JPH1184735A - Magenta toner for developing electrostatic charge image and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain high image quality, a high density and a clear magenta color and to improve the transparency and highlight reproducibility of a fixed image on an OHP sheet by using a specified solid soln. pigment as a magenta pigment. SOLUTION: This magenta toner contains magenta toner particles contg. a bonding resin and a magenta pigment which is a solid soln. pigment of C.I. Pigment Red 122, C.I. Pigment Red 202 and C.I. Pigment Violet 19. In 1 pt.wt. of the solid soln. pigment, C.I. Pigment Red 122, C.I. Pigment Red 202 and C.I. Pigment Violet 19 are contained in a ratio satisfying 0.3<=A/C<=5.0 and 0.1<=A×C/B<=10.0 (A, B and C are weights of the C.I. Pigment Red 122, C.I. Pigment Red 202 and C.I. Pigment Violet 19, respectively).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a magenta toner for developing an electrostatic image formed by an image forming method such as electrophotography and electrostatic printing, and a method for producing the same.

More specifically, the present invention relates to a magenta toner for developing an electrostatic image for forming a full-color image, which is high in image quality, has excellent color reproducibility, and is triboelectrically stable, and a method for producing the same.

[0003]

2. Description of the Related Art In recent years, digital full-color copying machines and printers have been put into practical use, and high-quality images excellent in color reproducibility without color unevenness as well as in resolving power and gradation can be obtained.

In a digital full-color copying machine, a color image original is color-separated by B (blue), G (green), and R (red) color filters, and then dots of about 20 μm to about 70 μm corresponding to the original image are formed. A black-and-white copy in which a latent image having a diameter is reproduced using toner of each color of Y (yellow), M (magenta), C (cyan), and B (black) and utilizing a subtractive color mixing effect at the time of heat and pressure fixing. A large amount of toner is transferred from the photoconductor to the intermediate transfer
Alternatively, it is necessary to transfer to a transfer material without intervention.

[0005] Among the color toners, magenta toner is important for reproducing skin color, and furthermore, excellent developability is required because the skin tone of a human image is halftone.

Hitherto, quinacridone colorants, thioindigo colorants, xanthene colorants, monoazo colorants, perylene colorants, and diketopyrrolopyrrole colorants have been known as colorants for magenta toners.

For example, JP-B-49-46951 proposes a 2,9-dimethylquinacridone pigment, JP-A-55-26574 proposes a thioindigo pigment, and JP-A-59-57256. A gazette of xanthene type is proposed in the gazette, and a diketopyrrolopyrrole-type pigment is proposed in JP-A-2-210449.
Japanese Patent No. 42383 proposes an anthraquinone dye.

Further, in order to adjust the transparency and color of the colorant, a pigment compound is not used alone,
No. 477, and a quinacridone pigment in a mixed crystal state as disclosed in JP-A-62-291669 (corresponding to US Pat. No. 4,777,105). Methods are also known.

These magenta colorants have good affinity for the binder resin and good light fastness. A magenta toner excellent in triboelectric charging characteristics and color tone can be obtained, but it satisfies transparency and is more faithful to the original. In order to obtain a proper image, a magenta toner having further improved color tone, saturation, and electrophotographic characteristics has been desired.

[0010]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a magenta toner for developing an electrostatic image, which solves the above-mentioned problems.

SUMMARY OF THE INVENTION An object of the present invention is to provide a magenta toner for developing an electrostatic charge image capable of obtaining a very clear magenta color with high image density.

An object of the present invention is to provide a magenta toner for developing an electrostatic image, which is excellent in transparency in a fixed image of an OHP sheet.

An object of the present invention is to provide a magenta toner for developing an electrostatic image, which is excellent in reproducibility of a highlight portion (halftone portion).

An object of the present invention is to provide a magenta toner for developing an electrostatic image, which is excellent in negative chargeability and excellent in electrophotographic characteristics.

An object of the present invention is to provide a manufacturing method for producing the magenta toner.

[0016]

SUMMARY OF THE INVENTION The present invention is a magenta toner for developing an electrostatic image having magenta toner particles containing at least a binder resin and a magenta pigment, wherein the magenta pigment is C.I. C.
I. Pigment Red 122), C.I.
Pigment Red 202 (CI Pigment R)
ed 202) and C.I. Pigment Violet 19 (CI Pigment Violet 1)
9) A magenta toner for developing an electrostatic image, which is a solid solution pigment.

Further, according to the present invention, a polymerizable monomer composition is prepared by mixing a polymerizable monomer, a magenta pigment and a polymerization initiator, and the polymerizable monomer composition is dispersed in an aqueous medium. Magenta toner that produces polymerizable monomer composition particles by polymerization and polymerizes styrene monomer in the polymerizable monomer composition particles in an aqueous medium to form a binder resin to produce magenta toner particles Wherein the magenta toner particles contain a binder resin formed from a polymerizable monomer, and the magenta pigment is C.I. Pigment Red 122 (C.I.
Pigment Red 122), C.I. Pigment Red 202 (CI Pigment Red 122)
202) and C.I. Pigment Violet 1
The present invention relates to a method for producing a magenta toner, which is a solid solution pigment of CI Pigment Violet 19 (CI Pigment Violet 19).

[0018]

DETAILED DESCRIPTION OF THE INVENTION One of the features of the present invention is that a specific solid solution pigment is contained in magenta toner particles.

The solid solution pigment used in the present invention is generally obtained by mixing at least three types of magenta pigments in a step prior to the dehydration step and the pigmentation step in the pigment production process, followed by dehydration and pigmentation. . Since the solid solution pigment used in the present invention is easily crushed, the pigment particles can be easily dispersed to near the primary particle size.

As the combination of solid solutions, those having a structure as close as possible are used in combination due to the stability of the structure and the ease of production. Particularly, in view of the balance of light resistance, tinting strength, negative triboelectric charging property and color mixing property, two kinds of substituted quinacridone pigments having the following structures and an unsubstituted quinacridone pigment are used in combination.

