JP2010020019A - Magenta toner, developer, manufacturing method for the toner, image forming method, image forming apparatus and process cartridge - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a magenta toner or the like having an excellent spectral reflection characteristic for color reproduction, high chromaticity and a high reflection density characteristic, having a clear magenta color, improved in dispersibility to binder resin to attain high coloring performance, and improved in transparency. <P>SOLUTION: This magenta toner is characterized in that: the toner contains at least binder resin, a pigment and a pigment dispersing agent; the pigment contains C.I. Pigment Red 122 and C.I. Pigment Violet 19; a solution obtained by dissolving 10 g of the toner in 40 g of tetrahydrofuran is applied on a base material by using a 0.3 mm wire bar; and the haze degree of a coating film is from 0.1 to 25. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a magenta toner suitable for forming a color image, which is used for developing an electrostatic latent image in an electrophotographic copying machine, a laser printer, a facsimile machine, and the like. Further, a developer using this magenta toner, The present invention relates to a manufacturing method, an image forming method, an image forming apparatus, and a process cartridge.

An electrophotographic technique for forming a visible image by developing an electric latent image with a developer is known. In this method, an electrical latent image is formed on a photoconductor containing a photoconductive substance, and the obtained latent image is developed with a developer containing toner to form a toner image, and this toner is recorded on a recording medium such as paper. After the image is transferred, the image is fixed by heating and pressing to form a fixed image.
In order to form a full-color image using such an electrophotographic method, for example, light from an original is exposed on a photoconductor through a color separation filter, or an image read by a scanner is applied on a photoconductor with a laser. By writing and exposing, an electric latent image of the yellow image portion is formed on the photoreceptor. A yellow toner image obtained by developing the electrical latent image with yellow toner is transferred to a recording medium such as paper. Next, in the same process, a magenta toner image obtained using magenta toner and cyan toner, and a cyan toner image are sequentially superimposed on the yellow toner image to form a full color image.

  Conventionally, pulverized toner formed by melt-kneading and pulverizing a thermoplastic resin, a pigment as a colorant, and a charge control agent has been used for image formation by the electrophotographic method described above. A magenta toner used for forming a full-color image generally has C.I. I. Pigment Red 122 is used. The produced magenta toner has a problem that the image saturation is insufficient and the optical reflection density of the image is low.

  In order to solve this problem, individual improvements of pigments or dyes used in magenta toners, improvements by the combined use of pigments and dyes, and the like have been proposed. However, these proposals have a problem that the saturation is lowered. It was.

Patent Document 1 describes an invention of a color toner for electrostatic charge development. In the emulsion polymerization aggregation method toner, C.I. I. Pigment Red122 and C.I. I. It is described that both Pigment Violet 19 can be included.
However, the obtained magenta toner does not have excellent spectral reflection characteristics for color reproduction, and does not have the desired saturation and reflection density characteristics. Therefore, the magenta toner has a clear magenta color and dispersibility in the binder resin. The present situation is that a magenta toner having good coloration and transparency is not yet obtained.
Further, Patent Documents 2 to 3 relating to the invention of the toner of the present applicant are also known.

Japanese Patent No. 3970441 JP 2007-279585 A JP 2007-279707 A

The present invention has focused on the viewpoint that various problems of the magenta toner in the prior art are in the dispersibility of the pigment in the toner. As the dispersibility, a magenta toner in which a haze degree of a coating film obtained by applying a solution obtained by dissolving 10 g of toner in 40 g of tetrahydrofuran on a substrate with a 0.3 mm wire bar is in a specific range is the same as that in the prior art. We found that there is a possibility of solving various problems at once.
That is, the present invention has excellent spectral reflection characteristics for color reproduction, high saturation and high reflection density characteristics, a clear magenta color, good dispersibility for the binder resin, high coloration, and transparency. An object is to provide a magenta toner that is good.
Another object of the present invention is to provide a developer using such an excellent magenta toner, a method for producing the toner, an image forming method, an image forming apparatus, and a process cartridge.

In view of the problems of the prior art, the present inventors have conducted intensive research. As a result, the present invention is solved by the following means.
That is, the present invention
(1) A magenta toner containing at least a binder resin, a pigment, and a pigment dispersant, wherein the pigment is C.I. I. Pigment Red122 and C.I. I. Pigment Violet 19, and a coating film obtained by applying a solution obtained by dissolving 10 g of the toner in 40 g of tetrahydrofuran onto a substrate with a 0.3 mm wire bar has a haze degree of 0.1 to 25%. A magenta toner characterized by being.
(2) In the above (1), the C.I. I. Pigment Red122 and C.I. I. The mass ratio of Pigment Violet 19 is 95: 5 to 60:40.
(3) In any one of the above (1) to (2), a polyester pigment dispersant is contained as the pigment dispersant.
(4) In any one of the above (1) to (2), an acrylic pigment dispersant is contained as the pigment dispersant.
(5) In any one of the above (1) to (2), a polyurethane pigment dispersant is contained as the pigment dispersant.
(6) In any one of (1) to (5), C.I. I. Pigment Red122 and C.I. I. The total content of Pigment Violet 19 is 1% by mass to 20% by mass.
(7) In any one of the above (1) to (6), the amount of the pigment dispersant added is 1 part by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the pigment.
(8) The volume average particle diameter (Dv) of the magenta toner according to any one of (1) to (7) is 2.5 μm to 5.5 μm.
(9) In any one of (1) to (7), the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) of the magenta toner is 1.0 to 1.2.
(10) In any one of the above (1) to (9), a compound having an active hydrogen group in an organic solvent, a polymer having a site capable of reacting with the compound having an active hydrogen group, a pigment, and the pigment It is obtained by dissolving or dispersing a toner material containing at least a dispersant, reacting the dissolved or dispersed material in an aqueous medium, and removing the organic solvent from the obtained emulsified dispersion.
(11) In the above (10), the polymer having a site reactive with the compound having an active hydrogen group is a modified polyester resin (i) having a reactive substituent.
(12) In the above (11), the reactive substituent of the polymer having the reactive site is an isocyanate group.
(13) In any one of the above (11) to (12), the binder resin is a modified polyester resin (i) obtained by reacting with a compound having an active hydrogen group, and an unmodified polyester resin (ii) And the mass ratio [(i) / (ii)] is 5/95 to 30/70.
(14) An electrostatic charge developer using the toner according to any one of (1) to (13).
(15) Dissolving or dispersing a toner material containing at least a compound having an active hydrogen group in an organic solvent, a polymer having a site capable of reacting with the compound having an active hydrogen group, and a pigment and a pigment dispersant; A method for producing a toner in which an organic solvent is removed from an emulsified dispersion obtained by reacting the dissolved or dispersed material in an aqueous medium. I. Pigment Red122 and C.I. I. Pigment Violet 19, and the pigment dispersant is at least one of a polyester pigment dispersant, an acrylic pigment dispersant, or a polyurethane pigment dispersant.
(16) In an image forming method for developing an electrostatic latent image formed on an image carrier with toner, the toner uses the magenta toner described in any one of (1) to (13). .
(17) An image forming apparatus for developing an electrostatic latent image formed on an image carrier with toner, wherein the toner is the magenta toner according to any one of claims 1 to 13.
(18) Integrating at least the image carrier and developing means for developing the electrostatic image formed on the image carrier using the magenta toner according to any one of claims 1 to 13 into a visible image. And a process cartridge which is detachably attached to the main body of the image forming apparatus.

  According to the present invention, it has excellent spectral reflection characteristics for color reproduction, high saturation and high reflection density characteristics, a clear magenta color, good dispersibility for the binder resin, high coloration, and transparency. It is possible to provide a magenta toner having good toner. In addition, the present invention can provide an excellent developer by using such a magenta toner, a method for producing the toner, an image forming method, an image forming apparatus, and a process cartridge.

The magenta toner of the present invention includes at least a binder resin, a pigment, and a pigment dispersant, and includes a release agent, a charge control agent, and, if necessary, other components.
The haze degree of the magenta toner of the present invention is 0.1 to 25%, preferably 0.1 to 20%. When the haze degree is less than 0.1%, the hiding power is lost and the coloring power is lowered. When the haze degree exceeds 25%, the dispersion is insufficient and the coloring power and saturation may be lowered.
The haze degree is determined by preparing a coating film in which 10 g of a pigment-containing toner is dissolved or dispersed in 40 g of tetrahydrofuran (THF) and applied onto a substrate with a 0.3 mm wire bar. The haze degree can be determined by measuring with a TM double beam type automatic haze computer (manufactured by Suga Test Instruments Co., Ltd.).
A transparent film is suitable as the substrate for obtaining such a haze degree, and examples thereof include a PET (polyethylene terephthalate) film, a PP (polypropylene) film, and a PE (polyethylene) film.
Examples of the pigment used in the present invention include C.I. I. Pigment Red122 and C.I. I. Pigment Violet 19, preferably having a mass ratio of 95: 5 to 60:40, more preferably 90:10 to 70:30. C. above. I. If the ratio (mass ratio) of Pigment Red 122 exceeds 95, the image saturation and the image reflection density may be low, and if it is less than 60, the image reflection density may be low.

