2G) having a mass ratio of 90:10, 1000 parts of a mixed pigment and 1000 parts of a polyester resin (Tg 60 ° C. Mw 20000 T1 / 2 110 ° C.) are added, and a Henschel mixer (Mitsui Mining Co., Ltd.) The mixture was kneaded at 130 ° C. for 30 minutes using two rolls, rolled and cooled, and pulverized with a pulverizer to obtain [Masterbatch 1].

<Creation of oil phase>
(Production Example 7)
In a container equipped with a stir bar and a thermometer, 378 parts of [Low molecular weight polyester 1], 110 parts of Carnauba WAX, and 947 parts of ethyl acetate were charged, heated to 80 ° C. with stirring, and kept at 80 ° C. for 5 hours. It was cooled to 30 ° C at 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 1].
[Raw material solution 1] 1324 parts are transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads are 80% by volume. Pigment red and WAX were dispersed under conditions of filling and 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] was added, followed by one pass with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 1]. The solid content concentration of [Pigment / WAX Dispersion 1] (130 ° C., 30 minutes) was 50%.

[Example 1]
<Emulsification and desolvation>
[Pigment / WAX Dispersion 1] 749 parts, [Prepolymer 1] 115 parts, [Ketimine Compound 1] 2.9 parts in a container, and TK homomixer (manufactured by Tokushu Kika) at 5,000 rpm for 1 minute After mixing, 1200 parts of [Aqueous phase 1] was added to the container, and mixed with a TK homomixer at 13,000 rpm for 20 minutes to obtain [Emulsion slurry 1].
[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 4 hours to obtain [Dispersion slurry 1]. [Dispersion Slurry 1] had a volume average particle size of 4.78 μm and a number average particle size of 5.16 μm (measured with Multisizer II).

<Washing and drying>
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(2) 10% hydrochloric acid was added to the filter cake of (1) above to adjust to pH 2.8, mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(3) Add 300 parts of ion exchange water to the filter cake of (2) above, mix with TK homomixer (10 minutes at 12,000 rpm), and then filter twice to obtain [Filter cake 1]. It was.
[Filtration cake 1] was dried at 45 ° C. for 48 hours in a circulating drier, and sieved with a mesh of 75 μm to obtain [Toner 1].

<Synthesis of MB>
(Production Example 8)
260 parts of water, C.I. I. Pigment Black 7 (NIPex70 manufactured by Degussa) and C.I. I. Pigment Blue 15: 4 (4937, manufactured by Dainichi Seika Co., Ltd.) having a mass ratio of 90:10, 1000 parts of a mixed pigment and 1000 parts of a polyester resin (Tg 60 ° C. Mw 20000 T1 / 2 110 ° C.) were added, and a Henschel mixer (Mitsui Mining Co., Ltd.). The mixture was kneaded at 130 ° C. for 30 minutes using two rolls, rolled and cooled, and pulverized with a pulverizer to obtain [Masterbatch 2].

[Example 2]
[Toner 2] was obtained in the same manner as in Example 1 except that [Masterbatch 2] was used instead of [Masterbatch 1] in Example 1.

<Synthesis of MB>
(Production Example 9)
260 parts of water, C.I. I. Pigment Black 7 (NIPex70 manufactured by Degussa) and C.I. I. Pigment Blue 15: 3 (Clearant's HOSTAPERM BLUE B2G) having a mass ratio of 65:35, 1000 parts of mixed pigment and 1000 parts of polyester resin (Tg 60 ° C. Mw 20000 T1 / 2 110 ° C.) are added, and Henschel mixer (Mitsui Mining Co., Ltd.) The mixture was kneaded for 30 minutes at 130 ° C. using two rolls, rolled and cooled, and pulverized with a pulverizer to obtain [Masterbatch 3].

[Example 3]
[Toner 3] was obtained in the same manner as in Example 1 except that [Masterbatch 3] was used instead of [Masterbatch 1] in Example 1.