[0021]

[Outside 13]

C. I. Pigment Violet
No. 19 is liable to change in light resistance and coloring power depending on its crystal structure. I. Pigment Red 122 and C.I. I. Pigment Red 202 to form a solid solution. Further, the hue of the solid solution is C.I. I. By changing the mixing ratio of Pigment Violet 19 and the setting of conditions during crystallization, it is possible to expand the hue space of the solid solution without impairing the saturation and brightness of the pigment.

The solid solution pigment is C.I. I. Pi
gment Red 122, C.I. I. Pigment
Red 202 and C.I. I. Pigment Vio
It is preferable that let 19 be contained in the following ratio.

0.3 ≦ A / C ≦ 5.0 0.1 ≦ A × C / B ≦ 10.0 wherein A is C.C. I. Pigment Red 12
2 shows the compounding weight of B. I. Pigment R
ed 202, wherein C is C.E. I. Pigm
ent Violet 19 is shown)

When the solid solution pigment satisfies the above conditions,
Improves the negative chargeability of magenta toner, improves dispersibility in polymerizable monomers, improves dispersibility in binder resin, improves coloring power, and improves color mixing with other color toners As a result, the color reproduction range of the chromaticity diagram comes to a suitable position.

When the value of A / C is less than 0.3, the coloring power of the solid solution pigment decreases, and the image density of the magenta toner decreases. When the value of A / C exceeds 5.0, the negative frictional charging property of the solid solution pigment is reduced and the positive frictional charging property is improved. Therefore, when the magenta toner has the negative frictional charging property, the negative frictional charging of the magenta toner is And fog is likely to occur. On the other hand, when the value of A / C exceeds 5.0, the dispersibility in the polymerizable monomer or the binder resin decreases, and the coloring power of the magenta toner particles decreases.

When the value of A × C / B is less than 0.1,
The color tone of the magenta toner is likely to deviate from a suitable range. Further, when the value of A × C / B is less than 0.1,
Since the solid solution pigment has a strong negative triboelectric charging property and the solid solution pigment particles have a strong electrostatic self-aggregation force, the dispersibility of the solid solution pigment in the polymerizable monomer or the binder resin is reduced. A × C
When the value of / B exceeds 10.0, the negative frictional charging property of the solid solution pigment is reduced, and the positive frictional charging property is improved. Therefore, when the magenta toner has the negative frictional charging property, the negative frictional charging property of the magenta toner is reduced. As a result, fog is easily generated, and magenta toner is easily scattered from the developing device.

The solid solution pigment is C.I. I. P
0.5 to 0.85, i.g.
More preferably, it contains 0.55 to 0.80 parts by weight, and C.I.
I. Pigment Red 202 from 0.03-0.
35, more preferably 0.05 to 0.30 parts by weight. I. Pigment Violet 19 is 0.06 to 0.40, more preferably 0.10 to 0.3.
It is good to contain 5 parts by weight.

The production of solid solution pigments is described, for example, in US Pat.
No. 60510, the solid solution component is simultaneously recrystallized from sulfuric acid or a suitable solvent and subsequently subjected to a solvent treatment (after salt grinding), DE-A-12173.
No. 33, a method of subjecting an appropriately substituted diaminoterephthalic acid mixture to a solvent treatment after cyclization.

The magenta toner particles of the present invention are prepared by mixing a polymerizable monomer such as a styrene monomer, if necessary, another vinyl monomer, a magenta solid solution pigment, a polar resin and a polymerization initiator to form a polymerizable monomer composition. The polymerizable monomer composition is dispersed in an aqueous medium to produce particles of the polymerizable monomer composition, and the styrene monomer in the particles of the polymerizable monomer composition is polymerized in the aqueous medium. It is preferably generated as follows.

When magenta toner particles are produced by such a production method, the magenta solid solution pigment is dispersed to near the primary particles when preparing the polymerizable monomer composition. When a polar resin having an acid value of 3.0 to 20.0 mgKOH / g is used, the re-aggregation of the particles of the magenta solid solution pigment having a nitrogen atom is suppressed, so that the coloring power, brightness and chroma of the magenta toner particles are improved. Because you do.

The polar resin used in the present invention is capable of reaggregating a solid solution pigment while being uniformly dispersed in the polymerizable monomer composition at the initial stage of polymerization of the polymerizable monomer in the polymerizable monomer composition particles. Has both a function of suppressing the water content and a function of stabilizing the particles of the polymerizable monomer composition in an aqueous medium, so that the acid value of the polar resin is 3.0 to 20.0 (mgKOH /
g) is preferable.

If the acid value of the polar resin is less than 3.0 mgKOH / g, the affinity between the polar resin and the solid solution pigment is low, and the pigment is easily separated. Is likely to decrease. If the acid value of the polar resin exceeds 20.0 mgKOH / g, the dispersibility of the polar resin in the styrene monomer (non-polar liquid) decreases because the cohesiveness between the molecular chains of the polar resin increases. for that reason,
The stabilization of the particles of the polymerizable monomer composition by the polar resin in the aqueous medium is reduced, and the production stability of the magenta toner particles is reduced.

Considering the suppression of re-aggregation of the solid solution pigment,
It is preferable that the polar resin is contained in an amount of 1 to 20% by weight, more preferably 2.0 to 10.0 (wt%), based on the magenta toner particles. More preferably, it is performed.

[0035]

[Outside 14]

When the amount of the polar resin is less than 1 wt%, the effect of the addition is small and the toner tends to have a low negative triboelectric chargeability. If the amount of the polar resin exceeds 20% by weight, the viscosity of the polymerizable monomer composition will increase, making granulation in an aqueous medium difficult and reducing the production stability.

Further, when the value of the above expression is less than 5, fog and toner scattering tend to appear on the magenta toner.

On the other hand, when the value of the above formula exceeds 20, the amount of the fine powder component tends to increase during the production of magenta toner particles by a polymerization method in an aqueous medium, which is not preferable.