C. above. I. Pigment Red122 and C.I. I. The total content of Pigment Violet 19 in the toner is preferably 1% by mass to 20% by mass, and more preferably 4% by mass to 10% by mass.
In the toner, it is preferable that a pigment as a colorant is uniformly dispersed in the toner. In addition, although a dye can also be used as a coloring agent, a pigment is used from the point etc. which are excellent in light resistance.
In the present invention using a pigment as a colorant, it is preferable to use a pigment dispersant because the pigment is uniformly dispersed and stabilized in the toner. In this case, the dispersed particle diameter of the pigment can be measured by, for example, a laser scattering / diffraction method, a laser Doppler method, a centrifugal sedimentation method, an ultrasonic attenuation method, or the like.
However, the laser scattering / diffraction method needs to be diluted with a large dilution ratio, and parameter setting is difficult. Further, the laser Doppler method can be measured at a relatively low dilution, but dilution is necessary. The centrifugal sedimentation method takes a long time for measurement. Furthermore, the ultrasonic attenuation method has many parameters necessary for measurement, and needs to be set for each material type.
As described above, the conventional methods for measuring the dispersed particle size are complicated, time-consuming and require large dilution, and the measurement method takes time. It is difficult.
In contrast, the toner of the present invention employs the above-described haze degree as a measure of transparency correlated with the dispersed particle diameter, and when the haze degree falls within a specific numerical range, The degree of pigment dispersion can be satisfied.

  The magenta toner is formed by using a pigment dispersant together with the colorant having the two types of pigments. The pigment dispersant includes at least one of a polyester pigment dispersant, an acrylic pigment dispersant, and a polyurethane pigment dispersant.

In the magenta toner of the present invention, a derivative having a structure similar to that of a pigment called a synergist can be used in order to improve the dispersion of the pigment in the toner. Since this synergist has a structure similar to that of a pigment, it has a good compatibility with the pigment (that is, has a strong interaction) and also has a strong interaction with the dispersant. In other words, a portion similar to the pigment acts as an adsorbing group on the pigment, and other portions (such as substituents) act so as to have an affinity with the dispersant.
For this reason, by using such a synergist in combination with the pigment dispersant as described above, it is possible to effectively disperse even a pigment having a small amount of acid or base through a medium between the pigment and the pigment dispersant. Thus, it is considered that a toner having excellent dispersibility can be formed. In addition, it seems that the familiarity with the binder resin is improved, and the pigment improves the dispersion performance in the binder resin. For the magenta toner of the present invention, a commercial product can be used as a synergist. For example, as a commercial product, Solsperse manufactured by ICI, such as Solsperse 5000, Solsperse 12000, Solsperse 22000, Solsperse 24000, and the like can be used.
When such a synergist is added, it is preferable to add about 0.1 to 1% by mass in the toner.

Examples of the polyester pigment dispersant include Ajisper PB821, Azisper PB822, Azisper PB711 (all manufactured by Ajinomoto Fine Techno Co., Ltd.); Disparon DA-705, Disparon DA-325, Disparon DA-725, Disparon DA-703 50, Disparon DA-234 (both manufactured by Enomoto Kasei Co., Ltd.), and the like.
Examples of the acrylic pigment dispersant include Disperbyk 2000, Disperbyk 2001, Disperbyk 2020, Disperbyk 2050, Disperbyk 2150 (all manufactured by BYK Chemie).
Examples of the polyurethane dispersant include EFKA4010, EFKA4009, EFKA4015, EFKA4047, EFKA4050, EFKA4055, EFKA4060, EFKA4080, EFKA4080, and EFKA4520 (all manufactured by Ciba Specialty Chemicals).

  The addition amount of the pigment dispersant is preferably 1 part by mass or more and 100 parts by mass or less, and more preferably 5 parts by mass to 50 parts by mass with respect to 100 parts by mass of the pigment. When the addition amount is less than 1 part by mass, the pigment may not be sufficiently dispersed and stabilized and may not be stabilized, and when it exceeds 100 parts by mass, the binder resin may be plasticized, The charging characteristics may be deteriorated and the quality may be deteriorated, and the cost may be adversely affected.

As a method of dispersing the pigment in the resin, the binder resin and the dispersing agent are heat-melted using a disperser such as a two-roller, and the pigment is added and kneaded to be dispersed in the binder resin. A master batch may be prepared.
Further, as a method of dispersing the pigment, it is more preferable to disperse the pigment in the solution with a bead mill. In this case, a pigment dispersion in which only the pigment is previously dispersed in the organic solvent may be used, or a dispersion in which the pigment is directly dispersed in the organic solvent together with the binder resin, the dispersant, and the dispersion resin may be used. Even when the pigment is dispersed in advance, the viscosity may be adjusted by adding a part of a binder resin in order to apply an appropriate shearing force when dispersing the pigment.

  The beads used for dispersion are preferably dispersed using high specific gravity and small particle size. For example, dispersion is generally performed using glass or zirconia materials as beads. In this case, it is preferable to use zirconia beads having a high specific gravity in order to obtain sufficient dispersion. Although the bead diameter depends on the performance of the bead mill, it is preferable to use a finer one because it does not cause overdispersion and prevents reaggregation. Further, a master batch in which a binder resin and a dispersant are melted by heat using a disperser such as a two-roller, a pigment is added thereto, kneaded, and dispersed in the binder resin may be used.

The binder resin used in the toner of the present invention is not particularly limited, and known resins can be used, for example, styrenes such as styrene, parachlorostyrene, and α-methylstyrene; methyl acrylate, acrylic Esters having an unsaturated bond such as ethyl acetate, n-propyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate Nitriles having unsaturated bonds such as acrylonitrile and methacrylonitrile; vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone and vinyl isopropenyl ketone; ethylene, pro Ren, polymers or copolymers with monomers such as olefins such as butadiene, or mixtures thereof.
Further, non-vinyl condensation resins such as epoxy resins, polyester resins, polyurethane resins, polyamide resins, cellulose resins, and polyether resins; a mixture of these condensation resins with the vinyl resins, or vinyl in the presence of these polymers. Examples thereof include a graft polymer obtained by polymerizing a monomer. Among these, a polyester resin is particularly preferable in terms of excellent low-temperature fixability and color reproducibility.

As the polyester resin, modified polyester resin (i) or unmodified polyester resin (ii) can be used. These may be used singly, but the modified polyester resin (i) and the unmodified polyester resin (ii) are used for improving low-temperature fixability and gloss when used in a full-color apparatus. It is preferable to use together.
Hereinafter, the modified polyester resin (i) and the unmodified polyester resin (ii) will be described in detail.

In the present invention, the modified polyester resin means a resin in which a functional group contained in an acid or alcohol monomer unit that is a polymerization raw material and a bonding group other than an ester bond are present in the polyester resin. . It also means a resin in which resin components having different structures are bonded to each other by a covalent bond, an ionic bond or the like in the polyester resin. For example, a compound obtained by reacting a polyester terminal or the like with other than the monomer unit forming an ester bond, specifically, reacting a compound having an acid group such as a terminal of a polyester resin or a compound having an isocyanate group that reacts with a hydroxyl group. Or a functional group such as an isocyanate group introduced therein and further reacted with a compound having an active hydrogen group to modify the terminal or undergo an extension reaction. Also included are urea-modified polyesters, urethane-modified polyesters, and the like in which a compound having a plurality of active hydrogen groups and a polyester into which a group capable of reacting with an active hydrogen group such as an isocyanate group is bonded. In addition, a reactive group such as a double bond is introduced into the polyester main chain to cause radical polymerization, and a carbon-carbon bond graft component is introduced into the side chain or the like, and the double bonds are bridged together. The modified polyester resin is also included.
In addition, a resin component having a different structure is copolymerized in the main chain of the polyester, or reacted with a carboxyl group or a hydroxyl group at the terminal, for example, a silicone having a terminal modified with a carboxyl group, a hydroxyl group, an epoxy group, or a mercapto group Those copolymerized with a resin are also included.
Furthermore, examples include silicone-modified polyesters such as those obtained by copolymerizing resin components having different constitutions in the main chain of the polyester or reacting with carboxyl groups or hydroxyl groups present as groups in the polyester resin.
More specifically, a silicone resin modified with a carboxyl group, a hydroxyl group, an epoxy group, or a mercapto group, and a product reacted with a double bond, a carboxyl group, a hydroxyl group, or the like present in the polyester resin (silicone-modified polyester, etc.) Is also included.

  As a more specific example of the above-described modified polyester resin, as a polyester modified with a urea bond (urea-modified polyester) (i), a reaction product of a modified polyester (A) having an isocyanate group and amines (B) Etc. As the modified polyester (A) having an isocyanate group, a polyester (I) having a polycondensate of a polyol (1) and a polycarboxylic acid (2) and having an active hydrogen group is further reacted with a polyisocyanate (3). And the like. Examples of the active hydrogen group possessed by the polyester (I) include hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups, and the like. Among these, alcoholic hydroxyl groups are particularly preferable.

Examples of the polyol (1) include a diol (1-1) and a trihydric or higher polyol (1-2). (1-1) alone or (1-1) and a small amount of (1-2) Mixtures are preferred.
Examples of the diol (1-1) include alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (Diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); Alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); Bisphenols (bisphenol A) Bisphenol F, bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the alicyclic diol; bis Alkylene oxide phenol compound (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts. Among these, alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols are preferable, and the combination of alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms is particularly preferable.

  Examples of the trivalent or higher polyol (1-2) include 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); (Trisphenol PA, phenol novolak, cresol novolac, etc.); alkylene oxide adducts of the above-mentioned trihydric or higher polyphenols.

  Examples of the polycarboxylic acid (2) include dicarboxylic acid (2-1) and trivalent or higher polycarboxylic acid (2-2). (2-1) alone and (2-1) and a small amount of ( The mixture of 2-2) is preferred.

