JP5885455B2 - toner - Google Patents

Description

  The present invention relates to a toner used in an electrophotographic system, an electrostatic recording system, an electrostatic printing system, and a toner jet system.

In recent years, with the rapid spread of electrophotographic color image forming apparatuses, their uses have expanded to a wider variety, and the demand for image quality has been increasing than ever.
For example, full-color video communication has become widespread as the price of computer equipment for personal users has decreased. Even in an image forming apparatus such as a printer or a copying machine which is one of the output means, it is required to faithfully reproduce even a minute portion.
Along with this, the demand for vividness of colors has been increasing, and the expansion of the color reproduction range has been demanded.
In recent years, the advancement to the printing field has been remarkable, and for electrophotographic output images, at the same time as improving the printing speed, image quality such as high definition, high definition, and graininess equal to or higher than the printing quality is required. It is becoming.
At the same time, improvement in printing speed, reduction in running cost, stability of image quality that does not depend on the use environment, and the like are also required, and a toner that satisfies these various required characteristics is desired.
In general, an electrophotographic method forms an electrical latent image on a photoreceptor, then develops the latent image with toner, transfers the toner image to a medium such as paper, and then heats and / or heats by a fixing unit. It is fixed by pressing to obtain a color image.
In the case of a full-color image, color reproduction is performed with three chromatic toners of three primary colors, yellow toner, magenta toner, and cyan toner, or four toners including black toner.
Various proposals have been made for magenta toner pigments, and dimethylquinacridone, which is a quinacridone pigment, is often used in terms of excellent color sharpness and light resistance.
However, since dimethylquinacridone does not have a high coloring power, it is necessary to add a large amount to the toner in order to increase the coloring power of the toner.
In addition, dimethylquinacridone tends to aggregate and coarsen in the toner, and the coloring power may be further reduced or the color tone may change to reddish due to the deterioration of dispersibility. The color reproducibility of blue, which is a color made by mixing the primary colors with, tends to deteriorate.
For these reasons, it is a challenge to achieve both the coloring power of magenta toner and the blue reproducibility, and proposals have been made to use quinacridone pigments in combination with other pigments and to improve quinacridone pigments.
For example, Patent Document 1 proposes a toner using a quinacridone pigment and a naphthol pigment in combination.
Patent Document 2 proposes a toner using dimethylquinacridone and unsubstituted quinacridone in combination as an improvement of the quinacridone pigment. Further, Patent Document 3 proposes a toner using a combination of symmetric quinacridone and asymmetric quinacridone.
However, when any toner is used in an image forming apparatus for high-speed printing that is required in the printing field, it is difficult to mix the toner in the fixing unit, and the coloring power and blue reproducibility of the magenta toner may be reduced. It was.

Japanese Patent Laid-Open No. 2006-267641 JP-A-10-97102 Japanese translation of Japanese translation of PCT publication 2007-5000025

  The present invention provides a toner that solves the above problems. Specifically, the present invention provides a magenta toner having high coloring power and excellent blue reproducibility even when used in an image forming apparatus for high-speed printing required in the printing field.

As a result of diligent investigations, the present inventors have obtained a magenta toner having high coloring power and excellent blue reproducibility by including a specific compound at a specific ratio in the magenta colorant contained in the toner. As a result, the present invention has been completed.
That is, the present invention
A toner having toner particles containing a binder resin and a magenta colorant,
The magenta colorant includes a compound A represented by the following formula (1), a compound B represented by the following formula (2), and Pigment Red 150, Pigment Red 57: 1, Pigment Red 238, and Pigment Red 269. Containing one or more pigments C selected from the group consisting of:
When the content of the compound A with respect to 100 parts by mass of the binder resin is Ya parts by mass and the content of the compound B is Yb parts by mass, Yb / (Ya + Yb) is 0.10 or more and 0.90 or less. And Yb is 0.50 or more and 10.00 or less.

  According to the present invention, it is possible to provide a magenta toner having high coloring power and excellent blue reproducibility even when used in an image forming apparatus for high-speed printing required in the printing field.

The toner of the present invention is a toner having toner particles containing a binder resin and a magenta colorant,
The magenta colorant includes a compound A represented by the following formula (1), a compound B represented by the following formula (2), and Pigment Red 150, Pigment Red 57: 1, Pigment Red 238, and Pigment Red 269. Containing one or more pigments C selected from the group consisting of:
When the content of the compound A with respect to 100 parts by mass of the binder resin is Ya parts by mass and the content of the compound B is Yb parts by mass, Yb / (Ya + Yb) is 0.10 or more and 0.90 or less. And Yb is 0.50 or more and 10.00 or less.

By using the toner having the above configuration, a magenta toner having high coloring power and excellent blue reproducibility can be provided.
The present inventors have found that the magenta colorant comprises Compound A, Compound B, and Pigment C, and the content of Compound B and the content ratio of Compound B to the total content of Compound A and Compound B are It has been found that by being in a specific range, a magenta toner having high coloring power and excellent blue reproducibility can be obtained.
By including the compound A, the compound B, and the pigment C, the interaction between the compound A and the compound B and the interaction between the compound B and the pigment C are expressed.
The magenta colorant of the present invention improves the dispersibility of the compound A, the compound B, and the pigment C in the toner due to these interactions, and changes the absorption spectrum of visible light, so that the coloring power is high. Presumed to be excellent in blue reproducibility.
First, the effect of the interaction between Compound B and Compound A will be described.
In general, a quinacridone compound has a simple molecular structure and high regularity, and forms a hydrogen bond between molecules when the molecules overlap each other in layers, so that a stable and strong crystal is easily formed.
Among them, since compound A has a high symmetry of steric hindrance due to substituents, it forms a particularly strong crystal and becomes coarse due to crystal growth and aggregation, so that the dispersibility tends to deteriorate.
The coloring of the toner decreases due to the deterioration of the dispersibility of Compound A. Furthermore, the color tone of the aggregated and coarsened compound A changed to red, and the blue reproducibility of the toner was deteriorated.
On the other hand, the present inventors can improve the dispersibility of the compound A and the compound B in the toner by adding the compound B together with the compound A in the toner together with the compound B having different steric hindrance due to the substituents on the left and right. It was found that a toner having a high blue color and excellent blue reproducibility can be obtained.
This is because the formation of a mixed crystal (solid solution) of compound A and compound B suppresses the formation of crystals (single crystals) formed only of the same molecule that is strong and highly cohesive, and their growth and It is presumed that coarsening due to aggregation could be suppressed.
If the magenta colorant of the present invention does not contain Compound B, the effect of improving the dispersibility of Compound A and Compound B due to the formation of the mixed crystal cannot be obtained, so that the coloring power and blue reproducibility of the toner are insufficient. Therefore, it is not preferable.
In addition, for the production of the mixed crystal, it is important to control the abundance ratio of the compound A and the compound B in the toner particles.
In the present invention, when the content of the compound A with respect to 100 parts by mass of the binder resin is Ya parts by mass and the content of the compound B is Yb parts by mass, Yb / (Ya + Yb) is 0.10 or more and 0.90 or less. is there. Further, Yb / (Ya + Yb) is preferably 0.20 or more and 0.80 or less.
When Yb / (Ya + Yb) is less than 0.10, since the ratio of Compound B is too low, it becomes difficult to form a mixed crystal of Compound A and Compound B, and the dispersibility of Compound A and Compound B deteriorates. The coloring power of the toner decreases. Further, the single crystal of compound A becomes coarse, and the blue reproducibility of the toner is deteriorated.
On the other hand, when Yb / (Ya + Yb) exceeds 0.90, since the ratio of compound B is too high, it becomes difficult to form a mixed crystal of compound A and compound B, and the dispersibility of compound A and compound B deteriorates. This reduces the coloring power of the toner. Further, the single crystal of compound B is coarsened, and the blue reproducibility of the toner is deteriorated.