As the polar resin, those which do not contain an unsaturated group capable of reacting with the styrene monomer in the molecule are preferred. It is not preferable to use a polar resin having a reactive unsaturated group, since a cross-linking reaction occurs between the styrene monomer and the polar resin, and the color mixing property decreases.

Examples of the polar resin include a saturated polyester resin, an epoxy resin, a styrene-acrylic acid copolymer, a styrene-methacrylic acid copolymer, and a styrene-maleic acid copolymer. Among them, a saturated polyester resin or an epoxy resin is preferable as the polar resin, and a saturated polyester resin is particularly preferable in terms of easy control of an acid value in terms of fluidity, negative triboelectric charging characteristics, and transparency of toner particles.

The polar resin has a number average molecular weight (Mn) of 2,5.
When it is from 00 to 10,000, the solubility in the styrene monomer, the suppression of re-aggregation of the solid solution pigment particles, the ease of granulation of the polymerizable monomer composition in an aqueous medium, and the large number of magenta toner particles This is preferable from the viewpoint of improvement in sheet durability.

In the present invention, the solid solution pigment may be dispersed in a styrene monomer together with a polar resin in advance and mixed well, and then a polymerization initiator is added to prepare a weight monomer composition. preferable.

In the present invention, the styrene monomer o (m, p) -methylstyrene, m
A substituted styrene monomer such as (p) -ethylstyrene;
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, ( (Meth) acrylate monomers such as behenyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and diethylaminoethyl (meth) acrylate; butadiene, isoprene, cyclohexene, A monomer such as (meth) acrylonitrile and acrylamide may be added. Preferably, the publication Polymer Handbook, 2nd edition III-
According to calculations using the theoretical glass transition temperature (Tg) described in P139 to 192 (manufactured by John Wiley & Sons), a styrene monomer and another monomer are appropriately mixed and used so as to show 50 to 85 ° C. If the theoretical glass transition temperature is less than 50 ° C., problems tend to occur in terms of the storage stability of the toner and the durability stability of the toner.
Is exceeded in the case of full-color image formation.
The transparency of the HP image decreases.

The styrene polymer, styrene copolymer or a mixture thereof and the polar resin have a number-average molecular weight (Mn) of 5,000 to 1, as measured by gel permeation chromatography (GPC) of a THF-soluble component. 00
The weight average molecular weight (Mw) and the number average molecular weight (Mn) ratio (Mw / Mn) is preferably 2 to 100 (preferably 5 to 50).

In the present invention, the magenta toner particles comprise 65 to 98% by weight of a binder resin (that is, a styrene polymer, a styrene copolymer or a mixture thereof), 1 to 15% by weight of a magenta pigment, and 1 to 15% by weight of a polar resin. It is good to contain 20 weight% (more preferably 2.0 to 10.0 weight%).

In the magenta toner of the present invention, the endothermic main peak in the DSC endothermic curve measured in accordance with ASTM D3418-8 to improve the offset resistance of the toner and the dispersibility of the solid solution pigment is from 50 to 1.
It is preferable that a low softening point substance of 30 ° C (more preferably 55 to 110 ° C) is contained.

When the maximum main peak value is less than 50 ° C., the self-cohesive force of the low softening point substance becomes weak, and as a result, the high temperature offset property becomes weak, which is not preferable as a magenta toner for forming a full-color image. On the other hand, when the maximum main peak value exceeds 130 ° C., it is not preferable in terms of low-temperature fixability and transparency of the magenta toner.

The temperature of the maximum main peak value is measured in a temperature range of 20 to 200 ° C. using, for example, DSC-7 manufactured by Perkin Elmer. The temperature correction of the device detection unit uses the melting points of indium and zinc, and the heat quantity correction uses the heat of fusion of indium. An aluminum pan was used as a sample, an empty pan was set as a control, and the temperature was raised at a rate of 10 ° C./min. Perform the measurement with.

Considering the offset resistance and the durability of a large number of sheets of magenta toner, the low softening point substance
It is good to contain 25 weight%.

The low softening point substance is preferably a wax because of ease of melting at the time of fixing by heating and pressing. Among them, the carbon number is 1
5 or more long-chain ester moiety

[0051]

[Outside 15] (In the formula, R ₁ represents an organic group having 15 or more carbon atoms.) A wax containing an ester compound is preferred from the viewpoint of offset resistance and transparency. Particularly, a wax containing an ester compound represented by the following formulas (1) to (5) is preferable.

Formula (1) R ₂ —COO—R _{3 wherein} R ₂ and R ₃ represent a saturated hydrocarbon group having 15 to 45 carbon atoms. R ₂ and R ₃ are preferably alkyl groups.

[0053]

[Outside 16] [In the formula, R ₄ and R ₆ each represent an organic group having 15 to 32 carbon atoms, and R ₅ represents an organic group having 2 to 200 carbon atoms. ] Preferably R ₄ and R ₆ are alkyl groups, R ₅
Is preferably an alkylene group.

[0054]

[Outside 17] [In the formula, R ₇ and R ₉ each represent an organic group having 15 to 32 carbon atoms, and R ₈ represents an organic group having 2 to 20 carbon atoms. ] Preferably R ₇ and R ₉ are alkyl groups, R ₈
Is preferably an alkylene group.

[0055]

[Outside 18] [Wherein, R ₁₀ and R ₁₁ represent an organic group having 15 to 40 carbon atoms, a and b each represent an integer of 0 to 4, a + b is 4, m and n are each an integer of 0 to 25, , M + n is 1
That is all. R ₁₀ and R ₁₁ are preferably an alkyl group.

[0056]

[Outside 19] [Wherein, R ₁₂ and R ₁₄ represent an organic group having 15 to 40 carbon atoms, R ₁₄ represents a hydrogen atom or an organic group having 1 to 40 carbon atoms, c and d each represent an integer of 0 to 3, c + d is 1 to 3, and z is an integer of 1 to 3. R ₁₂ , R ₁₃ and R ₁₄ are preferably an alkyl group.