Examples of the dicarboxylic acid (2-1) 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.). Among these, alkenylene dicarboxylic acid having 4 to 20 carbon atoms and aromatic dicarboxylic acid having 8 to 20 carbon atoms are particularly preferable.
Examples of the trivalent or higher polycarboxylic acid (2-2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid). In addition, as polycarboxylic acid (2), you may make it react with polyol (1) using the acid anhydride or lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.) of the above-mentioned thing.

  When obtaining a polycondensate of the polyol (1) and the polycarboxylic acid (2), the ratio of the polyol (1) to the polycarboxylic acid (2) is such that the hydroxyl group [OH] and the carboxyl group [COOH] The equivalent ratio [OH] / [COOH] is preferably 2/1 to 1/1, more preferably 1.5 / 1 to 1/1, and still more preferably 1.3 / 1 to 1.02 / 1.

  Examples of the polyisocyanate (3) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.) Aromatic diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; Those blocked with caprolactam or the like, or a combination of two or more of these may be mentioned.

  The ratio of the polyisocyanate (3) is preferably 5/1 to 1/1 when the equivalent ratio of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group is [NCO] / [OH]. 4/1 to 1.2 / 1 is more preferable, and 2.5 / 1 to 1.5 / 1 is still more preferable. If the [NCO] / [OH] exceeds 5, the low-temperature fixability may be deteriorated. If the molar ratio of [NCO] is less than 1, the urea content in the modified polyester is lowered, and the hot offset resistance is reduced. May get worse.

The content of the polyisocyanate (3) component in the modified polyester (A) having an isocyanate group at the terminal is preferably 0.5% by mass to 40% by mass, more preferably 1% by mass to 30% by mass, and 2% by mass. % To 20% by mass is more preferable. When the content is less than 0.5% by mass, the hot offset resistance deteriorates and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. When the content exceeds 40% by mass, low-temperature fixability is obtained. May get worse.
The number of isocyanate groups contained per molecule in the modified polyester (A) having an isocyanate group at the end is preferably 1 or more, more preferably 1.5 to 3 on average, and 1.8 to 2.5 on average. Further preferred. When the number of the isocyanate groups is less than 1 per molecule, the molecular weight of the urea-modified polyester is lowered, and the hot offset resistance may be deteriorated.

  Examples of the amines (B) include diamine (B1), trivalent or higher polyamine (B2), amino alcohol (B3), amino mercaptan (B4), amino acid (B5), and amino groups blocked from B1 to B5. (B6) etc. are mentioned.

Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diamines). Cyclohexane, isophoronediamine, etc.); and aliphatic diamines (ethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.) and the like.
Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine.
Examples of the amino alcohol (B3) include ethanolamine and hydroxyethylaniline.
Examples of the amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.
In addition, as the thing (B6) which blocked the amino group of B1-B5, the ketimine compound and oxazolidine compound which are obtained from amines and ketones (Acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) of said (B1)-(B5) Etc. 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 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 the amines (B) is the equivalent ratio [NCO] / [NHx] of the isocyanate group [NCO] in the modified polyester (A) having an isocyanate group and the amino group [NHx] in the amine (B). 1/2 to 2/1 is preferable, 1.5 / 1 to 1 / 1.5 is more preferable, and 1.2 / 1 to 1 / 1.2 is still more preferable. When the [NCO] / [NHx] exceeds 2 or less than 1/2, the molecular weight of the urea-modified polyester (i) is decreased, and the hot offset resistance may be deteriorated.

  In the present invention, the modified polyester resin (i) may contain a urethane bond together with a urea bond. The molar ratio between the urea bond content and the urethane bond content is preferably 100/0 to 10/90, more preferably 80/20 to 20/80, and still more preferably 60/40 to 30/70. When the molar ratio of the urea bond is less than 10%, the hot offset resistance may be deteriorated.

  The modified polyester resin (i) is produced by a one-shot method or a prepolymer method. The modified polyester resin (i) has a mass average molecular weight of preferably 10,000 or more, more preferably 20,000 to 10,000,000, and still more preferably 30,000 to 1,000,000. When the mass average molecular weight is less than 10,000, the hot offset resistance may be deteriorated. Further, the number average molecular weight of the modified polyester resin (i) is not particularly limited when the unmodified polyester resin (ii) described later is used, and the number average that is easily obtained to obtain the mass average molecular weight. Molecular weight is sufficient. (I) When used alone, the number average molecular weight is preferably 20,000 or less, more preferably 1,000 to 10,000, and still more preferably 2,000 to 8,000. When the number average molecular weight exceeds 20,000, low temperature fixability and gloss when used in a full color apparatus may be deteriorated.

  In the present invention, not only the modified polyester resin (i) is used alone, but also the unmodified polyester resin (ii) is contained as a toner binder component (binder resin component) together with the (i). You can also. Use of the unmodified polyester resin (ii) in combination improves low-temperature fixability and gloss when used in a full-color device, and is more preferable than single use. Examples of the unmodified polyester resin (ii) include the same polycondensates of polyol (1) and polycarboxylic acid (2) as the polyester component of the modified polyester resin (i). Those are the same as those of the modified polyester resin (i). The unmodified polyester resin (ii) is not limited to unmodified polyester, and may be modified with, for example, a urea bond or a urethane bond. It is preferable that (i) and (ii) are at least partially compatible with each other in terms of low-temperature fixability and hot offset resistance. Accordingly, the polyester component (i) and (ii) preferably have similar compositions.

  When the unmodified polyester resin (ii) is contained, the mass ratio of (i) to (ii) is preferably 5/95 to 30/70, more preferably 5/95 to 25/75, and 7/93. ~ 20/80 is more preferred. When the mass ratio of (i) is less than 5%, hot offset resistance is deteriorated, and it may be disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.

-Release agent-
The magenta toner of the present invention may contain a release agent together with the binder resin and the pigment.
The release agent is not particularly limited, and known ones can be used, such as polyolefin wax (polyethylene wax, polypropylene wax, etc.); long chain hydrocarbon (paraffin wax, sazol wax, etc.); carbonyl group-containing wax, etc. Is mentioned. Of these, carbonyl group-containing waxes are preferred. Carbonyl group-containing waxes include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1, 18-octadecanediol distearate etc.); polyalkanol esters (tristearyl trimellitic acid, distearyl maleate etc.); polyalkanoic acid amides (ethylenediamine dibehenyl amide etc.); polyalkylamides (trimellitic acid tristearyl amide etc.) ); And dialkyl ketones (such as distearyl ketone). Of these carbonyl group-containing waxes, polyalkanoic acid esters are particularly preferred.

The melting point of the wax is preferably 40 ° C to 160 ° C, more preferably 50 ° C to 120 ° C, and still more preferably 60 ° C to 90 ° C. If the melting point is less than 40 ° C., the wax may adversely affect the heat resistant storage stability. If the melting point exceeds 160 ° C., a cold offset tends to occur during fixing at a low temperature. The melt viscosity of the wax is preferably 5 cps to 1,000 cps, more preferably 10 cps to 100 cps, as a measured value at a temperature 20 ° C. higher than the melting point. The wax having a melt viscosity exceeding 1,000 cps is poor in improving hot offset resistance and low temperature fixability.
The content of the wax in the toner is preferably 0% by mass to 40% by mass, and more preferably 3% by mass to 30% by mass.

  The magenta toner of the present invention may contain a charge control agent as necessary. The charge control agent is not particularly limited and known ones can be used. For example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, Quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, salicylic acid metal salts and metal salts of salicylic acid derivatives. Specifically, Bontron 03 of nigrosine dye, Bontron P-51 of quaternary ammonium salt, Bontron S-34 of metal-containing azo dye, E-82 of oxynaphthoic acid metal complex, E of salicylic acid metal complex -84, phenolic condensate E-89 (both manufactured by Orient Chemical Co., Ltd.); quaternary ammonium salt molybdenum complex TP-302, TP-415 (both manufactured by Hodogaya Chemical Co., Ltd.) Quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 (all from Hoechst); LRA-901, boron Complex LR-147 (Nippon Carlit Co., Ltd.); Nin, perylene, quinacridone, azo pigments, sulfonate group, a carboxyl group, and the like and polymeric compounds having a functional group such as a quaternary ammonium salt.

The content of the charge control agent is determined by the toner production method including the type of the binder resin, the presence or absence of additives used as necessary, and the dispersion method. Although it is not, 0.1 mass-10 mass parts are preferable with respect to 100 mass parts of said binder resin, and 0.2 mass part-5 mass parts are more preferable. When the content exceeds 10 parts by mass, the chargeability of the toner is too large, the effect of the main charge control agent is reduced, the electrostatic attractive force with the developing roller is increased, and the flowability of the developer is reduced. The image density may be lowered.
In addition, these charge control agents and mold release agents can be melt-kneaded with the master batch and the resin, and may be added when dissolved and dispersed in the organic solvent.

-External additive-
An external additive can be used to assist the fluidity, developability and chargeability of the toner. There is no restriction | limiting in particular as an external additive, According to the objective, it can select suitably from well-known things, For example, an inorganic fine particle can be used conveniently.
The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and more preferably 5 nm to 500 nm. In addition, the specific surface area by BET method is ^{20m 2} / ^g~500m 2 / g are preferred.
The addition amount of the inorganic fine particles is preferably 0.01% by mass to 5% by mass, and more preferably 0.01% by mass to 2.0% by mass with respect to the toner.

The inorganic fine particles are not particularly limited and can be appropriately selected depending on the purpose. For example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, Tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride, Etc.
Resin fine particles can also be added as the external additive. For example, polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, or dispersion polymerization; copolymer of methacrylic acid ester, acrylic acid ester; polycondensation system such as silicone, benzoguanamine, nylon; polymer particles made of thermosetting resin It is done.