Next, the effect by the interaction between the compound B and the pigment C will be described.
In the present invention, the interaction between the compound B and the pigment C refers to a phenylene ring that is not substituted with a methyl group among the two phenylene rings that the compound B has on the left and right sides (hereinafter referred to as an unsubstituted phenylene ring). And π-π interaction due to the naphthalene ring of pigment C.
In general, the π-π interaction is an interaction force acting between aromatic rings of an organic compound, and is stabilized in an arrangement in which two aromatic rings are stacked. At this time, orbits of π electrons are pseudo-overlapped, and each aromatic ring has abundant delocalized π electrons.
In the colorant of the present invention, the aromatic ring of Compound B or Pigment C has an apparent excess of π electrons due to the effect of the π-π interaction.
Therefore, the π electrons of the phenylene ring of compound B and the naphthalene ring of pigment C can be transitioned with lower energy than usual, the absorption wavelength is shifted to the longer wavelength side, and absorption in the blue wavelength region is suppressed. It is estimated that excellent blue reproducibility appears.
Further, the π-π interaction suppresses aggregation and coarsening of single crystals of Compound B and Pigment C in the toner, and increases dispersibility, so that the coloring power of the toner can be improved.
In the toner of the present invention, when the content of compound B with respect to 100 parts by mass of the binder resin is Yb parts by mass, Yb is 0.50 or more and 10.00 or less. Preferably, Yb is 0.75 or more and 7.50 or less.
When Yb is less than 0.50, the π-π interaction between the compound B and the pigment C becomes difficult to develop, and the blue reproducibility improving effect cannot be obtained. Moreover, the dispersibility of the compound B and the pigment C deteriorates, and the coloring power also decreases.
On the other hand, when Yb exceeds 10.00, the dispersibility of compound B deteriorates due to the growth or aggregation of the single crystal of compound B, and the coloring power decreases, and the blue reproducibility also deteriorates.

The magenta colorant of the present invention contains one or more pigments C selected from the group consisting of Pigment Red 150, Pigment Red 57: 1, Pigment Red 238, and Pigment Red 269.
The pigment C may be one kind of these pigments or may contain two or more kinds.
Pigment C has a naphthalene ring in the molecular chain skeleton, and since there are few steric hindrances due to substituents of the naphthalene ring, the effect of the above-described π-π interaction between compound B and pigment C is manifested. In addition, the coloring power is high, and blue reproducibility can be obtained.
When the magenta colorant of the present invention does not contain the pigment C, the effect due to the π-π interaction with the compound B described above does not appear, and the blue reproducibility and coloring power are insufficient.
In the toner of the present invention, it is preferable that Yc / (Ya + Yb + Yc) is 0.20 or more and 0.80 or less when the content of the pigment C with respect to 100 parts by mass of the binder resin is Yc parts by mass. More preferably, Yc / (Ya + Yb + Yc) is 0.25 or more and 0.75 or less.
When Yc / (Ya + Yb + Yc) is 0.20 or more, the π-π interaction between Compound B and Pigment C is promoted, and even when used in an image forming apparatus having a high printing speed, stable and high coloring power. And excellent blue reproducibility can be expressed.
Further, when Yc / (Ya + Yb + Yc) is 0.80 or less, the growth and aggregation of the single crystal of pigment C can be further suppressed, and even when used in an image forming apparatus having a high printing speed, stable and high coloring power. And excellent blue reproducibility can be expressed.

In the present invention, the magenta colorant preferably contains a compound D represented by the following formula (3) in addition to the compound A, the compound B, and the pigment C.

The compound D is preferable because the coloring power and blue reproducibility of the toner can be further improved.
This is presumably because the dispersibility of the colorant is further improved by the formation of a three-component mixed crystal of compound A, compound B, and compound D.
Further, in addition to the π-π interaction between the compound B and the pigment C, the π-π interaction between the compound D and the pigment C is also expressed, so that the absorption wavelength of the colorant is shifted to the longer wavelength side, Further, it is estimated that excellent blue reproducibility appears.
When the content of the compound D with respect to 100 parts by mass of the binder resin is Yd parts by mass, Yd / (Ya + Yb + Yc + Yd) is preferably 0.01 or more and 0.05 or less. More preferably, Yd / (Ya + Yb + Yc + Yd) is 0.02 or more and 0.04 or less.
Compound D is a quinacridone compound that has higher crystallinity and is more likely to aggregate than Compound A. By setting Yd / (Ya + Yb + Yc + Yd) to 0.05 or less, aggregation of Compound D in the toner can be easily suppressed. Therefore, the toner has higher coloring power and excellent blue reproducibility.
On the other hand, when Yd / (Ya + Yb + Yc + Yd) is 0.01 or more, the above-described effect due to the addition of the compound D is easily exhibited, and the toner has excellent coloring power and blue reproducibility.

In the present invention, (Ya + Yb + Yc + Yd) is preferably 5.00 parts by mass or more and 20.00 parts by mass or less.
It is preferable that (Ya + Yb + Yc + Yd) is 5.00 parts by mass or more because coloring power as a toner is increased. On the other hand, when (Ya + Yb + Yc + Yd) is 20.00 parts by mass or less, the dispersibility of the compound A, the compound B, the pigment C, and the compound D can be maintained high, and the toner is excellent in blue reproducibility, which is preferable. .