The wax preferably used in the present invention is:
Those having a hardness of 0.5 to 5.0 are preferred. The hardness of the wax is a value obtained by preparing a cylindrical sample having a diameter of 20 mm and a thickness of 5 mm, and then measuring Vickers hardness using, for example, a dynamic ultra-micro hardness tester (DUH-200) manufactured by Shimadzu Corporation. The measurement conditions are as follows. After displacing 10 μm under a load speed of 9.67 mm / sec with a load of 0.5 g and holding it for 15 seconds, the resulting dent shape is measured to determine the Vickers hardness. When the hardness is less than 0.5, the pressure dependency and the process speed dependency of the fixing device are increased, and the low-temperature offset resistance is reduced. On the other hand, when the hardness is more than 5.0, the storage stability of the toner is reduced. Since its own self-cohesive force is also small, high-temperature offset resistance is reduced.

Specific examples of the ester compound contained in the ester wax are shown below.

[0059]

[Outside 20]

[0060]

[Outside 21]

[0061]

[Outside 22]

[0062]

[Outside 23]

In the present invention, the toner particles preferably contain 5 to 25% by weight of the ester wax. If the content of the ester wax is less than 5 wt%, the effect of the present invention is not sufficiently exhibited, and the offset resistance is slightly reduced.

When the content of the ester wax is 25
If the amount exceeds wt%, the durability of a large number of sheets tends to decrease, and the blocking resistance also decreases.

The magenta toner of the present invention may contain a negative charge control agent. A negative charge control agent which is colorless or light-colored, has a fast charging speed of the magenta toner, and can stably maintain a constant charge amount is preferable.

In the case where magenta toner particles are produced directly by a polymerization method, a charge control agent which has no polymerization inhibition and has a small amount of a solubilized substance in an aqueous medium is particularly preferable. Specific compounds include metal compounds of salicylic acid, alkylsalicylic acid, dialkylsalicylic acid, naphthoic acid, or dicarboxylic acid as negative charge control agents; sulfonic acids, high molecular compounds having carboxylic acids in their side chains, boron compounds,
Examples include a urea compound, a silicon compound, and carricks arene.

Among them, a metal compound of an aromatic hydroxycarboxylic acid is preferable because it is colorless or pale and has excellent controllability of negative charge.

The content of the charge control agent is preferably 0.5 to 10% by weight based on the magenta toner particles.

As the polymerization initiator used in the polymerizable monomer composition, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,
Azo polymerization initiators such as 4-dimethylvaleronitrile and azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide;
Peroxide-based polymerization initiators such as 2,4-dichlorobenzoyl peroxide and lauroyl peroxide are exemplified.

The amount of the polymerization initiator to be added varies depending on the desired degree of polymerization, but is generally 0.1 to the polymerizable monomer.
5 to 20% by weight is added. The polymerization initiator varies slightly depending on the type of polymerization method, but is used alone or in combination with reference to the 10-hour half-life temperature. If necessary, a crosslinking agent, a chain transfer agent, and a polymerization inhibitor may be further used to control the degree of polymerization.

Aqueous media used for producing magenta toner particles include inorganic dispersants such as tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, and water. Magnesium oxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate,
Bentonite, silica, and alumina are exemplified. Examples of organic dispersants include polyvinyl alcohol, gelatin,
Examples include methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salts of carboxymethylcellulose, and starch. These dispersants are used in an amount of 0.2 to 2.0 based on 100 parts by weight of the polymerizable monomer.
It is preferred to use parts by weight. The dispersant is preferably used in an amount of 0.01 to 0.5 parts by weight based on 100 parts by weight of water.

As these dispersants, commercially available ones may be used as they are, but in order to obtain finely dispersed particles having a uniform particle size, it is necessary to form the inorganic compound under high-speed stirring in an aqueous medium. Is also preferred. For example, in the case of tricalcium phosphate, a dispersant suitable for a suspension polymerization method can be obtained by mixing an aqueous solution of sodium phosphate and an aqueous solution of calcium chloride under high-speed stirring. A surfactant may be used in an amount of 0.001 to 0.1 part by weight to make these dispersants finer. Specific examples include commercially available nonionic, anionic and cationic surfactants. For example, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate,
There are sodium oleate, sodium laurate, potassium stearate and calcium oleate.

When the direct polymerization method is used, magenta toner particles can be preferably produced by the following production method. A magenta colorant, a polar resin, a low softening point substance, and other additives are added to a polymerizable monomer containing a styrene monomer, and the mixture is dispersed with an attritor. Then, a polymerization initiator is added, and the mixture is homogenized with a homogenizer or an ultrasonic disperser. The polymerizable monomer composition is dissolved or dispersed to prepare a polymerizable monomer composition, and the polymerizable monomer composition is dispersed in an aqueous medium containing a dispersion stabilizer using a stirrer, a homomixer, a homogenizer, or the like, and granulated.

Preferably, the agitation speed and time are adjusted so that the droplet particles of the polymerizable monomer composition have the desired size of the magenta toner particles, and granulation is performed. Thereafter, by the action of the dispersion stabilizer, the particles may be stirred to such an extent that the particle state is maintained and the particles are prevented from settling. The polymerization is carried out at a polymerization temperature of the polymerizable monomer of 40 ° C. or higher, generally 50 to 90 ° C. The temperature may be raised in the latter half of the polymerization reaction, and furthermore, in the latter half of the reaction to remove unreacted polymerizable monomers and by-products that cause odor at the time of fixing the toner image, or partially after the completion of the reaction. The aqueous medium may be distilled off from the reaction vessel. After completion of the reaction, the generated magenta toner particles are filtered, washed, and dried. In the suspension polymerization method, it is usually preferable to use 300 to 3000 parts by weight of the aqueous medium based on 100 parts by weight of the polymerizable monomer composition.

The magenta toner particles used in the magenta toner of the present invention have a shape factor SF-1 of 10
It is preferably from 0 to 150, particularly preferably from 100 to 125.