-Other ingredients-
Other components can be used in the toner of the present invention. There is no restriction | limiting in particular as another component, According to the objective, it can select suitably, For example, a fluidity improver, a cleaning property improver, a magnetic material, metal soap, etc. are mentioned.

  The fluidity improver can be surface-treated to increase hydrophobicity and prevent deterioration of fluidity and charging characteristics even under high humidity. For example, a silane coupling agent, a silylating agent, and a fluoride can be used. Silane coupling agents having an alkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils, and the like.

  The cleaning property improver is added to the toner in order to remove the developer after transfer remaining on the electrostatic latent image carrier or the intermediate transfer member. For example, fatty acid such as zinc stearate, calcium stearate, stearic acid, etc. Metal salts; polymer fine particles produced by soap-free emulsion polymerization such as polymethyl methacrylate fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and those having a volume average particle size of 0.01 μm to 1 μm are suitable.

  There is no restriction | limiting in particular as said magnetic material, According to the objective, it can select suitably from well-known things, For example, iron powder, a magnetite, a ferrite etc. are mentioned. Among these, white is preferable in terms of color tone.

-Manufacturing method of magenta toner-
The method for producing the magenta toner of the present invention is not particularly limited, and can be appropriately selected from conventionally known toner production methods according to the purpose. Examples thereof include a kneading / pulverizing method, a polymerization method, a dissolution suspension method, and a spray granulation method. Among these, the polymerization method is particularly preferable. As such a polymerization method, a toner material containing at least a compound having an active hydrogen group, a polymer having a site capable of reacting with the compound having an active hydrogen group, a pigment and a pigment dispersant in an organic solvent is dissolved or dispersed. A method of reacting the dissolved or dispersed material in an aqueous medium and removing the organic solvent from the obtained emulsified dispersion is preferred.

When urea-modified polyester is used as the toner material used when the magenta toner of the present invention is manufactured, the toner binder can be manufactured by the following method.
First, the polyol (1) and the polycarboxylic acid (2) are heated to 150 ° C. to 280 ° C. in the presence of an esterification catalyst such as tetrabutoxy titanate or dibutyltin oxide, and water generated while reducing the pressure as necessary is stored. To obtain a polyester having a hydroxyl group. Next, this is reacted with polyisocyanate (3) at 40 to 140 ° C. to obtain a modified polyester (A) having an isocyanate group. Further, the modified polyester (A) having an isocyanate group is reacted with the amines (B) at 0 ° C. to 140 ° C. to obtain a polyester modified with a urea bond (urea modified polyester). When reacting the polyisocyanate (3) and reacting the modified polyester (A) having the isocyanate group and the amines (B), a solvent may be used as necessary.

  Usable solvents include aromatic solvents (toluene, xylene, etc.); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.); esters (ethyl acetate, etc.); amides (dimethylformamide, dimethylacetamide, etc.) and ethers And those inert to the isocyanate (3), such as tetrahydrofuran (such as tetrahydrofuran).

  When polyester (ii) not modified with urea bond is used in combination, (ii) is produced in the same manner as polyester having a hydroxyl group, and this is dissolved in the solution after completion of the reaction of (i) and mixed. To do. The dry toner can be produced by the following method, but is not limited thereto.

  The aqueous medium used in the present invention may be water alone, or a solvent miscible with water may be used in combination. Examples of the solvent miscible with water include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.) and the like.

  The toner particles may be formed by reacting a dispersion composed of the modified polyester (A) having an isocyanate group having a substituent capable of reacting in an aqueous medium with the amines (B). Modified polyester (i) may be used. As a method for stably forming a dispersion comprising a modified polyester (i) or a modified polyester (A) having an isocyanate group having a reactive substituent in an aqueous medium, the modified polyester (i) or Examples thereof include a method of adding a toner material composition comprising a modified polyester (A) having a reactive substituent and dispersing the composition by shearing force. Modified polyester (A) having a reactive substituent and other toner compositions (sometimes referred to as toner materials), pigments, pigment master batches, release agents, charge control agents, unmodified polyester resins, etc. Mixing may be performed when the dispersion is formed in the aqueous medium, but it is more preferable to mix the toner material in advance and then add and disperse the mixture in the aqueous medium.

The dispersion method is not particularly limited, and known equipment such as a low-speed shear type, a high-speed shear type, a friction type, a high-pressure jet type, and an ultrasonic wave can be applied. In order to make the particle size of the dispersion 2 μm to 20 μm, a high-speed shearing method is preferable. When a high-speed shearing disperser is used, the number of rotations is not particularly limited, but is preferably 1,000 to 30,000 rpm, and more preferably 5,000 to 20,000 rpm.
Although there is no limitation in particular as said dispersion | distribution time, in the case of a batch system, 0.1 minute-5 minutes are preferable normally. As the temperature during dispersion, a higher temperature is preferable in that the dispersion of the modified polyester (i) or the modified polyester (A) having a reactive substituent has a low viscosity and is easily dispersed.

  The amount of the aqueous medium used relative to 100 parts by mass of the toner composition containing the modified polyester resin (i) and the modified polyester resin (A) having a reactive substituent is preferably 50 parts by mass to 2,000 parts by mass. Mass parts to 1,000 parts by mass are more preferable. When the amount used is less than 50 parts by mass, the dispersion state of the toner composition is poor, and toner particles having a predetermined particle size may not be obtained. When the amount exceeds 2,000 parts by mass, it is not economical.

If necessary, a dispersant (emulsified dispersant or surfactant) for emulsifying and dispersing the oily phase in which the toner material is dispersed in a liquid (aqueous phase) containing water can also be used. Use of such a dispersant is preferable because the particle size distribution becomes sharp and the dispersion becomes stable.
Examples of the dispersant (emulsifying dispersant or surfactant) include anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives. Cation surfactants of amine salts such as imidazoline, and quaternary ammonium salts such as alkyltrimethylammonium, dialkyldimethylammonium, alkyldimethylbenzylammonium, pyridinium, alkylisoquinolinium and benzethonium chloride , Nonionic surfactants such as fatty acid amide derivatives and polyhydric alcohol derivatives such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium beta Amphoteric surfactants such as emissions and the like.

  Further, by using a surfactant having a fluoroalkyl group, the effect can be increased in a very small amount. Examples of the anionic surfactant having a fluoroalkyl group include a fluoroalkyl carboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, disodium perfluorooctanesulfonyl glutamate, 3- [omega-fluoroalkyl (6 to 11 carbon atoms). ) Oxy] -1-alkyl (3 to 4 carbon atoms) sodium sulfonate, 3- [omega-fluoroalkanoyl (6 to 8 carbon atoms) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (carbon 11-20) Carboxylic acid or metal salt thereof, perfluoroalkyl carboxylic acid (carbon number 7-13) or metal salt thereof, perfluoroalkyl (carbon number 4-12) sulfonic acid or metal salt thereof, perfluorooctane sulfone Acid diethanolamide, N-propyl-N- (2hydroxyethyl Perfluorooctanesulfonamide, perfluoroalkyl (carbon number 6-10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (carbon number 6-10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (carbon number 6-6) 16) Ethyl phosphate ester and the like.

  Commercially available products include, for example, Surflon S-111, S-112, S-113 (all manufactured by Asahi Glass Co., Ltd.); Fluorard FC-93, FC-95, FC-98, FC-129 (all Sumitomo 3M shares) Unidyne DS-101, DS-102 (both manufactured by Daikin Industries, Ltd.); MegaFuck F-110, F-120, F-113, F-191, F-812, F-833 ( All are manufactured by Dainippon Ink & Chemicals, Inc.); Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (all manufactured by Tochem Products Co., Ltd.) And [Fantent F-100, F150 (both manufactured by Neos)], and the like.

In addition, as the cationic surfactant, aliphatic quaternary ammonium salts such as aliphatic primary, secondary or secondary amine acids having a fluoroalkyl group, and perfluoroalkyl (carbon number 6 to 10) sulfonamidopropyltrimethylammonium salt. Benzalkonium salt, benzethonium chloride salt, pyridinium salt, imidazolinium salt and the like.
Commercially available products include, for example, Surflon S-121 (manufactured by Asahi Glass Co., Ltd.), Florard FC-135 (manufactured by Sumitomo 3M Co., Ltd.), Unidyne DS-202 (manufactured by Daikin Industries, Ltd.); Megafuck F-150, F-824 ( All include Dainippon Ink and Chemicals, Inc.); Xtop EF-132 (manufactured by Tochem Products Co., Ltd.), and Footgent F-300 (manufactured by Neos).

Examples of the inorganic compound dispersant (emulsifying dispersant or surfactant) that is hardly soluble in water include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.
Further, the dispersed droplets may be stabilized by a polymer protective colloid. Examples of the polymeric protective colloid include acids such as acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride; Containing (meth) acrylic monomer (for example, β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, methacryl Γ-hydroxypropyl acid, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate Tacric acid ester, N-methylol acrylamide, N-methylol methacrylamide, etc.); Vinyl alcohol or ethers with vinyl alcohol (for example, vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, etc.); Contains vinyl alcohol and carboxyl group Esters of compounds (eg, pinyl acetate, vinyl propionate, vinyl butyrate, etc.); acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds; acid chlorides such as acrylic acid chloride, methacrylic acid chloride; pinylviridine, vinyl Homopolymers or copolymers such as those having a nitrogen atom such as pyrrolidone, vinylimidazole, ethyleneimine or the heterocyclic ring thereof; polyoxyethylene, polyoxypropylene, Reoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonyl Examples thereof include polyoxyethylenes such as phenyl esters; celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.