The binder resin used in the toner of the present invention is not particularly limited, and a known polymer or resin can be used. Specific examples are given below.
Styrene such as polystyrene, poly-p-chlorostyrene, polyvinyltoluene, and homopolymers thereof; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene -Acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether Styrene copolymers such as copolymers, styrene-vinyl methyl ketone copolymers, styrene-acrylonitrile-indene copolymers; polyvinyl chloride, phenol resins, natural modified phenol resins, natural resin modified maleic resins, acrylic resins , Methacrylic tree , Polyvinyl acetate, silicone resins, polyester resins, polyurethane, polyamide resins, furan resins, epoxy resins, xylene resins, polyvinyl butyral, terpene resins, coumarone - indene resins, and petroleum resins.
Among these, a polyester resin having an aromatic ring is used in that it has high affinity with the magenta colorant and can further improve the dispersibility of Compound A, Compound B, Pigment C, and Compound D. Is preferred.
The polyester resin is a resin having a “polyester unit” in the binder resin chain. Specifically, the component constituting the polyester unit includes a bivalent or higher alcohol monomer component and a divalent And acid monomer components such as the above carboxylic acids, divalent or higher carboxylic acid anhydrides, and divalent or higher carboxylic acid esters.
For example, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis (4- Hydroxyphenyl) propane, polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2-bis Alkylene oxide adducts of bisphenol A such as (4-hydroxyphenyl) propane and polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol, 1,2- Propylene glycol, 1,3-propylene glycol, 1,4-butanediol Neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, sorbit, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2 -Methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene and the like.
Among them, the alcohol monomer component preferably used is a monomer component containing an aromatic ring. In the alcohol monomer component constituting the polyester resin, the monomer component containing an aromatic ring should be contained in a proportion of 80 mol% or more. Is preferred.
On the other hand, as acid monomer components such as divalent or higher carboxylic acid, divalent or higher carboxylic acid anhydride and divalent or higher carboxylic acid ester, aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid, or anhydrides thereof. Alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof; succinic acid or anhydrides substituted with alkyl or alkenyl groups having 6 to 18 carbon atoms; fumaric acid, maleic acid And unsaturated dicarboxylic acids such as citraconic acid or anhydrides thereof.
Of these, the acid monomer component preferably used is a polyvalent carboxylic acid such as terephthalic acid, succinic acid, adipic acid, fumaric acid, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, or an anhydride thereof.
In the present invention, when the binder resin is a polyester resin, and the acid value of the polyester resin is 1 mgKOH / g or more and 20 mgKOH / g or less, the dispersibility of the colorant is further excellent, and the coloring power is high. This is preferable because the toner has excellent blue reproducibility.
In addition, the acid value of a polyester resin can be made into the said range by adjusting the kind and compounding quantity of the monomer used for resin. Specifically, it can be controlled by adjusting the alcohol monomer component ratio / acid monomer component ratio and molecular weight during resin production. It can also be controlled by reacting the terminal alcohol with a polyvalent acid monomer (for example, trimellitic acid) after ester condensation polymerization.

It is preferable to add a wax to the toner of the present invention as necessary. Although it does not specifically limit as this wax, The following are mentioned.
Low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymer, hydrocarbon wax such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax; oxide of hydrocarbon wax such as oxidized polyethylene wax or block copolymer thereof; Waxes mainly composed of fatty acid esters such as carnauba wax; those obtained by partially or fully deoxidizing fatty acid esters such as deoxidized carnauba wax. Furthermore, the following are mentioned. Saturated linear fatty acids such as palmitic acid, stearic acid and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid and valinalic acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvyl alcohol, seryl alcohol, Saturated alcohols such as sil alcohols; polyhydric alcohols such as sorbitol; fatty acids such as palmitic acid, stearic acid, behenic acid, montanic acid, and stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvyl alcohol, seryl alcohol, Esters with alcohols such as sil alcohols; Fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; Methylene bis stearic acid amide, ethylene biscapric acid Saturated fatty acid bisamides such as amide, ethylene bis lauric acid amide, hexamethylene bis stearic acid amide; ethylene bis oleic acid amide, hexamethylene bis oleic acid amide, N, N 'dioleyl adipic acid amide, N, N' dioleyl Unsaturated fatty acid amides such as sebacic acid amides; aromatic bisamides such as m-xylene bis-stearic acid amide, N, N ′ distearyl isophthalic acid amide; calcium stearate, calcium laurate, zinc stearate, magnesium stearate Aliphatic metal salts such as those commonly referred to as metal soaps; waxes grafted to aliphatic hydrocarbon waxes using vinylic monomers such as styrene and acrylic acid; fatty acids such as behenic acid monoglycerides Alcohol Partial ester; methyl ester compounds having hydroxyl groups obtained by hydrogenation of vegetable fats and oils.
Among these waxes, hydrocarbon waxes such as paraffin wax and Fischer-Tropsch wax are preferable from the viewpoint of low-temperature fixability and frictional charging stability.
The content of the wax is preferably 0.5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin. Further, from the viewpoint of achieving both the storage stability of the toner and the high temperature offset property, the maximum existing in the temperature range of 30 ° C. or more and 200 ° C. or less in the endothermic curve at the time of temperature rise measured by a differential scanning calorimeter (DSC) The peak temperature of the endothermic peak is preferably 50 ° C. or higher and 110 ° C. or lower.

The toner of the present invention may contain a charge control agent as necessary. As the charge control agent contained in the toner, known ones can be used. In particular, a metal compound of an aromatic carboxylic acid that is colorless, has a high toner charging speed, and can stably maintain a constant charge amount is preferable.
Negative charge control agents include salicylic acid metal compounds, naphthoic acid metal compounds, dicarboxylic acid metal compounds, polymeric compounds having sulfonic acid or carboxylic acid in the side chain, sulfonates or sulfonated compounds in the side chain. Examples thereof include a polymer compound, a polymer compound having a carboxylate or a carboxylic acid ester in the side chain, a boron compound, a urea compound, a silicon compound, and calixarene. Examples of the positive charge control agent include a quaternary ammonium salt, a polymer compound having the quaternary ammonium salt in the side chain, a guanidine compound, and an imidazole compound. The charge control agent may be added internally or externally to the toner particles. The addition amount of the charge control agent is preferably 0.2 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the binder resin.

If necessary, an external additive may be added to the toner of the present invention to improve fluidity and adjust the triboelectric charge amount.
As the external additive, inorganic fine particles such as silica, titanium oxide, aluminum oxide, and strontium titanate are preferable. The inorganic fine particles are preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil, or a mixture thereof.
The specific surface area of the external additive used is preferably 10 m ² / g or more and 200 m ² / g or less from the viewpoint of suppressing embedding of the external additive.
The amount of the external additive added is preferably 0.1 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the toner particles.
For mixing the toner particles and the external additive, a known mixer such as a Henschel mixer can be used. However, the mixing is not particularly limited as long as the mixing is possible.

Although the toner of the present invention can be used as a one-component developer, it is mixed with a magnetic carrier as a two-component developer in order to improve dot reproducibility and to obtain a stable image over a long period of time. It is preferable to use it.
Examples of the magnetic carrier include metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, and rare earth, and alloy particles and oxide particles thereof, magnetic materials such as ferrite, and magnetic materials. Generally known materials such as a magnetic material-dispersed resin carrier (so-called resin carrier) containing a binder resin that holds the magnetic material in a dispersed state can be used.
When the toner of the present invention is mixed with a magnetic carrier and used as a two-component developer, the mixing ratio of the magnetic carrier is preferably 2% by mass or more and 15% by mass or less as the toner concentration in the developer. More preferably, it is 4 mass% or more and 13 mass% or less. If the toner concentration is less than 2% by mass, the image density tends to decrease, and if it exceeds 15% by mass, fogging or in-machine scattering tends to occur.

The method for producing the toner of the present invention is not particularly limited, and a known production method can be used. Here, a toner manufacturing method using a pulverization method will be described as an example.
In this invention, the manufacturing method of the compound A, the compound B, and the compound D which are colorants does not have a restriction | limiting in particular, It can manufacture by the technique conventionally known as a manufacturing method of a quinacridone compound. Further, the production method of the pigment C is not particularly limited, and can be produced by a conventionally known method.
The quinacridone compounds A, B and D may be synthesized separately or may be synthesized simultaneously and / or sequentially in the same reaction vessel.
It is preferable to synthesize simultaneously and / or sequentially in the same reaction vessel from the viewpoint of facilitating the formation of a mixed crystal of Compound A, Compound B, and Compound D to easily increase the dispersibility in the toner.
On the other hand, in order to promote the formation of mixed crystals of Compound A, Compound B, and Compound D and the π-π interaction between Compound B and Pigment C, these colorants are added in advance to the toner before being added to the toner. It is preferable to produce a colorant masterbatch comprising a binder resin.
The colorant masterbatch may be a colorant masterbatch in which one kind of colorant is blended, or a mixed colorant masterbatch in which a plurality of kinds of colorants are blended in the same masterbatch.
Furthermore, in order to promote the formation of mixed crystals and the π-π interaction, it is preferable to produce a mixed colorant masterbatch in which compound B is combined with another colorant.