In the present invention, SF-1 indicating the shape factor is used.
Means, for example, FE-SEM (S-800) manufactured by Hitachi, Ltd.
, 100 toner images enlarged at a magnification of 500 times are sampled at random, and the image information is transmitted via an interface to, for example, an image analyzer (Luzex I, manufactured by Nicole).
Introduced in II) and analyzed, the value calculated by the following equation is defined as shape factor SF-1.

[0077]

[Outside 24] [Wherein, MXLNG indicates the absolute maximum length of the toner particles,
AREA indicates the projected area of the toner particles. ]

The shape factor SF-1 indicates the degree of roundness of the toner particles.

The toner particles having a toner particle shape factor SF-1 larger than 150 gradually change from a spherical shape to an irregular shape, and a decrease in the transfer efficiency is recognized. When using an intermediate transfer body to correspond to various types of transfer materials,
Since the transfer step is performed substantially twice, a decrease in transfer efficiency causes a decrease in toner use efficiency. In recent digital full-color copying machines and digital full-color printers, color image originals are previously stored in B (blue), G (green),
After color separation using an R (red) filter, a dot latent image of 20 to 70 μm is formed on the photoreceptor and Y (yellow), M (magenta), C (cyan), and B (black)
It is necessary to reproduce a multicolor image faithful to a document or color information by utilizing the subtractive color mixing operation using the respective color toners. At this time, since a large amount of Y, M, C, and B toners are applied on the photoreceptor or the intermediate transfer member in accordance with the color information of the document or the CRT, each color toner used in the present invention is extremely High transferability is required. Therefore, in order to maintain good transferability of the toner, it is preferable to use a magenta toner having a large triboelectric charge amount and a toner particle having a shape factor SF-1 of 100 to 150.

To faithfully develop minute latent image dots for higher image quality, the weight average diameter measured by a Coulter counter is 3 to 9 μm (more preferably, 3 to 9 μm).
８8 μm) and a number variation coefficient of 35% or less is preferable. A toner having a weight average diameter of less than 3 μm has a low transfer efficiency, generates a large amount of untransferred toner on a photoreceptor or an intermediate transfer member, and is likely to cause non-uniform unevenness of an image due to fog or poor transfer. When the weight average diameter of the toner exceeds 9 μm, the resolution and dot reproducibility decrease, and fusion to each member is apt to occur. When the number variation coefficient of the toner exceeds 35%, the tendency is further increased. Strengthen.

The various measuring methods in the present invention will be described.

The molecular weights of the binder resin and the polar resin are measured by gel permeation chromatography (GPC).

As a specific method of measuring GPC, a toner was previously prepared by using a Soxhlet extractor with a toluene solvent.
After the time extraction, toluene is distilled off with a rotary evaporator, and further, a low softening point substance such as a release agent is dissolved, but the resin component is sufficiently washed or extracted with an organic solvent (eg, chloroform or the like) which cannot be dissolved. After going, THF
(Tetotahydrofuran) was dissolved in a solution having a pore size of 0.
A sample filtered through a 3 μm solvent-resistant membrane filter is measured using 150C manufactured by Waters. The column configuration is A-801, 802, 803, 8 manufactured by Showa Denko
04, 805, 806, and 807 are connected, and the molecular weight distribution is measured using a standard polystyrene resin calibration curve.

Next, a method of measuring the triboelectric charge amount will be described.

FIG. 1 is a schematic explanatory view of an apparatus for measuring a triboelectric charge amount of a toner. Prepare the magenta toner to be measured. A mixture of magenta toner (without external additives) and carrier whose triboelectric charge is to be measured is 50 to 100 m
Place in a 1-liter polyethylene bottle and shake by hand for about 5 minutes to tribocharge. The carrier is a ferrite carrier coated with silicone resin (average particle size 35 μm)
And the mixing weight ratio of the magenta toner and the carrier is 7:93.

Next, the mixture (toner and carrier) W ₀ (g: about 0.5-1.5 g) is placed in a metal measuring container 2 having a 500-mesh screen 3 at the bottom and a metal lid 4. do. At this time, the weight of the entire measurement container 2 is weighed and
₁ (g). Next, in the suction device 1 (the part in contact with the measurement container 2 is at least insulative), the air is sucked from the suction port 7 and the air volume control valve 6 is adjusted to adjust the pressure of the vacuum gauge 5 to 2450 (h).
pa). In this state, suction is sufficiently performed, preferably for 2 minutes, to remove the toner by suction.

At this time, the frictional charge amount Q (mC /
kg) is defined as follows when the toner is corrected by 100%.

[0088]

[Outside 25] (V (volts) indicates the potential of the electrometer 9, C (μF) indicates the capacity of the condenser 8, W ₂ (g) indicates the weight of the measuring container 2 after suction, and T is the weight of the toner / carrier. Shows the ratio)

The environmental charging stability of the magenta toner is determined by measuring the triboelectric charge amount Q of the toner at high temperature and high humidity (35 ° C., 90% R
H), normal temperature and normal humidity (23 ° C., 60% RH), low temperature and low humidity (1
(5 ° C., 10% RT).

Next, a method for measuring the acid value will be described.

A resin sample (2 to 10 g) was weighed into a 200 ml Erlenmeyer flask, and methanol: toluene = 30: 7.
About 50 ml of a mixed solvent of 0 is added to dissolve the resin. Then, using a mixed indicator of 0.1% promthymol blue and phenol red, titration was performed with a 0.1N potassium hydroxide / ethanol solution evaluated in advance, and the acid value was calculated by the following calculation from the consumption amount of the potassium alcohol solution. Ask for.

Acid value = KOH (ml number) × F × 56.1 /
Sample weight (g) (F indicates a factor of 0.1N potassium hydroxide / ethanol solution)

Next, a method for evaluating coloring power will be described.