  In addition, when an acid such as calcium phosphate salt or a substance soluble in alkali is used as the dispersion stabilizer, the calcium phosphate salt is dissolved from the fine particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and washing with water. Remove. In addition, it can be removed by an operation such as enzymatic degradation. When a dispersant is used, the dispersant can remain on the surface of the toner particles. However, it is preferable from the charged surface of the toner that the dispersant is washed and removed after the elongation and / or crosslinking reaction.

Further, in order to lower the viscosity of the toner material, a solvent in which the modified polyester resin (i) and the modified polyester resin (A) having a reactive substituent can be used may be used. The use of a solvent is preferable in that the particle size distribution becomes sharp. This solvent is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal.
Examples of the solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, Examples thereof include methyl ethyl ketone and methyl isobutyl ketone. Among these, aromatic solvents such as toluene and xylene, and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride are particularly preferable. These may be used individually by 1 type and may use 2 or more types together.
300 mass parts or less are preferable, as for the usage-amount of the solvent with respect to 100 mass parts of said modified polyester (A) which has a reactive substituent, 100 mass parts or less are more preferable, and 25 mass parts-70 mass parts are still more preferable. When a solvent is used, the solvent is removed by heating under normal pressure or reduced pressure after the elongation and / or crosslinking reaction.

  In the case of a urea-modified polyester, the elongation and / or crosslinking reaction time is selected depending on the reactivity of the isocyanate group structure of the modified polyester (A) having a reactive substituent and the amines (B). Minute to 40 hours are preferable, and 2 hours to 24 hours are more preferable. The reaction temperature is preferably 0 ° C to 150 ° C, more preferably 40 ° C to 98 ° C. Moreover, a well-known catalyst can be used as needed, Specifically, a dibutyltin laurate, a dioctyltin laurate, etc. are mentioned.

  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. It is also possible to spray the emulsified dispersion in a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner fine particles, and to evaporate and remove the aqueous dispersant 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. A spray dryer, belt dryer, rotary kiln, etc. can sufficiently achieve the desired quality in a short time.

  When the particle size distribution at the time of emulsification dispersion is wide and washing and drying processes are performed while maintaining the particle size distribution, the particle size distribution can be adjusted by classifying into a desired particle size distribution. In the classification operation, the fine particle portion can be removed in the liquid by a cyclone, a decanter, centrifugation, or the like. Although classification operation may be performed after obtaining as powder after drying, it is preferable in terms of efficiency to be performed in a liquid. The obtained unnecessary fine particles or coarse particles can be returned to the kneading step and used for forming 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.

  The obtained toner powder after drying is mixed with different particles such as release agent fine particles, charge control fine particles, fluidizing agent fine particles, and colorant fine particles, or mechanical impact force is applied to the mixed powder. By applying, it is possible to immobilize and fuse on the surface, and to prevent dissociation of the different 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 into 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.) was remodeled to reduce pulverization air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), Kryptron System (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar and the like.
According to such a production method, it is possible to obtain a toner that is excellent in powder flowability and transferability, and that provides a high-quality image with a small particle diameter. Furthermore, it is excellent in low-temperature fixability and hot offset resistance, and does not cause filming or spent. As described above, since the toner satisfying various required characteristics, including the pulverized toner, has not been obtained conventionally, it is preferably used for producing the magenta toner of the present invention.

-Physical properties of toner-
The volume average particle size (Dv) of the magenta toner of the present invention is preferably 2.5 μm to 5.5 μm. When the adhesion amount is 0.3 mg / cm ² , if the volume average particle size exceeds 5.5 μm, it becomes difficult to obtain a high-quality image, and if it is less than 2.5 μm, In addition, the cleaning property is deteriorated, filming, spent on the carrier, etc. are likely to occur.

  The ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) of the toner is preferably 1.0 to 1.2. With such a toner, it is excellent in all of heat-resistant storage stability, low-temperature fixability, and hot offset resistance, particularly excellent in image glossiness when used in a full-color copying machine, etc. Even if the toner balance is extended over a wide range, fluctuations in the toner particle size in the developer are reduced, and good and stable developability can be obtained even with long-term stirring in the developing device. Further, even when the balance of toner is used when used as a one-component developer, the fluctuation of the toner particle size is reduced, the toner filming on the developing roller, a blade for thinning the toner, etc. The toner is not fused to the member, and good and stable developability and images can be obtained even when the developing device is used (stirred) for a long time.

  The volume average particle diameter and the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) are measured using a particle size measuring device (“Multisizer III”, manufactured by Beckman Coulter, Inc.). Then, measurement was performed with an aperture diameter of 100 μm, and analysis was performed with analysis software (Beckman Coulter Multisizer 3 Version 3.51). Specifically, 0.5 ml of 10% by weight surfactant (alkylbenzene sulfonate, Neogen SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is added to a 100 ml beaker made of glass, and 0.5 g of each toner is added. Stir with a spatula and then add 80 ml of ion-exchanged water. The obtained dispersion is subjected to a dispersion treatment for 10 minutes with an ultrasonic disperser (W-113MK-II, manufactured by Honda Electronics Co., Ltd.). The dispersion is measured using the Multisizer III and Isoton III (manufactured by Beckman Coulter, Inc.) 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 peak molecular weight of the magenta toner is preferably 1,000 to 30,000, more preferably 1,500 to 10,000, and still more preferably 2,000 to 8,000. When the peak molecular weight is less than 1,000, the heat resistant storage stability may be deteriorated, and when it exceeds 30,000, the low temperature fixability may be deteriorated.
Here, the peak molecular weight of the toner in the present invention is specifically determined by the following procedure.

-Measurement of peak molecular weight of toner-
Gel permeation chromatography (GPC) measuring device: GPC-8220 GPC (manufactured by Tosoh Corporation) Column: TSKgel SuperHZM-H 15 cm triple (manufactured by Tosoh Corporation)
・ Temperature: 40 ℃
・ Solvent: THF
・ Flow rate: 0.35 ml / min
-Sample: 0.4 ml of 0.15% sample was injected-Sample pretreatment: Toner was dissolved in tetrahydrofuran THF (containing stabilizer, manufactured by Wako Pure Chemical Industries, Ltd.) at 0.15% by mass, and then 0.2 μm filter was used. Filter and use the filtrate as a sample. 100 μl of the THF sample solution is injected and measured.

  In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, Showd STANDARD Std. No. S-7300, S-210, S-390, S-875, S-1980, S-10.9, S-629, S-3.0, S-0.580, and toluene were used. An RI (refractive index) detector was used as the detector.

The hydroxyl value of the magenta toner is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g to 120 mgKOH / g, and still more preferably 20 mgKOH / g to 80 mgKOH / g. If the hydroxyl value is less than 5 mgKOH / g, it may be disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.
The acid value of the magenta toner is preferably 1 mgKOH / g to 40 mgKOH / g, more preferably 5 mgKOH / g to 30 mgKOH / g, and still more preferably 15 mgKOH / g to 28 mgKOH / g. By giving an acid value, it tends to be negatively charged, and the affinity with paper at the time of fixing is increased, and the fixing power is increased.

Here, the acid value (AV) and the hydroxyl value (OHV) in the toner are specifically determined by the following procedure.
・ Measuring device: potentiometric automatic titrator DL-53 Titrator (Metler Toledo)
-Electrode used: DG113-SC (manufactured by METTLER TOLEDO)
・ Analysis software: LabX Light Version1.00.000
-Calibration of apparatus: Use a mixed solvent of 120 ml of toluene and 30 ml of ethanol.
・ Measurement temperature: 23 ℃
The measurement conditions are as follows.
Stir
Speed [%] 25
Time [s] 15
EQP titration
Titrant / Sensor
Titrant CH ₃ ONa
Concentration [mol / L] 0.1
Sensor DG115
Unit of measurement mV
Predispensing to volume
Volume [mL] 1.0
Wait time [s] 0
Titrant addition Dynamic
dE (set) [mV] 8.0
dV (min) [mL] 0.03
dV (max) [mL] 0.5
Measure mode Equilibrium controlled
dE [mV] 0.5
dt [s] 1.0
t (min) [s] 2.0
t (max) [s] 20.0
Recognition
Threshold 100.0
Steepest jump only No
Range No
Tendency None
Termination
At maximum volume [mL] 10.0
At potential No
At slope No
After number EQPs Yes
n = 1
comb. Termination conditions No
Evaluation
Procedure Standard
Potential 1 No
Potential 2 No
Stop for reevaluation No

-Method of measuring acid value-
The acid value (AV) can be measured under the following conditions based on the measurement method described in JIS K0070-1992.
Sample preparation: 0.5 g of toner (0.3 g for ethyl acetate-soluble component) is added to 120 ml of toluene and dissolved by stirring for about 10 hours at room temperature (23 ° C.). Furthermore, 30 ml of ethanol is added to prepare a sample solution.
The measurement can be calculated and performed after using the above-described apparatus. Specifically, the measurement is performed as follows.
Titrate with a pre-standardized (N / 10) caustic potash to alcohol solution, and determine the acid value from the consumption of the alcohol potash solution by the following calculation.
Acid value = KOH (ml) x N x 56.1 / sample weight (where N is a factor of (N / 10) -KOH)

-Measurement method of hydroxyl value-
The hydroxyl value (OHV) can be measured under the following conditions based on the measurement method described in JIS K0070-1966.
Weigh accurately 0.5 g of sample into a 100 ml volumetric flask and add 5 ml of acetylating reagent correctly. Then, it is immersed in a bath at 100 ° C. ± 5 ° C. and heated. After 1-2 hours, the flask is removed from the bath, allowed to cool, water is added and shaken to decompose acetic anhydride. Next, in order to complete the decomposition, the flask is again heated in a bath for 10 minutes or more and allowed to cool, and then the wall of the flask is thoroughly washed with an organic solvent. This solution is subjected to potentiometric titration with (N / 2) -potassium hydroxide ethyl alcohol solution using the electrode to determine the hydroxyl value.