First, in the raw material mixing step, a predetermined amount of a binder resin, a colorant and / or a colorant masterbatch, and other components such as a wax and a charge control agent as necessary are weighed as materials constituting the toner particles. Mix and mix.
Examples of the mixing apparatus include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, a nauter mixer, and a mechano hybrid (manufactured by Nippon Coke Industries, Ltd.).
Next, the mixed material is melt-kneaded to disperse the colorant and the like in the binder resin. In the melt-kneading step, a batch kneader such as a pressure kneader or a Banbury mixer or a continuous kneader can be used. It is preferable to use a twin screw extruder from the viewpoint that the shearing force applied to the molten mixture and the temperature can be easily controlled and continuous production is possible.
As the twin screw kneader used, a KTK type twin screw extruder (manufactured by Kobe Steel Co., Ltd.), a TEM type twin screw extruder (manufactured by Toshiba Machine Co., Ltd.), a PCM kneader (manufactured by Ikekai Tekko), a twin screw extruder ( And Kneader (manufactured by NIPPON Coke Industries Co., Ltd.).
The toner of the present invention is mixed by shearing force through the melt-kneading process in order to promote the formation of mixed crystals of compound A, compound B, and compound D and the π-π interaction between compound B and pigment C. It is preferred that
Furthermore, the resin composition obtained by melt-kneading may be rolled with two rolls or the like and cooled with water or the like in the cooling step.
Next, the cooled product of the resin composition is pulverized to a desired particle size in the pulverization step. In the pulverization step, for example, after coarse pulverization with a pulverizer such as a crusher, a hammer mill, or a feather mill, for example, a kryptron system (manufactured by Kawasaki Heavy Industries), a super rotor (manufactured by Nisshin Engineering), a turbo mill Finely pulverize with a turbomill (made by Turbo Industries) or air jet type fine pulverizer.
Then, if necessary, classification such as inertial class elbow jet (manufactured by Nippon Steel & Mining Co., Ltd.), centrifugal classification turboplex (manufactured by Hosokawa Micron), TSP separator (manufactured by Hosokawa Micron), Faculty (manufactured by Hosokawa Micron) The toner particles are obtained by classification using a machine or a sieving machine.
In addition, if necessary, after pulverization, a hybridization system (manufactured by Nara Machinery Co., Ltd.), a mechano-fusion system (manufactured by Hosokawa Micron), a faculty (manufactured by Hosokawa Micron), or Meteole Inbo MR Type (manufactured by Nippon Pneumatic Co., Ltd.) is used. Thus, the toner particles can be subjected to a surface treatment such as a spheroidizing treatment.

A method for measuring various physical properties of the toner and raw materials in the present invention will be described below.
<Measurement Method of Resin Peak Molecular Weight (Mp), Number Average Molecular Weight (Mn), and Weight Average Molecular Weight (Mw)>
The peak molecular weight (Mp), number average molecular weight (Mn), and weight average molecular weight (Mw) are measured using gel permeation chromatography (GPC) as follows.
First, a sample (resin) is dissolved in tetrahydrofuran (THF) at room temperature over 24 hours. The obtained solution is filtered through a solvent-resistant membrane filter “Maescho Disc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is about 0.8% by mass. Using this sample solution, measurement is performed under the following conditions.
Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Shodex KF-801, 802, 803, 804, 805,
7 series of 806, 807 (made by Showa Denko)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml
In calculating the molecular weight of the sample, standard polystyrene resin (for example, trade name “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F— 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Tosoh Corporation) are used.

<Method for measuring acid value of resin>
The “acid value” of the resin is measured according to JIS-K0070.
Here, the acid value is represented by the number of mg of potassium hydroxide required to neutralize free fatty acid, resin acid and the like contained in 1 g of a sample, and a specific measuring method is as follows.
(1) Reagent (a) Solvent ethyl ether-ethyl alcohol mixed solution (1 + 1 or 2 + 1) or benzene-ethyl alcohol mixed solution (1 + 1 or 2 + 1), these solutions were subjected to N / 10 hydroxylation using phenolphthalein as an indicator immediately before use. Neutralize with potassium ethyl alcohol solution.
(B) Phenolphthalein solution 1 g of phenolphthalein is dissolved in 100 ml of ethyl alcohol (95 v / v%).
(C) N / 10 potassium hydroxide-ethyl alcohol solution Dissolve 7.0 g of potassium hydroxide in as little water as possible, add ethyl alcohol (95 v / v%) to 1 liter, leave it for 2 to 3 days, and filter. The standardization is performed according to JIS K 8006 (basic matters concerning titration during the reagent content test).
(2) Operation Weigh correctly 1 to 20 g of sample, add 100 ml of solvent and a few drops of phenolphthalein solution as an indicator, and shake well until the sample is completely dissolved. In the case of a solid sample, dissolve it by heating on a water bath. After cooling, this is titrated with an N / 10 potassium hydroxide ethyl alcohol solution, and the end point of neutralization is defined as the time when the indicator is slightly red for 30 seconds.
(3) Calculation formula The acid value is calculated by the following formula.
A = (B × f × 5.611) / S
A: Acid value (KOHmg / g)
B: Use amount of N / 10 potassium hydroxide ethyl alcohol solution (ml)
f: Factor of N / 10 potassium hydroxide ethyl alcohol solution S: Sample (g)

<Measurement method of softening point of resin>
The softening point of the resin is measured by using a constant load extrusion type capillary rheometer “flow characteristic evaluation device Flow Tester CFT-500D” (manufactured by Shimadzu Corporation) according to the manual attached to the device. In this device, while applying a constant load from the top of the measurement sample with the piston, the measurement sample filled in the cylinder is heated and melted, and the melted measurement sample is pushed out from the die at the bottom of the cylinder, and the piston drop amount at this time A flow curve showing the relationship between temperature and temperature can be obtained.
In the present invention, the “melting temperature in the 1/2 method” described in the manual attached to the “flow characteristic evaluation apparatus Flow Tester CFT-500D” is the softening point. The melting temperature in the 1/2 method is calculated as follows. First, ½ of the difference between the piston lowering amount Smax at the time when the outflow ends and the piston lowering amount Smin at the time when the outflow starts is obtained (this is X. X = (Smax−Smin) / 2). Then, the temperature of the flow curve when the piston descending amount is X in the flow curve is the melting temperature in the 1/2 method.
As a measurement sample, about 1.0 g of resin is compression-molded at about 10 MPa using a tablet molding compressor (for example, NT-100H, manufactured by NPA System Co., Ltd.) in an environment of 25 ° C. for about 60 seconds. A cylindrical shape having a diameter of about 8 mm is used.
The measurement conditions of CFT-500D are as follows.
Test mode: Temperature rising start temperature: 50 ° C
Achieving temperature: 200 ° C
Measurement interval: 1.0 ° C
Temperature increase rate: 4.0 ° C./min
Piston cross-sectional area: 1.000 cm ²
Test load (piston load): 10.0 kgf (0.9807 MPa)
Preheating time: 300 seconds Die hole diameter: 1.0 mm
Die length: 1.0mm