A two-component developer is prepared by mixing 7 parts by weight of magenta toner and 93 parts by weight of a ferrite carrier coated with silicone resin. Using the obtained developer, the fixing temperature is made variable, and the toner image is transferred onto a transfer material by a modified full-color copier (CLC500) manufactured by Canon, omitting the fixing oil application mechanism, to obtain a fixed image. At this time, the fixing conditions were as follows: a transfer material used was a weighed 99 g / m ² paper having a gloss level of 4, and the amount of applied toner was 0.5 mg / c.
m ² magenta solid image was obtained, and the image
The fixing temperature is adjusted to be 15. The coloring power is defined as the image density of the single-color solid image.

The gloss was measured according to JIS Z8741 Method 2, and the image density was measured using a reflection densitometer RD918.
(Macbeth).

Next, a method for evaluating the image quality of an image will be described.

A two-component developer is prepared by mixing 7 parts by weight of magenta toner and 93 parts by weight of a ferrite carrier coated with an acrylic resin. Using the obtained developer, the fixing temperature is made variable, the surface material of the upper and lower rollers is made of a fluorine-based resin, and the full color copying machine made by Canon (CLC500) is modified so as to omit the fixing oil applying mechanism.
Transfer the magenta toner image on the transfer material with the remodeling machine,
Obtain a fixed image.

At this time, the fixing conditions were as follows. A monochromatic solid image having a magenta toner amount of 0.5 to 0.7 mg / cm ² was obtained by using a weighed 99 g / m ² paper having a glossiness of 4 as a transfer material. The fixing temperature is adjusted so that the glossiness becomes 10 to 15. The density condition is adjusted so that a gray scale and color patches manufactured by Kodak Co., Ltd. are used as a document and the gray scale is reproduced as faithfully as possible in a full-color copy image, and the maximum density of the magenta (M) single-color copy is 1.1 or more. Adjust the concentration as follows.

The lightness L on a solid image having a magenta (M) color image density of 1.2 was obtained using a modified full-color copying machine.
*, The color reproducibility is evaluated based on the saturation C *, and the image quality uniformity is evaluated using a highlight image having an image density of 0.2.

The evaluation was performed in five stages. The color reproduction range E of the image of Comparative Example 1 was defined by the following equation, and when the value was 100, the color reproduction range: E = ((lightness L *) ² × (color Degree C *) ² )
^1/2 E> 110 = A 105 <E ≦ 110 = B 90 <E ≦ 105 = C 80 <E ≦ 90 = DE ≦ 80 = E

Comparative Example 1
Is evaluated by visual evaluation of five stages of A, B, C, D and E, where B is B.

Next, a transparency image (OHP)
An evaluation method is described for the transparency of.

The transmittance of an OHP transmission image is evaluated as follows.

A commercially available full-color copying machine (CLC500;
Using a remodeling machine manufactured by Canon Inc.), the image is developed and transferred on a transparency sheet at a developing contrast of 320 V under an environment of a temperature of 23 ° C. and a humidity of 65% RH to obtain an unfixed toner image having a gradation. . The obtained unfixed toner image was fixed at an external fixing machine (without an oil coating function; roller diameter of 40 mm) having a fixing roller surface formed of a fluororesin at a fixing temperature of 180 ° and a fixing process speed of 30 mm / sec. Obtain a fixed image.

The image density of the obtained fixed image is 0.4 to 0.1.
6 (halftone portion), the transmittance T% was measured, and when the transmittance of Comparative Example 1 was taken as 100, T%> 110 = A 100 <T% ≦ 110 = B 90 <T% ≦ 105 = C80 <T% ≦ 90 = D T% ≦ 80 = E The relative value was evaluated.

The transmittance was measured using a Shimadzu self-spectrophotometer UV.
2200 (manufactured by Shimadzu Corporation) was used for the measurement. Then, the transmittance of the imaging sheet alone is set to 100%,
The transmittance at the maximum absorption wavelength at 650 nm was measured.

[0107]

The present invention will be described more specifically with reference to the following examples.

Production Example 1 of Solid Solution Pigment

[0109]

[Outside 26] Was cyclized in phosphoric acid to produce 2,9-dimethylquinacridone. The phosphoric acid with 2,9-dimethylquinacridone is dispersed in water, then the 2,9-dimethylquinacridone is filtered off and the crude 2,9-dimethylquinacridone wetted in water (CI Pigmen) is dispersed.
t Red 122) was prepared.

Separately, the following formula

[0111]

[Outside 27] Was cyclized in phosphoric acid to produce 3,10-dichloroquinacridone. Phosphoric acid with 3,10-dichloroquinacridone is dispersed in water and then
Dichloroquinacridone is filtered off and crude 3,10-dichloroquinacridone moistened with water (CI Pig
Ment Red 202) was prepared.

Separately, the following formula

[0113]

[Outside 28] Was cyclized in phosphoric acid to produce unsubstituted quinacridone. The phosphoric acid with quinacridone is dispersed in water, then the quinacridone is filtered off and the crude quinacridone moistened with water (CI Pigment Vi.
olet 19) was adjusted.

Crude 2,9-dimethylquinacridone 70
Parts by weight and crude 3,10-dichloroquinacridone 10
Parts by weight and 20 parts by weight of crude unsubstituted quinacridone are added to a container equipped with a condenser having a mixture of 600 parts by weight of water and 300 parts by weight of ethanol, and 2,9 for 6 hours. -Dimethylquinacridone, 3,
The mixture was heated and refluxed while grinding 10-dichloroquinacridone and unsubstituted quinacridone. After 6 hours, the solid solution pigment was filtered off, washed, and dried to obtain a solid solution magenta pigment (1).

The value of A of the solid solution magenta pigment (1) is 0.1.
70, the value of B is 0.10, and the value of C is 0.2
0, A / C is 3.50, and A × C / B is 1.50.
It was 40.