<Synthesis of MB>
(Production Example 10)
260 parts of water, C.I. I. Pigment Black 7 (Negex 70 manufactured by Degussa) 1000 parts and 1000 parts of polyester resin (Tg 60 ° C. Mw 20000 T1 / 2 110 ° C.) are added and mixed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). The mixture was kneaded at 30 ° C. for 30 minutes, cooled and rolled, and pulverized with a pulverizer to obtain [Masterbatch 4].

[Comparative Example 1]
[Toner 4] was obtained in the same manner as in Example 1 except that [Masterbatch 4] was used instead of [Masterbatch 1] in Example 1.

<Synthesis of MB>
(Production Example 10)
260 parts of water, C.I. I. Pigment Blue 15: 3 (Clariant's HOSTAPERM BLUE B2G) 1000 parts, polyester resin 1000 parts (Tg60 ° C. Mw 20000 T1 / 2 110 ° C.) are added and mixed with a Henschel mixer (Mitsui Mining Co., Ltd.), and the mixture is rolled into two rolls. After being kneaded at 130 ° C. for 30 minutes, the product was cooled and rolled, and pulverized with a pulverizer to obtain [Masterbatch 5].

[Comparative Example 2]
[Toner 5] was obtained in the same manner as in Example 1 except that the mass ratio of [Masterbatch 4] and [Masterbatch 5] was 90:10 instead of [Masterbatch 1] in Example 1.

[Comparative Example 3]
[Toner 6] was obtained in the same manner as in Example 1 except that the mass ratio of [Masterbatch 4] and [Masterbatch 5] was set to 65:35 instead of [Masterbatch 1] in Example 1.

<Evaluation of toner>
(Chargeability)
10 g of each toner thus obtained and 100 g of ferrite carrier were mixed in an environment having a temperature of 28 ° C. and a humidity of 80%, and the charge amount of the toner was measured by a blow-off method. In addition, the charge distribution at this time was sharp.

(Particle size)
The particle diameter of the toner was measured using a particle size measuring device “Coulter Counter TAII” manufactured by Coulter Electronics Co., Ltd., with an aperture diameter of 100 μm. The volume average particle diameter and the number average particle diameter were determined by the particle size measuring instrument. The surface shape of the toner was observed with a scanning electron microscope.

(Fixability)
A belt fixing method by remodeling Ricoh's imgio Neo 450, a solid image on plain paper and cardboard transfer paper (Ricoh type 6200 and NBS Ricoh's copy printing paper), 1.0 ± 0.1 mg / cm ² The fixing was evaluated by the toner adhesion amount. A fixing test was performed by changing the temperature of the fixing belt, and an upper limit temperature at which hot offset did not occur on plain paper was defined as an upper limit fixing temperature. Further, the minimum fixing temperature was measured with a thick paper.
The lower limit fixing temperature was determined as the fixing lower limit temperature at the fixing roll temperature at which the residual ratio of the image density after rubbing the obtained fixed image with a pad was 70% or more. The case where the upper limit fixing temperature was 190 ° C. or higher and the lower limit fixing temperature was 140 ° C. or lower was evaluated as “◯”, and the case where it was not satisfied was evaluated as “X”.

(Image density)
The image density is solid image on plain paper and cardboard transfer paper (Ricoh type 6200 and NBS Ricoh copy printing paper <135>) using Ricoh's imgio Neo 450, and 0.4 mg / cm ² of toner is used. Adjustment is performed so that the image is developed, and adjustment is made so that the temperature of the fixing belt is variable. After outputting a solid image, the image density is measured by X-Rite 938 (manufactured by X-Rite). This was measured at five points for each color alone, and the average was obtained for each color.

(Turbidity)
Next, 1 part by weight of “Silica R972” (manufactured by Nippon Aerosil Co., Ltd.) as an external additive is added to 100 parts by weight of the toner, and the silica externally added toner mixed for 1 minute in a sample mill is added to an electrophotographic full color copying machine “imageio”. With a modified machine of Neo 450 "(manufactured by Ricoh), fixing was performed without a fixing fuser oil, and an OHP fixed image was created. The turbidity was measured by fixing a solid color image on a transparent sheet for OHP and using a direct reading haze degree computer HGM-2DP manufactured by Suga Test Instruments Co., Ltd. This haze degree is also referred to as haze, and is measured as a measure of the transparency of the toner. The lower the value, the higher the transparency and the better the color developability when an OHP sheet is used.