<Measurement method of peak temperature of maximum endothermic peak of wax>
The peak temperature of the maximum endothermic peak of the wax is measured according to ASTM D3418-82 using a differential scanning calorimeter “Q1000” (manufactured by TA Instruments). The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium.
Specifically, about 10 mg of wax is precisely weighed, placed in an aluminum pan, and an empty aluminum pan is used as a reference. Measurement is performed at ° C / min. In the measurement, the temperature is once raised to 200 ° C., subsequently lowered to 30 ° C., and then the temperature is raised again. The temperature showing the maximum endothermic peak of the DSC curve in the temperature range of 30 to 200 ° C. in the second temperature raising process is defined as the peak temperature of the maximum endothermic peak of the wax.

<Method for measuring BET specific surface area of inorganic fine particles>
The BET specific surface area of the inorganic fine particles is measured according to JIS Z8830 (2001). A specific measurement method is as follows.
As a measuring device, an “automatic specific surface area / pore distribution measuring device TriStar 3000 (manufactured by Shimadzu Corporation)” which employs a gas adsorption method by a constant volume method as a measuring method is used. Setting of measurement conditions and analysis of measurement data are performed using dedicated software “TriStar3000 Version 4.00” attached to the apparatus, and a vacuum pump, a nitrogen gas pipe, and a helium gas pipe are connected to the apparatus. The value calculated by the BET multipoint method using nitrogen gas as the adsorption gas is taken as the BET specific surface area of the inorganic fine particles in the present invention.
The BET specific surface area is calculated as follows.
First, nitrogen gas is adsorbed onto the inorganic fine particles, and the equilibrium pressure P (Pa) in the sample cell and the nitrogen adsorption amount Va (mol · g ⁻¹ ) of the inorganic fine particles at that time are measured. The relative pressure Pr, which is a value obtained by dividing the equilibrium pressure P (Pa) in the sample cell by the saturated vapor pressure Po (Pa) of nitrogen, is plotted on the horizontal axis, and the nitrogen adsorption amount Va (mol · g ⁻¹ ) is plotted on the vertical axis. The adsorption isotherm is obtained. Next, a monomolecular layer adsorption amount Vm (mol · g ⁻¹ ), which is an adsorption amount necessary for forming a monomolecular layer on the surface of the inorganic fine particles, is obtained by applying the following BET equation.
Pr / Va (1-Pr) = 1 / (Vm * C) + (C-1) * Pr / (Vm * C)
(Here, C is a BET parameter, which is a variable that varies depending on the measurement sample type, adsorbed gas type, and adsorption temperature.)
The BET equation is interpreted as a straight line with an inclination of (C-1) / (Vm × C) and an intercept of 1 / (Vm × C), where Pr is X axis and Pr / Va (1-Pr) is Y axis. Yes (this line is called a BET plot).
Straight line slope = (C-1) / (Vm × C)
Straight line intercept = 1 / (Vm × C)
When the measured value of Pr and the measured value of Pr / Va (1-Pr) are plotted on a graph and a straight line is drawn by the least square method, the slope and intercept value of the straight line can be calculated. Vm and C can be calculated by solving the simultaneous equations of the slope and intercept using these values.
Furthermore, the BET specific surface area S (m ² / g) of the inorganic fine particles is calculated from the calculated Vm and the molecular occupation cross-sectional area of the nitrogen molecule (0.162 nm ² ) based on the following formula.
S = Vm × N × 0.162 × 10 ⁻¹⁸
(N is Avogadro's number (mol- ¹ ).)
The measurement using this apparatus follows the “TriStar 3000 Instruction Manual V4.0” attached to the apparatus, and specifically, the measurement is performed according to the following procedure.
Thoroughly weigh the tare of a dedicated glass sample cell (stem diameter 3/8 inch, volume about 5 ml) that has been thoroughly cleaned and dried. Then, about 0.1 g of inorganic fine particles are put into this sample cell using a funnel.
The sample cell containing the inorganic fine particles is set in a “pretreatment device Bacrepprep 061 (manufactured by Shimadzu Corporation)” connected with a vacuum pump and a nitrogen gas pipe, and vacuum degassing is continued at 23 ° C. for about 10 hours. During vacuum deaeration, the inorganic fine particles are gradually deaerated while adjusting the valve so that the inorganic fine particles are not sucked into the vacuum pump. The pressure in the cell gradually decreases with deaeration and finally becomes about 0.4 Pa (about 3 mTorr). After completion of vacuum degassing, nitrogen gas is gradually injected to return the inside of the sample cell to atmospheric pressure, and the sample cell is removed from the pretreatment device. Then, the mass of the sample cell is precisely weighed, and the accurate mass of the inorganic fine particles is calculated from the difference from the tare. At this time, the sample cell is covered with a rubber plug during weighing so that the inorganic fine particles in the sample cell are not contaminated by moisture in the atmosphere.
Next, a dedicated “isothermal jacket” is attached to the stem portion of the sample cell containing the inorganic fine particles. Then, a dedicated filler rod is inserted into the sample cell, and the sample cell is set in the analysis port of the apparatus. The isothermal jacket is a cylindrical member having an inner surface made of a porous material and an outer surface made of an impermeable material capable of sucking liquid nitrogen to a certain level by capillary action.
Subsequently, the free space of the sample cell including the connection tool is measured. The free space is measured by measuring the volume of the sample cell using helium gas at 23 ° C., and then measuring the volume of the sample cell after cooling the sample cell with liquid nitrogen using helium gas. It is calculated by converting from the difference in volume. The saturated vapor pressure Po (Pa) of nitrogen is automatically measured separately using a Po tube built in the apparatus.
Next, after performing vacuum deaeration in the sample cell, the sample cell is cooled with liquid nitrogen while continuing the vacuum deaeration. Thereafter, nitrogen gas is gradually introduced into the sample cell to adsorb nitrogen molecules on the inorganic fine particles. At this time, since the adsorption isotherm is obtained by measuring the equilibrium pressure P (Pa) as needed, the adsorption isotherm is converted into a BET plot. Note that the points of the relative pressure Pr for collecting data are set to a total of 6 points of 0.05, 0.10, 0.15, 0.20, 0.25, and 0.30. A straight line is drawn from the obtained measurement data by the least square method, and Vm is calculated from the slope and intercept of the straight line. Furthermore, using the value of Vm, the BET specific surface area of the inorganic fine particles is calculated as described above.