The glass transition temperature of the magenta toner of the present invention is preferably 40 ° C to 70 ° C. If the glass transition temperature is less than 40 ° C, the heat-resistant storage stability may be insufficient, and if it exceeds 70 ° C, the low-temperature fixability may be adversely affected.
Here, the glass transition temperature (Tg) is specifically determined by the following procedure. The measurement was performed under the following measurement conditions using TA-60WS and DSC-60 manufactured by Shimadzu Corporation.

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

  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 on the lowest temperature side of the DrDSC curve which is the DSC differential curve of the second temperature rise, and the peak temperature is determined using the peak analysis function of the analysis software. 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 glass transition temperature (Tg) of the toner.

-Developer-
The magenta toner of the present invention may be used as a one-component developer composed only of magenta toner, or may be used as a two-component developer together with a carrier.
When used as the two-component developer, the toner is used by mixing with a magnetic carrier. The content ratio of the carrier and the toner in the developer is preferably 1 to 10 parts by mass of the toner with respect to 100 parts by mass of the carrier.

Examples of the magnetic carrier include iron powder, ferrite powder, magnetite powder having a particle size of about 20 μm to 200 μm, and a coated carrier obtained by coating the surface of the magnetic carrier with a resin. Among these, a coated carrier is particularly preferable.
Examples of the coating resin in the coated carrier include urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, epoxy resin, polyvinyl resin, polyvinylidene resin, acrylic resin, polymethyl methacrylate resin, polyacrylonitrile. Resin, polyvinyl acetate resin, polyvinyl alcohol resin, polyvinyl butyral resin, polystyrene resin, styrene-acrylic copolymer resin, polyvinyl chloride resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride Resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, Copolymers of vinylidene fluoride and vinyl fluoride, fluoro terpolymers such as of tetrafluoroethylene and vinylidene fluoride and non-fluoride monomers including, and a silicone resin.

  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. The conductive powder preferably has an average particle size of 1 μm or less. When the average particle size is larger than 1 μm, it becomes difficult to control the electric resistance.

The magenta toner of the present invention has excellent spectral reflection characteristics for color reproduction, high saturation and high reflection density characteristics, a clear magenta color, good dispersibility for the binder resin, high coloration, and transparency. Good properties. Therefore, it can be suitably used in various fields, and can be more suitably used for image formation by electrophotography, such as a container containing a toner, a developer, a process cartridge, an image forming apparatus, and an image forming method. It can be particularly preferably used. It is preferable to use the magenta toner of the present invention, and these can be easily performed by using a known toner container, developer, process cartridge, image forming apparatus, image forming method, and the like. These inventions are also included in the present invention.
The toner container is not limited to a conventional bottle type or cartridge type.
The image forming apparatus may be an apparatus for forming an image by electrophotography, and includes, for example, a copying machine and a printer.

  An embodiment of an image forming method using the magenta toner of the present invention will be described with reference to FIG. The tandem image forming apparatus shown in FIG. 1 is a tandem type color image forming apparatus. The tandem image forming apparatus includes a copying machine main body (150), a paper feed table (200), a scanner (300), and an automatic document feeder (ADF) (400).

  The copying apparatus main body (150) is provided with an endless belt-shaped intermediate transfer body (1050) at the center. The intermediate transfer member (1050) is stretched around support rollers (1014), (1015), and (1016), and can rotate clockwise in FIG. An intermediate transfer member cleaning device (1017) for removing residual toner on the intermediate transfer member (1050) is disposed in the vicinity of the support roller (1015). The intermediate transfer member (1050) stretched between the support roller (1014) and the support roller (1015) has at least a plurality of magenta (for example, four) image forming units (1018) along the conveyance direction. A tandem developing device (120) arranged opposite to each other is arranged. An exposure device (1021) is disposed in the vicinity of the tandem developing device (120). A secondary transfer device (1022) is disposed on the side of the intermediate transfer member (1050) opposite to the side on which the tandem developing device (120) is disposed. In the secondary transfer device (1022), a secondary transfer belt (1024), which is an endless belt, is stretched between a pair of rollers (1023), and a transfer sheet conveyed on the secondary transfer belt (1024) and The intermediate transfer member (1050) can contact each other. A fixing device (1025) is disposed in the vicinity of the secondary transfer device (1022). The fixing device (1025) includes a fixing belt (1026) that is an endless belt, and a pressure roller (1027) that is pressed against the fixing belt (1027).

  In the tandem image forming apparatus, in the vicinity of the secondary transfer device (1022) and the fixing device (1025), a sheet reversing device (1028) for reversing the transfer paper for image formation on both sides of the transfer paper. ) Is arranged.

  Next, formation of a color image (color copy) using at least magenta 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 (1032) 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 and a document is set on the automatic document feeder (400), the document is transported and moved onto the contact glass (1032). ) Immediately after setting the original on the scanner (300), the first traveling body (1033) and the second traveling body (1034) travel. At this time, light from the light source is irradiated by the first traveling body (1033) and reflected light from the document surface is reflected by the mirror in the second traveling body (1034), and is read through the imaging lens (1035). A color original (color image) is read at (1036) and read, and used as image information for forming magenta and other full-color images.

  The image information for each color of magenta and other colors is transmitted to each image forming unit (1018) (having at least a magenta image forming unit) in the tandem developing unit (120), and in each image forming unit, Each toner image such as magenta is formed. That is, each image forming unit (1018) (having at least a magenta image forming unit) in the tandem developing unit (120) has an electrostatic latent image carrier (1010) (for magenta) as shown in FIG. An electrostatic latent image carrier (1010M), a charging device (160) for uniformly charging the electrostatic latent image carrier (1010), and an image corresponding to each color image based on each color image information And exposing the electrostatic latent image carrier (L in FIG. 2) to form an electrostatic latent image corresponding to each color image on the electrostatic latent image carrier; A developing device (61) for developing an image with each color toner (including at least magenta toner) to form a toner image with each color toner, and for transferring the toner image onto the intermediate transfer body (1050) Transfer charger And 1062), a cleaning device (63), and a discharger (64), can form a single color image (such as magenta image) based on each color image information. The magenta image and the like thus formed are at least a magenta electrostatic latent image carrier (1010M) on an intermediate transfer member (1050) that is rotated by support rollers (1014), (1015), and (1016). ) The magenta image formed above is sequentially transferred (primary transfer). Then, the magenta image and other color images are superimposed on the intermediate transfer body (1050) 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 (1049). Alternatively, the sheet feed roller (142) is rotated to feed out the sheets (recording paper) on the manual feed tray (1054), separated one by one by the separation roller (1058), and put into the manual feed path (1053). It stops against the registration roller (1049). The registration roller (1049) 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 (1049) is rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member (1050), and the intermediate transfer member (1050), the secondary transfer device (1022), and the like. The sheet (recording paper) is sent 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 (1022). A color image is transferred and formed on (recording paper). The residual toner on the intermediate transfer member (1050) after image transfer is cleaned by the intermediate transfer member cleaning device (1017).

  The sheet (recording paper) on which a color image including a magenta image is transferred is transported by a secondary transfer device (1022) and sent to a fixing device (1025). In the fixing device (1025), 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 (1055) and discharged by the discharge roller (1056) and stacked on the paper discharge tray (1057) or switched by the switching claw (1055). After being reversed by the apparatus (1028) and guided again to the transfer position, an image is recorded also on the back surface, then discharged by the discharge roller (1056), and stacked on the discharge tray (1057).

[Process cartridge]
The developer using the magenta toner of the present invention can be used in, for example, an image forming apparatus provided with a process cartridge as shown in FIG.
In the present invention, a plurality of components selected from the components such as the photosensitive member 1, the charging unit 2, the developing unit 4, and the cleaning unit 7 are integrally combined as a process cartridge, and the process cartridge is copied. It is configured to be detachable from an image forming apparatus main body such as a printer or a printer.

  The magenta process cartridge shown in FIG. 3 includes a photoconductor, a charging unit, a developing unit, and a cleaning unit. Explaining the operation, the photosensitive member is rotationally driven at a predetermined peripheral speed. In the rotation process, the photosensitive member is uniformly charged with a positive or negative predetermined potential on its peripheral surface by the charging unit, and then receives image exposure light from an image exposing unit such as slit exposure or laser beam scanning exposure. An electrostatic latent image is sequentially formed on the peripheral surface of the body, and the formed electrostatic latent image is then developed with toner by a developing unit, and the developed toner image is transferred between the photosensitive member and the transfer unit from the paper feeding unit. Then, the image is sequentially transferred to the transfer material fed in synchronization with the rotation of the photosensitive member by the transfer means. The transfer material that has received the image transfer is separated from the surface of the photosensitive member, introduced into the image fixing means, and fixed on the image, and printed out as a copy (copy) or print (print). The surface of the photoconductor after the image transfer is cleaned by removing toner remaining after transfer by a cleaning unit, and after further static elimination, it is repeatedly used for image formation.

  Hereinafter, the magenta toner of the present invention will be described more specifically with reference to examples. However, the present invention is not construed as being limited to these descriptions.