(Evaluation of hue of image)
About the printed matter from which the black image (solid part) was obtained using the said developer, it measured with the reflection densitometer X-Rite938 (brand name: X-rite company make), and hue (a *, b *) was quantified. Evaluated. The hue is based on the definition of the color system standardized by the CIE (International Commission on Illumination). The chromaticity representing the hue is set in units of L * a * b *. a * b * indicates the color direction, a * is positive, hue is reddish, negative is greenish, b * is positive, hue is yellowish, and negative is blueish . Further, C.I. I. Pigment Black 7 used NIPex70 manufactured by Degussa.
These evaluation results are shown in Table 1.

    The black toner of the present invention is excellent in toner granulation properties and good coloring power, bluishness, storage stability, and transparency. Therefore, the black toner is good when used as a developer for an electrophotographic apparatus or an electrostatic recording apparatus. It is possible to form an image with excellent color development and excellent optical transparency in OHP.

It is a schematic block diagram which shows an example of the process cartridge of this invention. 1 is a schematic configuration diagram illustrating an example of an image forming apparatus. It is a schematic block diagram which shows another example of an image forming apparatus. It is a schematic block diagram which shows another example of an image forming apparatus. It is a schematic block diagram which shows another example of an image forming apparatus. It is a schematic block diagram which shows another example of an image forming apparatus. It is a schematic block diagram which shows another example of an image forming apparatus.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Photoconductor 2 Transfer device 3 Sheet conveyance belt 4 Intermediate transfer body 5 Secondary transfer device 6 Paper feed device 7 Fixing device 8 Photoconductor cleaning device 9 Intermediate transfer body cleaning device 10 Photoconductor (photoconductor drum)
10K black photoreceptor 10Y yellow photoreceptor 10M magenta photoreceptor 10C cyan photoreceptor 14 support roller 15 support roller 16 support roller 17 intermediate transfer cleaning device 18 image forming means 20 charging roller 20a charging roller 21 exposure device 22 secondary Transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure roller 28 Sheet reversing device 30 Exposure device 32 Contact glass 33 First traveling member 34 Second traveling member 35 Imaging lens 36 Reading sensor 40 Developer 41 Developing belt 42K Developer container 42Y Developer container 42M Developer container 42C Developer container 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer supply roller 44K Developer roller 44Y Developer roller 44M Development Roller 4 C developing roller 45K black developing unit 45Y yellow developing unit 45M magenta developing unit 45C cyan developing unit 49 registration roller 50 intermediate transfer member 50a corona charging device 51 roller 52 separation roller 53 manual feed tray 53a charging roller 55 switching claw 56 discharge Roller 57 Discharge tray 60 Cleaning device 61 Developing device 62 Transfer charger 63 Photoconductor cleaning device 64 Charger 70 Developing device housing 80 Collected toner transport device 90 Cleaning device 95 Transfer paper 100 Image forming device 101 Photoconductor 102 Charging device 103 Exposure device 104 Developing means 105 Image receiving paper 107 Cleaning means 108 Transfer means 120 Tandem developing device 130 Document table 142 Paper feed roller 143 Paper bank 144 Paper feed cassette 145 Separating roller 146 Paper feed path 147 Conveying roller 148 Feeding path 150 Copying device main body 200 Feeding table 300 Scanner 400 Automatic document feeder (ADF)
L exposure s sheet T tandem type image forming apparatus

Claims (20)