<Method for Measuring Weight Average Particle Size (D4) of Toner Particles>
The weight average particle diameter (D4) of the toner particles is measured with a precision particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) equipped with a 100 μm aperture tube. Measured data with 25,000 effective measurement channels using the dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) for condition setting and measurement data analysis Analyze and calculate.
As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.
Prior to measurement and analysis, the dedicated software is set as follows.
In the “Standard measurement method (SOM) change screen” of the dedicated software, set the total count in the control mode to 50000 particles, the number of measurements is 1 and the Kd value is “standard particles 10.0 μm” (Beckman Coulter Set the value obtained using The threshold and noise level are automatically set by pressing the threshold / noise level measurement button. Also, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the aperture tube flash after measurement is checked.
In the “pulse to particle size conversion setting screen” of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm or more and 60 μm or less.
The specific measurement method is as follows.
(1) About 200 ml of the electrolytic solution is placed in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the analysis software.
(2) About 30 ml of the electrolytic aqueous solution is put in a glass 100 ml flat bottom beaker, and "Contaminone N" (nonionic surfactant, anionic surfactant, organic builder pH 7 precision measurement is used as a dispersant therein. About 0.3 ml of a diluted solution obtained by diluting a 10% by weight aqueous solution of a neutral detergent for washing a vessel (made by Wako Pure Chemical Industries, Ltd.) 3 times with ion-exchanged water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated in a state where the phase is shifted by 180 degrees, and is placed in a water tank of an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikka Ki Bios) with an electrical output of 120 W. A predetermined amount of ion-exchanged water is put, and about 2 ml of the above-mentioned Contaminone N is added to this water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker of (1) installed in the sample stand, the electrolyte solution of (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . Measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) is calculated. The “average diameter” on the analysis / volume statistics (arithmetic average) screen when the graph / volume% is set with the dedicated software is the weight average particle diameter (D4).

Specific examples of the present invention will be described below, but the present invention is not limited to these examples. “Part” and “%” in the following formulations are based on mass unless otherwise specified.
<Binder Resin Production Example 1>
Polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane 76.90 parts by mass (0.167 mol), terephthalic acid 24.10 parts by mass (0.145 mol), and titanium tetra 0.40 parts by mass of butoxide was put into a 4-liter 4-neck flask made of glass, and a thermometer, a stirring rod, a condenser and a nitrogen introducing tube were attached and placed in a mantle heater. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 5 hours while stirring at a temperature of 195 ° C. (first reaction step). Thereafter, 1.90 parts by mass (0.010 mol) of trimellitic anhydride was added and reacted at 175 ° C. for 1 hour (second reaction step), whereby a binder resin 1 was obtained.
The acid value of the binder resin 1 was 8 mgKOH / g, and the hydroxyl value was 66 mgKOH / g. Moreover, the molecular weight by GPC was a weight average molecular weight (Mw) 8,000, a number average molecular weight (Mn) 3,500, a peak molecular weight (Mp) 5,700, and the softening point was 90 degreeC.

<Binder Resin Production Example 2>
71.30 parts by mass (0.155 mol) of polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane, 24.10 parts by mass (0.145 mol) of terephthalic acid, and titanium tetra 0.50 parts by mass of butoxide was placed in a 4-liter four-necked flask made of glass, and a thermometer, a stirring rod, a condenser and a nitrogen introduction tube were attached and placed in a mantle heater. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 3 hours while stirring at a temperature of 195 ° C. (first reaction step). Thereafter, 4.80 parts by mass (0.025 mol) of trimellitic anhydride was added and reacted at 175 ° C. for 12 hours (second reaction step), whereby a binder resin 2 was obtained.
The binder resin 2 had an acid value of 8 mgKOH / g and a hydroxyl value of 18 mgKOH / g. Moreover, the molecular weight by GPC was a weight average molecular weight (Mw) 210,000, a number average molecular weight (Mn) 5,500, a peak molecular weight (Mp) 10,500, and the softening point was 133 degreeC.

<Binder Resin Production Examples 3 to 6>
In the binder resin production example 1, in order to adjust the acid value of the resulting binder resin, the amount of trimellitic anhydride added was 1.15 parts by mass for the binder resin 3 and 3.5 for the binder resin 4. 50 parts by mass, Binder resin 5 was changed to 0.20 parts by mass, Binder resin 6 was changed to 4.70 parts by mass in the same manner as in Binder resin production example 1, except that binder resin 3 6 was obtained. The acid values of the binder resins 3 to 6 are shown below.
-Binder resin 3 Acid value 5mgKOH / g
-Binder resin 4 Acid value 15mgKOH / g
・ Binder resin 5 Acid value 1mgKOH / g
・ Binder resin 6 Acid value 20mgKOH / g
The physical properties other than the acid values of the binder resins 3 to 6 (weight average molecular weight (Mw), number average molecular weight (Mn), peak molecular weight (Mp), softening point) are shown in Table 1.

<Binder Resin Production Examples 7 to 10>
In Binder Resin Production Example 2, in order to adjust the acid value of the obtained binder resin, the amount of trimellitic anhydride added was 4.00 parts by mass for binder resin 7 and 6.6 for binder resin 8. 40 parts by mass,
The binder resins 7 to 10 were obtained in the same manner as in the binder resin production example 2 except that the binder resin 9 was changed to 3.10 parts by mass and the binder resin 10 was changed to 7.60 parts by mass. . The acid values of the binder resins 7 to 10 are shown below.
-Binder resin 7 Acid value 5mgKOH / g
・ Binder resin 8 Acid value 15mgKOH / g
・ Binder resin 9 Acid value 1mgKOH / g
-Binder resin 10 Acid value 20mgKOH / g
The physical properties other than the acid value of the binder resins 7 to 10 (weight average molecular weight (Mw), number average molecular weight (Mn), peak molecular weight (Mp), softening point) are shown in Table 2.

<Production Example 11 of Binder Resin>
-Styrene 80.00 parts by mass-N-butyl acrylate 20.00 parts by mass-2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane
0.80 parts by mass The above components were added dropwise over 3 hours after sufficiently replacing the inside of the container with nitrogen while stirring 200 parts by mass of xylene in a four-necked flask and raising the temperature to 130 ° C. Furthermore, the polymerization was completed under reflux of xylene, and the solvent was distilled off under reduced pressure to obtain a binder resin 11. The acid value of the obtained binder resin 11 was less than the detection lower limit. The glass transition temperature (Tg) is 56 ° C., and the molecular weight by GPC is 50,000 weight average molecular weight (Mw), number average molecular weight (Mn) 10,000, peak molecular weight (Mp) 18,000, and softening point is It was 108 ° C.

<Production Example 1 of Mixed Colorant Containing Compound A, Compound B, and Compound D>
In a pressure reactor autoclave, 30.00 parts by mass of dried dimethylsuccinillosuccinate (1,4-cyclohexanedione-2,5-di-carboxylic acid methyl ester), 7.00 parts by mass of aniline, p- Toluidine 22.00 parts by mass, methanol 300.00 parts by mass and hydrochloric acid (35% by mass) 1.00 parts by mass were added.
The autoclave was sealed and flushed with nitrogen gas to keep the internal pressure of the autoclave at a gauge pressure of 0.1 kg / cm ² . While stirring the mixture, the temperature in the autoclave was raised from 25 ° C. to 85 ° C. at a heating rate of 4.0 ° C./min, and the mixture was reacted at 85 ° C. for 5 hours.
Next, when the reaction mixture was cooled to 30 ° C. or lower, the pressure was released to atmospheric pressure. Thereafter, cooling was continued and the temperature in the autoclave was kept at 25 ° C.
In an autoclave, 40.00 parts by mass of an aqueous sodium hydroxide solution (50% by mass) and 34.60 parts by mass of sodium m-nitrobenzenesulfonate were placed and sealed.
The mixture was stirred for 10 minutes, and the temperature in the autoclave was raised from 25 ° C. to 85 ° C. at a heating rate of 4.0 ° C./min, and the mixture was reacted for 5 hours.
And it cooled again to 30 degrees C or less, and filtered and removed all the solids.
The remaining solution was heated to 40 ° C. while stirring, 18.00 parts by mass of hydrochloric acid (35% by mass) was added dropwise, and the mixture was kept at this temperature for 30 minutes.
Thereafter, the mixture was filtered, and the obtained filter cake was washed with a water / methanol (volume ratio 1/1) mixture and cold water, and then dried to obtain a product.
From the relative peak area ratio in HPLC, the product is a compound of formula (4) that is an intermediate of compound A, a compound of formula (5) that is an intermediate of compound B, and a formula that is an intermediate of compound D. The compound (6) was contained at a mass ratio of 71.80: 24.80: 3.40.