Production Examples 2 and 3 of Solid Solution Pigments Except that the amounts (weight ratio) of 2,9-dimethylquinacridone, 3,10-dichloroquinacridone and unsubstituted quinacridone were changed as shown in Table 1 below, Solid solution magenta pigments (2) and (3) in the same manner as in Production Example 1.
I got

[0117]

[Table 1]

Production Example of Solid Solution Pigment (a) (Reference Example) 66 parts by weight of crude 2,9-dimethylquinacridone prepared in the same manner as in Production Example 1 and 34 parts by weight of crude unsubstituted quinacridone were added to water. 600 parts by weight and 300 ethanol
The mixture was heated and refluxed while grinding the 2,9-dimethylquinacridone and quinacridone for 5 hours while adding the mixed solution consisting of parts by weight to the vessel equipped with a condenser. After 5 hours, the solid solution pigment was filtered off, washed, dried and ground to obtain a solid solution magenta pigment (a).

Production Example (b) of Solid Solution Pigment (Reference Example) 20 parts by weight of crude 3,10 dichloroquinacridone prepared in the same manner as in Production Example 1 and 80 parts by weight of crude unsubstituted quinacridone were mixed with 600 parts of water. 300 parts by weight and ethanol
The mixture was heated to reflux while grinding the 3,10-dichloroquinacridone and quinacridone for 5 hours while the mixture was added to a container having a mixed solution consisting of parts by weight and having a condenser. After 5 hours, the solid solution pigment was filtered off, washed, dried and pulverized to obtain a solid solution magenta pigment (b).

Example 1 A 0.1 M aqueous solution of Na ₃ PO ₄ and a 1 M aqueous solution of NOCaCl ₂ were prepared. In a four-necked flask equipped with a high-speed stirrer TK-homomixer, 710 parts by weight of ion-exchanged water and 450 parts by weight of a 0.1 mol-Na ₃ PO ₄ aqueous solution were added, and the number of revolutions was adjusted to 12.000. Warmed to 65 ° C. 68 parts by weight of a 1.0 mol-CaCl ₂ aqueous solution is gradually added thereto, and a fine soft water-soluble dispersant Ca ₃ (PO ₄ ) is added.
_An aqueous dispersion medium containing ₂ was prepared.

Styrene monomer 165 parts by weight n-butyl acrylate monomer 35 parts by weight Solid solution magenta pigment (1) 7 parts by weight Saturated polyester resin (polar resin) 10 parts by weight (terephthalic acid-propylene oxide modified) Bisphenol A-trimellitic acid polymer; acid value = 15 mg KO
H / g, Mn = 4500; peak molecular weight = 6000) 2 parts by weight of metal compound of dialkylsalicylic acid (negative charge control agent) 15 parts by weight of ester wax (endothermic main peak value 64.4 ° C.) 15 parts by weight (ester compound (1 ) Is a main component; hardness 3.2) The above mixture was dispersed using an attritor for 3 hours to prepare a pigment dispersion.

1 g of the pigment dispersion was mixed with 9 g of styrene monomer.
The solution was subjected to a sedimentation test in which the solution was allowed to stand for 60 hours while being heated to 70 ° C., and the solid solution magenta pigment (1)
No sedimentation was observed, and it was confirmed that the solid solution magenta pigment (1) had good dispersibility. 2 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator was added to the pigment dispersion to prepare a polymerizable monomer crude product. The polymerizable monomer crude product was charged into an aqueous dispersion medium and granulated for 15 minutes while maintaining the rotation speed of the high-speed stirrer at 12,000 rpm. Thereafter, the agitator of the propeller stirring blade was changed from the high-speed stirrer, and the internal temperature was raised to 60 ° C. for 4 hours while stirring at 50 rpm, and then the temperature was raised to 80 ° C. for 4 hours, and polymerization was continued for a total of 8 hours. After the polymerization was completed, the slurry was cooled, and diluted hydrochloric acid was added to remove the dispersant.

By further washing and drying, magenta toner particles (1) were obtained. The weight average diameter of the magenta toner particles (1) measured by a Coulter counter was 63 μm, the number variation coefficient was 24%, and the shape factor SF-1 was 106. The obtained magenta toner particles (1) are composed of styrene-n-butyl acrylate, about 200 parts by weight of a copolymer, about 7 parts by weight of a solid solution magenta pigment, about 10 parts by weight of a saturated polyester resin, and about 2 parts by weight of a metal compound of dialkylsalicylic acid. Parts and about 15 parts by weight of ester wax.

The obtained magenta toner particles (1) 100
2 parts by weight of hydrophobized titanium oxide fine powder was externally added to the parts by weight to obtain a magenta toner.
93 parts by weight of a magnetic ferrite carrier coated with an acrylic resin were mixed and evaluated for durability as a two-component developer using a modified full-color copying machine CLC500 manufactured by Canon. Under normal temperature and normal humidity (23 ° C., 60%), a stable, clear and good magenta image was obtained without a decrease in developability even after 20,000 sheets were run.

The coloring power was good, and the transparency of OHP was excellent. Table 3 shows the results.

Comparative Example 1 The coloring agent was C.I. I. Pigment Red 122-7
Except that the amount was changed to parts by weight, the same treatment as in Example 1 was carried out to obtain comparative magenta toner particles (1). The weight average diameter of the obtained comparative magenta toner particles (1) is 6.2.
In μm, the number variation coefficient is 58% and the shape factor SF-1 is 10
Nine.

In the same manner as in Example 1, the C.I. I.
Pigment Red 122 was subjected to a sedimentation test. I. Pigment Re
d122 has settled.

Comparative magenta toner particles (1) 1 obtained
2 parts by weight of hydrophobized titanium oxide fine powder was externally added to 00 parts by weight to obtain a magenta toner.
Acrylic resin coated ferrite carrier 9
3 parts by weight were mixed and used as a two-component developer to evaluate durability using a modified full-color copying machine CL500 manufactured by Canon. When 20,000 sheets were durable under normal temperature and normal humidity, a magenta image having fog on a non-image area was obtained due to low chargeability.

The coloring power was lower than that of Example 1, and the transparency of OHP was particularly insufficient for practical use.