  In a black toner produced in an aqueous medium and containing at least a binder resin and a colorant, the colorant is a mixed pigment of carbon black as a black pigment and copper phthalocyanine as a cyan pigment. Part of a binder resin and carbon black and / or copper phthalocyanine are mixed at least before mixing of carbon black and copper phthalocyanine. A black toner for developing an electrostatic image, characterized by not being broken.   In a black toner produced in an aqueous medium and containing at least a binder resin and a colorant, the colorant is a mixed pigment of carbon black as a black pigment and copper phthalocyanine as a cyan pigment. Used for a master batch obtained by kneading with a resin constituting a part, wherein the master batch is obtained by kneading carbon black and copper phthalocyanine simultaneously with a part of the binder resin. Black toner.   The black toner for developing an electrostatic charge image according to claim 1 or 2, wherein a mixing ratio of the carbon black and copper phthalocyanine is 99: 1 to 70:30.   The carbon black is C.I. I. Pigment Black 7, and the copper phthalocyanine is C.I. I. Pigment Blue 15: 3 and / or C.I. I. The black toner for developing an electrostatic charge image according to claim 2, which is Pigment Blue 15: 4.   5. The black toner for developing an electrostatic charge image according to claim 1, wherein 50 to 100% by weight of the binder resin is a polyester resin.   A toner raw material organic solvent liquid in which a black raw material is obtained by dissolving or dispersing a toner raw material containing at least an active hydrogen group-containing compound, a polymer having a site capable of reacting with an active hydrogen group, a colorant, and a release agent in an organic solvent. Is dispersed in an aqueous medium, and the organic solvent is removed, washed and dried after reacting or reacting the active hydrogen group-containing compound and the polymer having a site capable of reacting with the active hydrogen group. 6. The black toner for developing an electrostatic charge image according to claim 1, wherein the black toner is obtained by a method including a step.   The black toner is obtained by a method including a step of causing the aqueous medium to contain resin fine particles and adhering them to the toner particle surface of the toner. The black toner for developing an electrostatic image as described.   The black toner for developing an electrostatic charge image according to any one of claims 1 to 7, wherein a release agent is contained in the toner.   9. The black toner for developing an electrostatic charge image according to claim 6, wherein a melting point of the release agent is 160 ° C. or less.   The black toner for developing an electrostatic charge image according to claim 7, wherein the resin fine particles have an average particle diameter of 5 to 500 nm.   The polymer having a site capable of reacting with an active hydrogen group is a modified polyester resin and a non-modified polyester resin, and the weight ratio of the modified polyester resin to the non-modified polyester resin is 5/95 to 75/25. The black toner for developing an electrostatic charge image according to any one of claims 6 to 10, wherein:   The black toner for developing electrostatic images according to claim 11, wherein the acid value of the modified polyester resin and the non-modified polyester resin is 0 to 30 mg KOH / g.   The black toner for developing an electrostatic charge image according to any one of claims 6 to 12, wherein a blending ratio of the colorant and the organic solvent is in a range of 5:95 to 50:50 by weight.   The volume average particle diameter (Dv) of the toner particles of the black toner is 3.0 μm or more and 8.0 μm or less, and the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) is 14. The black toner for developing an electrostatic charge image according to claim 1, wherein the black toner is 1.00 or more and 1.30 or less.   The black toner for developing an electrostatic charge image according to claim 1, wherein the toner particles of the black toner have an average circularity of 0.95 to 0.995.   A one-component developer for developing an electrostatic latent image, comprising the black toner for developing an electrostatic image according to any one of claims 1 to 15.   A two-component developer for developing an electrostatic latent image, comprising the black toner for developing an electrostatic image according to any one of claims 1 to 15 and a carrier.   A toner-containing container filled with the black toner for developing an electrostatic charge image according to claim 1.   The electrostatic latent image developing black toner according to any one of claims 1 to 15, wherein the electrostatic latent image bearing member and the electrostatic latent image formed on the electrostatic latent image bearing member can be mounted on an image forming apparatus. A process cartridge comprising at least developing means for developing a visible image by using the developing cartridge.   An electrostatic latent image forming unit that forms an electrostatic latent image on an electrostatic latent image carrier and the electrostatic latent image developing black toner according to claim 1 at least. Development means for forming a visible image by developing, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transfer image transferred to the recording medium. Image forming apparatus.

Images