Next, 250.00 parts by mass of polyphosphoric acid containing P ₂ O ₅ (85.0% by mass) was charged into the stirring vessel, and the temperature was raised while stirring and maintained at 90 ° C.
And 45 mass parts of the mixture of this intermediate body was added, and the mixture was heated at 130 degreeC for 3 hours, and the ring-closure reaction was performed. The mixture was cooled to 110 ° C., and 6 parts by mass of water was gradually added over 10 minutes.
Thereafter, the mixture was poured into 750 parts by mass of water at 50 ° C. and stirred at 60 ° C. for 1.5 hours. The solid was collected by filtration and washed with water until the wash water was neutral.
100 parts by mass of the obtained press cake was reslurried in 170 parts by mass of methanol, and the slurry was heated in a pressure resistant reactor at 90 ° C. for 3 hours. The mixture was cooled and the pH was adjusted to the range of 9.0 to 9.5 with sodium hydroxide solution (50% by weight).
The solid was collected by filtration and washed with water. The wet presscake was dried in an oven at 80 ° C. to obtain a mixed colorant 1 in which Compound A, Compound B, and Compound D were mixed.
From the relative peak area ratio in HPLC of the mixed colorant 1, the mixed colorant 1 is represented by the compound A represented by the formula (7), the compound B represented by the formula (8), and the formula (3). Compound D at a mass ratio of 67.80: 28.25: 3.95.

<Production Example 1 of Colorant Master Batch>
Binder resin 1 100.00 parts by mass Mixed colorant 1 67.82 parts by mass C.I. I. Pigment Red 238 32.18 parts by mass / distilled water 100.00 parts by mass The above raw materials are first charged into a kneader-type mixer and heated while being mixed without pressure. After confirming that the raw material in the aqueous phase moves to the molten resin phase when the maximum temperature (necessarily determined by the boiling point of the solvent in the paste. In this case, about 90 to 100 ° C.) is reached, Heat-melt and knead for 30 minutes to sufficiently transfer the pigment in the paste. Then, once the mixer is stopped and the hot water is discharged, the temperature is further raised to 110 ° C., heated and melted and kneaded for about 30 minutes, and when the pigment is dispersed, the water is distilled off and the process is completed. Then, the mixture was cooled, the kneaded product was taken out, and after cooling, the mixture was pulverized to a particle size of about 1 to 2 mm using a hammer mill to obtain a colorant master batch 1.

<Production Examples 2 to 29 of colorant master batch>
In Production Example 1 of the colorant master batch, the formulation was changed as shown in Table 3 to obtain colorant master batches 2 to 29.

<Toner Production Example 1>
(Toner kneading, grinding, classification process)
Colorant master batch 1 (total colorant content 50 mass%) 20.88 parts by mass Binder resin 1 49.56 parts by mass Binder resin 2 40.00 parts by mass Paraffin wax (maximum endothermic peak; 78 ° C.) 5.00 parts by mass, 3,5-di-tert-butylsalicylic acid Al compound 1.00 parts by mass Preliminarily mixed with a Henschel mixer with the above formulation, and the barrel temperature was 150 with a twin screw extruder. The mixture is melt kneaded at a temperature of 0 ° C., and after cooling, coarsely pulverized to a particle size of about 1 to 2 mm using a hammer mill. Subsequently, it was pulverized to a particle size of 20 μm or less with an air jet type pulverizer. Further, the obtained finely pulverized product was classified to obtain toner particles 1 containing a magenta colorant having a weight average particle size distribution of 6.3 μm.
(External toner addition process)
-Toner particles 1 100.00 parts by mass-Titanium oxide fine particles 0.80 parts by mass-Silica fine particles 0.60 parts by mass External addition was performed with a Henschel mixer according to the above formulation to obtain magenta toner 1.
As the titanium oxide fine particles, those obtained by performing surface treatment with 10 parts by mass of isobutyltrimethoxysilane to 100 parts by mass of the titanium oxide raw material having an average primary particle diameter of 50 nm were used.
As silica fine particles, those obtained by subjecting 100 parts by mass of a silica base material having a BET specific surface area of 200 m ² / g produced by the fumed method to surface treatment with 7 parts by mass of hexamethyldisilazane were used.

<Toner Production Examples 2 to 49>
In toner production example 1, toners 2-49 shown in Table 5 were produced in the same manner except that the formulation in the toner kneading step was changed as shown in Table 4.

<Cyan toner production example 1>
In Toner Production Example 1, cyan toner 1 was prepared in the same manner as in Toner Production Example 1 except that the formulation of the colorant master batch and the formulation in the toner kneading, pulverization, and classification steps were changed as follows. Got.
(Prescription of colorant master batch of cyan toner 1)
Binder resin 1 100.00 parts by mass I. Pigment Blue 15: 3 100.00 parts by mass / distilled water 100.00 parts by mass (toner kneading, pulverization, classification step)
Cyan master batch 1 (total colorant content 50 mass%) 14.00 parts by mass Binder resin 1 53.00 parts by mass Binder resin 2 40.00 parts by mass Paraffin wax (maximum endothermic peak; 78 ° C) 5.00 parts by mass · 3,5-di-tert-butylsalicylic acid Al compound 1.00 parts by mass

<Production example 1 of magnetic core particles>
Process 1 (weighing / mixing process):
・ Fe ₂ O ₃ 60.2 mass%
· MnCO ₃ 33.9% by weight
Mg (OH) ₂ 4.8% by mass
・ SrCO ₃ 1.1 mass%
The ferrite raw material was weighed so as to achieve the above composition ratio. Thereafter, the mixture was pulverized and mixed for 2 hours in a dry ball mill using zirconia balls having a diameter of 10 mm.
Step 2 (temporary firing step):
After pulverization and mixing, firing was performed in the atmosphere at a temperature of 1000 ° C. for 1.5 hours using a burner-type firing furnace to prepare calcined ferrite. The composition of the ferrite was as follows.
(MnO) _0.387 (MgO) _0.108 (SrO) _0.010 (Fe ₂ O ₃ ) _0.495
Step 3 (grinding step):
After pulverizing to about 0.4 mm with a crusher, 30 parts by mass of water was added to 100 parts by mass of calcined ferrite using a ball of stainless steel having a diameter of 10 mm, and pulverized with a wet ball mill for 8 hours.
The slurry was pulverized for 4 hours by a wet bead mill using zirconia beads having a diameter of 1.0 mm to obtain a ferrite slurry.
Process 4 (granulation process):
To the ferrite slurry, 2.0 parts by mass of polyvinyl alcohol was added as a binder with respect to 100 parts by mass of calcined ferrite, and granulated into spherical particles of about 35 μm with a spray dryer (manufacturer: Okawahara Chemical).
Process 5 (main baking process):
In order to control the firing atmosphere, firing was performed at a temperature of 1400 ° C. for 2.5 hours in an electric furnace in a nitrogen atmosphere (oxygen concentration of 0.01% by volume or less).
Process 6 (screening process):
After the aggregated particles were crushed, coarse particles were removed by sieving with a sieve having an opening of 250 μm to obtain magnetic core particles 1.