[Example 1]
(Preparation of Toner 1)
-Preparation of fine particle dispersion 1-
In a reaction vessel in which a stir bar and a thermometer are set, 683 parts by mass of water, 11 parts by mass of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries Ltd.), 83 parts by mass of styrene Part, 83 parts by weight of methacrylic acid, 110 parts by weight of butyl acrylate, and 1 part by weight of ammonium persulfate were added and stirred at 400 rpm for 15 minutes to obtain a white emulsion. The system was heated to raise the temperature in the system to 75 ° C. and reacted for 5 hours. Further, 30 parts by mass of a 1% by mass aqueous ammonium persulfate solution was added, and the mixture was aged at 75 ° C. for 5 hours to be a vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). ) Aqueous dispersion [fine particle dispersion 1].
The obtained [Fine Particle Dispersion 1] was measured with a particle size distribution analyzer (LA-920, manufactured by Horiba, Ltd.), and the volume average particle size was 105 nm. Further, a portion of the obtained [fine particle dispersion 1] was dried to isolate the resin component. The glass transition temperature (Tg) of the resin was 59 ° C., and the mass average molecular weight was 150,000.

-Synthesis of polyester resin (1)-
229 parts by mass of bisphenol A ethylene oxide 2-mole adduct, 529 parts by mass of bisphenol A propylene oxide 3-mole adduct, 208 parts by mass of terephthalic acid, adipic acid 46 parts by mass and 2 parts by mass of dibutyltin oxide were added and reacted at 230 ° C. for 8 hours under normal pressure. Next, after reacting for 5 hours under a reduced pressure of 10 mmHg to 15 mmHg, 30 parts by weight of trimellitic anhydride was put into the reaction vessel and reacted at 180 ° C. for 2 hours under normal pressure to obtain a polyester resin (1). Was synthesized.
The obtained polyester resin (1) had a mass average molecular weight of 6,700, a glass transition temperature (Tg) of 43 ° C., and an acid value of 20 mgKOH / g.

-Preparation of aqueous phase-
990 parts by mass of water, 183 parts by mass of the fine particle dispersion, 37 parts by mass of an aqueous solution of 48.5% by mass of sodium dodecyl diphenyl ether disulfonate (“Eleminol MON-7” manufactured by Sanyo Chemical Industries, Ltd.), and 90 parts by mass of ethyl acetate The parts were mixed and stirred to obtain a milky white liquid (aqueous phase).

-Synthesis of low molecular weight polyester-
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 682 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 81 parts by mass of bisphenol A propylene oxide 2 mol adduct, 283 parts by mass of terephthalic acid, A low molecular weight polyester was synthesized by charging 22 parts by weight of merit acid and 2 parts by weight of dibutyltin oxide and reacting at 230 ° C. for 5 hours under normal pressure.
The obtained low molecular weight polyester has a number average molecular weight (Mn) of 2,100, a mass average molecular weight of 9,500, a glass transition temperature (Tg) of 55 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 51. Met.

-Synthesis of modified polyesters having reactive substituents-
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 410 parts by mass of the low molecular weight polyester, 89 parts by mass of isophorone diisocyanate, and 500 parts by mass of ethyl acetate were charged and reacted at 100 ° C. for 5 hours. Then, a modified polyester having a reactive substituent (polymer capable of reacting with the active hydrogen group-containing compound) was synthesized.
The free isocyanate content of the obtained modified polyester having a reactive substituent was 1.53% by mass.

-Preparation of master batch-
1200 parts by weight of water and C.I. I. Pigment Red122 (manufactured by Clariant Japan KK, TONER MAGENTA E02) 405 parts by mass, C.I. I. Pigment Violet 19 (manufactured by Clariant Japan Co., Ltd., PV FAST RED E5B) 135 parts by mass, polyester dispersant (“Ajisper PB822”, manufactured by Ajinomoto Fine Techno Co., Ltd.) 108 parts by mass, and 1200 parts by mass of the polyester resin (1) It mixed with the mixer (made by Mitsui Mining Co., Ltd.). The mixture was kneaded with two rolls at 150 ° C. for 30 minutes, rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron Corporation) to prepare a pigment dispersion.

-Preparation of organic solvent phase-
In a reaction vessel in which a stir bar and a thermometer are set, 378 parts by mass of the polyester resin (1), 110 parts by mass of carnauba wax, and 947 parts by mass of ethyl acetate are charged, and the temperature is raised to 80 ° C. with stirring. After maintaining at 80 ° C. for 30 hours, the mixture was cooled to 30 ° C. over 1 hour to obtain a raw material solution.
1324 parts by mass of the obtained raw material solution was transferred into a reaction vessel, and using a bead mill (“Ultra Visco Mill”, manufactured by Imex Co., Ltd.), the liquid feeding speed was 1 kg / hr, the disk peripheral speed was 6 m / sec, and 0.5 mm. The carnauba wax was dispersed by dispersing for 9 hours under the condition that 80% by volume of zirconia beads were filled.
Next, 1324 parts by mass of a 65% by mass ethyl acetate solution of the low molecular weight polyester was added to the dispersion, and 500 parts by mass of the master batch and 500 parts by mass of ethyl acetate were charged and mixed for 1 hour. Next, the mixed liquid was kept at 25 ° C. and passed 4 times with an Ebara milder (combination of G, M, and S from the inlet side) at a flow rate of 1 kg / min to prepare an organic solvent phase (pigment / wax dispersion).
The solid content concentration of the obtained organic solvent phase (130 ° C., 30 minutes) was 50% by mass.

-Emulsification or dispersion-
Into a reaction vessel, 749 parts by mass of the organic solvent phase, 115 parts by mass of the modified polyester having a reactive substituent, and 2.9 parts by mass of isophorone diamine (manufactured by Wako Pure Chemical Industries, Ltd.) were charged. After mixing for 1 minute at 5,000 rpm using TK Homomixer MKII manufactured by Meika Co., Ltd., 1200 parts by mass of the aqueous phase was added to the reaction vessel, and the rotation speed was adjusted to 9,000 rpm with the homomixer. And mixed for 3 minutes. Then, it stirred for 20 minutes with the stirrer and prepared the emulsion slurry.
Next, the emulsified slurry was charged into a reaction vessel equipped with a stirrer and a thermometer, and the solvent was removed at 25 ° C. After removing the organic solvent, aging was performed at 45 ° C. for 15 hours to obtain a dispersed slurry.

-Washing process-
After 100 parts by mass of the dispersion slurry was filtered under reduced pressure, 100 parts by mass of ion-exchanged water was added to the filter cake, mixed with a homomixer (rotation speed: 8,000 rpm for 10 minutes), and then filtered. 100 parts by mass of ion-exchanged water was added to the obtained filter cake, mixed with a homomixer (10 minutes at a rotation speed of 8,000 rpm), and then filtered under reduced pressure. 100 mass parts of 10 mass% sodium hydroxide aqueous solution was added to the filter cake obtained here, it mixed with the homomixer (10 minutes at the rotation speed of 8,000 rpm), and then filtered. 100 mass parts of 10 mass% hydrochloric acid was added to the filter cake obtained here, it mixed with the homomixer (10 minutes at the rotation speed of 8,000 rpm), and then filtered. 300 parts by mass of ion-exchanged water was added to the obtained filter cake, mixed with a homomixer (10 minutes at a rotation speed of 8,000 rpm), and then filtered twice to obtain a final filter cake. The obtained final filter cake was dried with a circulating dryer at 45 ° C. for 48 hours, and sieved with a mesh of 75 μm to prepare toner base particles of Example 1.

-External additive treatment-
100 parts by mass of the obtained toner base particles of Example 1 and 0.5 parts by mass of hydrophobic silica (H2000, manufactured by Clariant Japan, average particle size of primary particles = 10 nm) as an external additive were mixed with a Henschel mixer. Thus, Toner 1 of Example 1 was produced.

[Example 2]
(Preparation of Toner 2)
In Example 1, as a pigment dispersion method, the same as in Example 1 except that the preparation of the master batch was changed to the preparation of the pigment dispersion as follows and the preparation of the organic solvent phase was changed as follows. Thus, Toner 2 was produced.
-Preparation of pigment dispersion-
7,000 parts by mass of ethyl acetate, C.I. I. Pigment Red122 (manufactured by Clariant Japan Co., Ltd., TONER MAGENTA E02) 1050 parts by mass, C.I. I. Pigment Violet 19 (manufactured by Clariant Japan Co., Ltd., PV FAST RED E5B) 450 parts by mass, acrylic dispersant (Disperbyk 2000, manufactured by Big Chemie Co., Ltd.) 300 parts by mass, and 1,500 parts by mass of the polyester resin (1) are mixed. The mixture was filled with 80% by volume of 0.5 mm zirconia beads using a bead mill (manufactured by Shinmaru Enterprises Co., Ltd., horizontal wet disperser, dyno mill) at a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec. For 6 hours to prepare a pigment dispersion.

-Preparation of organic solvent phase-
In a reaction vessel equipped with a stirring bar and a thermometer, 378 parts by mass of the polyester resin (1), 110 parts by mass of carnauba wax, and 947 parts by mass of ethyl acetate were charged, and the temperature was raised to 80 ° C. with stirring. After maintaining at 80 ° C. for 30 hours, the mixture was cooled to 30 ° C. over 1 hour to obtain a raw material solution.
1,324 parts by mass of the obtained raw material solution was transferred to a reaction vessel, 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, The carnauba wax was dispersed by dispersing for 9 hours under the condition that 80% by volume of 5 mm zirconia beads were filled.
Next, 940 parts by mass of a 65% by mass ethyl acetate solution of the low molecular weight polyester was added to the dispersion, and 1,667 parts by mass of the pigment dispersion and 250 parts by mass of ethyl acetate were charged and mixed for 1 hour. Next, the mixed liquid was kept at 25 ° C., and an organic solvent phase (pigment / wax dispersion) was prepared by passing 4 passes at a flow rate of 1 kg / min with an Ebara milder (combination of G, M, and S from the inlet side). .
The solid content concentration of the obtained organic solvent phase (130 ° C., 30 minutes) was 50% by mass.