<Manufacture example 1 of a magnetic carrier>
・ Straight silicone resin (SR2411 Toray Dow Corning) 20.0% by mass
(Kinematic viscosity in 20% by weight toluene solution 1.1 × 10 ⁻⁴ m ² / sec)
・ Γ-aminopropyltriethoxysilane 0.5% by mass
・ Toluene 79.0% by mass
The said material was mixed so that it might become the said composition ratio, and the resin liquid 1 was obtained.
100 parts by mass of magnetic core particles 1 were charged into a Nauter mixer so that the resin liquid 1 was 1.2 parts by mass as a resin component. It heated at 70 degreeC under pressure reduction, mixed by 1.7S < ^-1 > (100 rpm), and solvent removal and application | coating operation were performed over 4 hours. Thereafter, the obtained sample was transferred to a Julia mixer, heat-treated for 3 hours at a temperature of 200 ° C. in a nitrogen atmosphere, and then classified with a sieve having an opening of 70 μm to obtain a magnetic carrier 1. 50 of volume distribution standard of the obtained magnetic carrier 1
The% particle size (D50) was 36.8 μm.

<Examples 1-42 and Comparative Examples 1-7>
The toner 1 and the magnetic carrier 1 are mixed with a V-type mixer (V-10 type: Tokusu Seisakusho Co., Ltd.) at 0.5 s ⁻¹ and a rotation time of 5 min so that the toner concentration becomes 8% by mass, and a two-component system. Developer 1 was obtained.
Further, the toner and magnetic carrier to be combined were changed as shown in Table 6 to obtain a two-component developer 2 to 49 and a two-component developer C. And it evaluated as the two-component system developer of Examples 1-42 and Comparative Examples 1-7. The results are shown in Table 7.

<Method for evaluating coloring power of toner>
A two-component developer 1 is used in the developer unit of the magenta station using a remodeled machine of imageRUNNER ADVANCE C5051 made by Canon as a full-color copying machine.
Was evaluated.
The printing speed was set to 1.5 times the normal speed (A4 horizontal feed 76.5 sheets / min).
The evaluation environment is a normal temperature and humidity environment (23 ° C., 50% RH), and the evaluation paper is copy paper CS-814 (A4, basis weight 81.4 g / m ² ) sold by Canon Marketing Japan Inc. It was.
First, in the evaluation environment, the relationship between the image density and the amount of applied toner on the paper was examined by changing the amount of toner applied on the paper.
Next, the image density of the FFH image (solid portion) was adjusted to 1.55, and the amount of applied toner was determined when the image density was 1.55.
The FFH image is a value in which 256 gradations are displayed in hexadecimal, and 00H is the first gradation (white background), and FFH is the 256th gradation (solid part).
The image density was measured using an X-Rite color reflection densitometer (500 series: manufactured by X-Rite).
From the applied toner amount (mg / cm ² ), the coloring power of the toner was evaluated according to the following criteria.
(Evaluation criteria)
A: Less than 0.45 Excellent B: 0.45 or more, less than 0.55 Good C: 0.55 or more, less than 0.65 D: 0.65 or more, which is a level that is not a problem in the present invention Unacceptable in the present invention

(Evaluation of blue color reproducibility of toner)
Using a modified machine of Canon full-color copier imageRUNNER ADVANCE C5051 as the image forming apparatus, the two-component developer 1 is introduced into the developer unit of the magenta station, and the two-component developer C is introduced into the developer unit of the cyan station. And evaluated.
The printing speed was set to 1.5 times the normal speed (A4 horizontal feed 76.5 sheets / min).
The evaluation environment is a normal temperature and humidity environment (23 ° C., 50% RH), and the evaluation paper is copy paper CS-814 (A4, basis weight 81.4 g / m ² ) sold by Canon Marketing Japan Inc. It was.
Using the two-component developer 1 and the two-component developer C, a blue image as a secondary color was formed. At this time, a separation image was formed from 00H (solid white) to FFH image (solid portion) with 16 gradations.
In the secondary color image formation, the applied amount of the FFH image (solid portion) of the two-component developer 1 was set to an applied amount at which the image density in a single color is 1.55.
For the two-component developer C, the loading amount of the FFH image (solid portion) was adjusted to 0.45 mg / cm ² . The applied amount of 0.45 mg / cm ² is an applied amount at which the image density of the two-component developer C in a single color is 1.55.
The obtained 16-tone secondary color (blue) image was subjected to L ^* , a ^* , b ^{* of} each tone image using SpectroScan Transmission (manufactured by GretagMacbeth) (measurement condition: D ₅₀ viewing angle 2 °) ^. And C ^* of each gradation was obtained from the following equation.
C ^* = {(a ^* ) ² + (b ^* ) ² } ^0.5
C ^* of each gradation was compared, and the largest C ^* (C ^* max) was obtained and used as an index for evaluating blue reproducibility. The larger C ^* max, the better the blue reproducibility, and the evaluation was performed according to the following criteria.
(Evaluation criteria)
A: 55 or more Excellent B: 50 or more, less than 55 Good C: 42 or more, less than 50 Level D: no problem in the present invention D: less than 42 Unacceptable in the present invention

Claims (5)

A toner having toner particles containing a binder resin and a magenta colorant,
The magenta colorant includes a compound A represented by the following formula (1), a compound B represented by the following formula (2), and Pigment Red 150, Pigment Red 57: 1, Pigment Red 238, and Pigment Red 269. Containing one or more pigments C selected from the group consisting of:
When the content of the compound A with respect to 100 parts by mass of the binder resin is Ya parts by mass and the content of the compound B is Yb parts by mass, Yb / (Ya + Yb) is 0.10 or more and 0.90 or less. And Yb is 0.50 or more and 10.00 or less.

  The Yc / (Ya + Yb + Yc) is 0.20 or more and 0.80 or less, when the content of the pigment C with respect to 100 parts by mass of the binder resin is Yc parts by mass. The toner described. The toner according to claim 1, wherein the magenta colorant further contains a compound D represented by the following formula (3).

  The Yd / (Ya + Yb + Yc + Yd) is 0.01 or more and 0.05 or less when the content of the compound D with respect to 100 parts by mass of the binder resin is Yd parts by mass. The toner described.   The toner according to any one of claims 1 to 4, wherein the binder resin is a polyester resin, and the acid value of the polyester resin is 1 mgKOH / g or more and 20 mgKOH / g or less.