Example 3
(Preparation of Toner 3)
In Example 1, 108 parts by mass of a polyester dispersant (“Ajisper PB822”, manufactured by Ajinomoto Fine Techno Co., Ltd.) was added to 360 parts by mass of a polyurethane pigment dispersant (“EFKA-4080”, manufactured by Ciba Specialty Chemicals). A toner 3 of Example 3 was produced in the same manner as Example 1 except for the change.

(Comparative Example 1)
(Preparation of Toner 4)
In Example 2, C.I. I. Toner 4 of Comparative Example 1 was produced in the same manner as in Example 2, except that Pigment Red 122 was changed to 1500 parts by mass alone.

[Comparative Example 2]
(Preparation of Toner 5)
In Example 2, C.I. I. Pigment Red122, 750 parts by mass, C.I. I. Toner 5 of Comparative Example 2 was produced in the same manner as in Example 2 except that Pigment Violet 19 was changed to 750 parts by mass.
Next, the volume average particle diameter (Dv), the number average particle diameter (Dn), the ratio (Dv / Dn), and the haze degree of each toner obtained were measured as follows. The results are shown in Table 1.

<Measurement of Volume Average Particle Size (Dv), Number Average Particle Size (Dn), and Ratio (Dv / Dn)>
The volume average particle diameter (Dv), the number average particle diameter (Dn), and the ratio (Dv / Dn) of each toner are measured using a particle size measuring device (“Multisizer III”, manufactured by Beckman Coulter, Inc.) and an aperture diameter of 100 μm. And analyzed with analysis software (Beckman Coulter Multisizer 3 Version 3.51). Specifically, 0.5 ml of 10% by weight surfactant (alkylbenzene sulfonate, Neogen SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is added to a 100 ml glass beaker, and 0.5 g of each toner is added. The mixture was stirred with a microspatel, and then 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 with the “Multisizer III” using Isoton III (manufactured by Beckman Coulter, Inc.) 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 to adjust the concentration to 8 ± 2% from the viewpoint of the reproducibility of the particle size. Within this concentration range, no error occurs in the particle size.

<Measurement of haze degree>
The toner was added to 10 g of each toner and 40 g of tetrahydrofuran (THF), and was stirred and dissolved by a magnetic stirrer. The obtained solution was applied on a transparent film (HA-88 manufactured by Higashiyama Film Co., Ltd.) with a 0.3 mm wire bar so as to have a thickness of 5 μm to obtain a thin film sample. The haze degree of the obtained thin film sample was measured with a TM double beam automatic haze computer (manufactured by Suga Test Instruments Co., Ltd.).

-Production of developer-
2.5 parts by mass of each toner thus obtained and 97.5 parts by mass of a silicone-coated ferrite carrier (core material particle size 45 μm) were stirred using a tumbler mixer (manufactured by Shinmaru Enterprises). A two-component developer was prepared as described above.

  Next, the reflection density (ID) and hue (a * b *) saturation were evaluated using the obtained developers as follows. The results are shown in Table 1.

<Measurement of reflection density (ID)>
Using an image forming apparatus (Imagio Neo 450, manufactured by Ricoh Co., Ltd.), 0.25 mg of a solid image and a thick paper transfer paper (type 6200 manufactured by Ricoh Co., Ltd. and copy printing paper <135> manufactured by NBS Ricoh Co., Ltd.) in a solid image Adjustment was made so that each toner of / cm ² was developed, the fixing belt temperature was set to 160 ° C., and fixing was performed, and a solid image was output. About the obtained solid image, reflection density (ID) was measured by X-Rite (made by X-Rite).

<Evaluation of saturation>
The saturation was calculated by calculating from saturation = √ (a ^{* 2} + b ^{* 2} ) based on a ^* b ^* measured by X-rite (manufactured by X-Rite) simultaneously with the reflection density (ID). .
The results are shown in Table 1.

  The magenta toner of the present invention has high chroma and high reflection density characteristics and good transparency, so that it can be suitably used in various fields and can be suitably used as a full-color image forming toner.

1 is a schematic cross-sectional view of a main part showing an example of an image forming apparatus of the present invention. FIG. 2 is a partially enlarged view of the image forming apparatus in FIG. 1. It is a schematic structure sectional view showing an example of the process cartridge of the present invention.

Explanation of symbols

1 Photoconductor (Photoconductor drum)
2 Charger 4 Developing means 7 Cleaning member (cleaning means)
61 Developing device 63 Cleaning device 64 Static eliminator 120 Tandem type developing device 130 Document table 142 Paper feed roller 143 Paper bank 144 Paper feed cassette 145 Separating roller 146 Paper feed route 147 Conveying roller 148 Paper feed route 150 Copying device main body 160 Charging device 200 Paper feed table 300 Scanner 400 Automatic document feeder (ADF)
1010K Electrostatic latent image carrier 1010K Black electrostatic latent image carrier 1010Y Yellow electrostatic latent image carrier 1010M Magenta electrostatic latent image carrier 1010C Cyan electrostatic latent image carrier 1014 Support roller 1015 Support roller 1016 Support roller 1017 Intermediate transfer cleaning device 1018 Image forming means 1021 Exposure device 1022 Secondary transfer device 1023 Roller 1024 Secondary transfer belt 1025 Fixing device 1026 Fixing belt 1027 Pressure roller 1028 Sheet reversing device 1032 Contact glass 1033 First traveling body 1034 First 2 traveling body 1035 imaging lens 1036 reading sensor 1049 registration roller 1050 intermediate transfer body 1053 manual feed path 1054 manual feed tray 1055 switching claw 1056 discharge roller 1057 Out tray 1058 separation roller 1062 transfer charger

Claims (18)

A magenta toner containing at least a binder resin, a pigment, and a pigment dispersant,
The pigment is C.I. I. Pigment Red122 and C.I. I. Pigment Violet 19,
A magenta toner characterized in that a haze degree of a coating film obtained by applying a solution obtained by dissolving 10 g of the toner in 40 g of tetrahydrofuran onto a substrate with a 0.3 mm wire bar is 0.1 to 25%. .   C. above. I. Pigment Red122 and C.I. I. 2. The magenta toner according to claim 1, wherein the mass ratio of Pigment Violet 19 is 95: 5 to 60:40.   The magenta toner according to claim 1, wherein the pigment dispersant contains a polyester pigment dispersant.   The magenta toner according to claim 1, wherein the pigment dispersant contains an acrylic pigment dispersant.   The magenta toner according to claim 1, wherein the pigment dispersant contains a polyurethane pigment dispersant.   C. in the magenta toner. I. Pigment Red122 and C.I. I. The magenta toner according to claim 1, wherein the total content of Pigment Violet 19 is 1% by mass to 20% by mass.   The magenta toner according to any one of claims 1 to 6, wherein an addition amount of the pigment dispersant is 1 part by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the pigment.   The magenta toner according to claim 1, wherein a volume average particle diameter (Dv) of the magenta toner is 2.5 μm to 5.5 μm.   The ratio (Dv / Dn) between the volume average particle diameter (Dv) and the number average particle diameter (Dn) of the magenta toner is 1.0 to 1.2. The magenta toner according to any one of the above.   In an organic solvent, a compound having an active hydrogen group, a polymer having a site capable of reacting with the compound having an active hydrogen group, a toner material containing at least the pigment and the pigment dispersant are dissolved or dispersed, and the dissolved or dispersed The magenta toner according to claim 1, wherein the magenta toner is obtained by reacting the dispersion in an aqueous medium and removing the organic solvent from the obtained emulsified dispersion.   11. The magenta toner according to claim 10, wherein the polymer having a site capable of reacting with the compound having an active hydrogen group is a modified polyester resin (i) having a reactive substituent.   The magenta toner according to claim 11, wherein the reactive substituent of the polymer having the reactive site is an isocyanate group.   The binder resin contains a modified polyester resin (i) reacted with a compound having an active hydrogen group and an unmodified polyester resin (ii), and their mass ratio [(i) / (ii) The magenta toner according to claim 11, wherein the toner is 5/95 to 30/70.   An electrostatic charge developer using the toner according to claim 1. In an organic solvent, a toner material containing at least a compound having an active hydrogen group, a polymer having a site capable of reacting with the compound having an active hydrogen group, a pigment, and a pigment dispersant is dissolved or dispersed. A method for producing a toner in which an organic solvent is removed from an emulsified dispersion obtained by reacting a dissolved or dispersed material in an aqueous medium;
The pigment is C.I. I. Pigment Red122 and C.I. I. Pigment Violet 19, and
The pigment dispersant is at least one of a polyester pigment dispersant, an acrylic pigment dispersant, or a polyurethane pigment dispersant,
A method for producing a magenta toner.   An image forming method for developing an electrostatic latent image formed on an image carrier with toner, wherein the toner uses the magenta toner according to any one of claims 1 to 13.   An image forming apparatus for developing an electrostatic latent image formed on an image carrier with toner, wherein the toner is the magenta toner according to claim 1.   An image carrier and at least a developing unit that develops the electrostatic image formed on the image carrier using the magenta toner according to claim 1 to form a visible image are integrally supported. A process cartridge which is detachable from the image forming apparatus main body.

Images