Comparative Example 2 The coloring agent was C.I. I. Pigment Violet 19
Comparative magenta toner particles (2) were produced in the same manner as in Example 1 except that the amount was changed to 7 parts by weight. The obtained comparative magenta toner particles (2) have a weight average particle size of 6.7.
μm, the number variation coefficient is 49%, and the shape coefficient S
F-1 was 106.

In the same manner as in Example 1, the C.I. I.
Pigment Violet 19 was subjected to a sedimentation test. I. Pigment V
Iolet 19 has settled.

When the durability of the obtained comparative magenta toner particles (2) was evaluated in the same manner as in Example 1, fog was generated from the beginning and the image quality was poor because the chargeability was lower than in Example 1. Met.

Further, since the dispersibility of the colorant in the toner particles was poor, the coloring power, the color reproducibility, and the OHP transmittance were poor.

Comparative Example 3 C. Instead of the solid solution magenta pigment, C.I. I. Pigment
4.6 parts by weight of Red 122 and C.I. I. Pigm
Comparative magenta toner particles (3) were produced in the same manner as in Example 1 except that 2.4 parts by weight of ent Violet 19 was used. The obtained comparative magenta toner particles (3) had a weight average particle size of 5.9 μm, a number variation coefficient of 56%, and a shape factor SF-1 of 113.

A settling test was conducted on the magenta pigment used in the same manner as in Example 1. As a result, the magenta pigment settled in about 10 hours.

A durability test was performed on the obtained magenta toner particles in the same manner as in Example 1. As a result, as the number of durable sheets was increased, fog occurred and the image quality was poor.

Further, since the dispersibility of the colorant in the toner particles is worse than that of Example 1, the coloring power, the OHP permeability,
In particular, the color reproducibility was poor.

Reference Example 1 Magenta toner particles (a) were produced in the same manner as in Example 1 except that the solid solution magenta pigment (a) was used instead of the solid solution magenta pigment (1). The weight average diameter of the magenta toner particles (a) was 6.2 μm, the number variation coefficient was 28%, and the shape factor SF-1 was 107. The obtained magenta toner particles (a) were composed of styrene-n-butyl acrylate, about 200 parts by weight of a copolymer, about 7 parts by weight of a solid solution magenta pigment, about 10 parts by weight of a saturated polyester resin, and about 2 parts by weight of a metal compound of dialkylsalicylic acid. Parts and about 15 parts by weight of ester wax.

A magenta toner was obtained in the same manner as in Example 1, and a two-component developer was prepared. The evaluation was performed in the same manner as in Example 1. Table 3 shows the results.

Reference Example 2 Magenta toner particles (b) were produced in the same manner as in Example 1 except that the solid solution magenta pigment (b) was used instead of the solid solution magenta pigment (1).

The obtained magenta toner particles (b) had a weight average of 7.7 μm, a number variation coefficient of 35%, and a shape factor SF-1 of 110.

A magenta toner was obtained in the same manner as in Example 1, and a two-component developer was prepared. The evaluation was performed in the same manner as in Example 1. Table 3 shows the results.

Example 2 Magenta toner particles (2) were obtained in the same manner as in Example 1 except that the solid solution magenta pigment (2) was used instead of the solid solution magenta pigment (1). The weight average particle diameter of the magenta toner particles (2) was 6.6 μm, the coefficient of variation was 32%, and the shape factor SF-1 was 109.

A magenta toner was obtained in the same manner as in Example 1, and a two-component developer was prepared. The evaluation was performed in the same manner as in Example 1. Table 3 shows the results.

Example 3 Magenta toner particles (2) were obtained in the same manner as in Example 1 except that the solid solution magenta pigment (3) was used instead of the solid solution magenta pigment (1). The weight average diameter of the magenta toner particles (3) was 6.2 μm, the coefficient of variation was 27%, and the shape factor SF-1 was 108.

A magenta toner was obtained in the same manner as in Example 1, and a two-component developer was prepared. The evaluation was performed in the same manner as in Example 1. Table 3 shows the results.

Example 4 The same treatment as in Example 1 was carried out except that the ester wax in Example 1 was changed to 7 parts by weight of alcohol-modified polypropylene wax (endothermic maximum peak value: 94 ° C.), and magenta toner particles ( 4) was obtained.

The obtained magenta toner particles (4) had a weight average diameter of 6.9 μm, a number variation coefficient of 27%, and a shape factor SF-1 of 114.

A durability test was performed on the obtained magenta toner particles (4) in the same manner as in Example 1. As a result, a clear and good magenta image with stable developing property was obtained.

Example 5 The saturated polyester resin of Example 1 was replaced with a styrene-acrylic resin (styrene-methacrylic acid-methyl methacrylate copolymer; acid value = 12 mg KOH / g; Mn = 6).
Magenta toner particles (5) were obtained in the same manner as in Example 1 except that the peak molecular weight was changed to 700 (peak molecular weight; 10000).

The obtained magenta toner particles (5) had a weight average diameter of 7.4 μm, a number variation coefficient of 31%, and a shape factor SF-1 of 106.

The durability of the obtained magenta toner particles (5) was evaluated in the same manner as in Example 1. As a result, a clear and good magenta image with stable developing property was obtained.

Example 6 The saturated polyester resin of Example 1 was replaced with an epoxy resin (bisphenol A-epichlorohydrin-phthalic anhydride-triethylenetetramine polymer; acid value = 3 mg KOH /
g; Mn = 2800; peak molecular weight: 7500) Magenta toner particles (6) were obtained in the same manner as in Example 1 except that the weight was changed to 5 parts by weight.

The obtained magenta toner particles (6) had a weight average diameter of 4.9 μm, a number variation coefficient of 42%, and a shape coefficient SF-1 of 111.

The obtained magenta toner particles (6) were evaluated for durability in the same manner as in Example 1. As a result, the fogging occurred slightly because the charging property was slightly lower than that in Example 1. A clear and good magenta image with stable properties was obtained.

[0156]

[Table 2]

[0157]

[Table 3]

[0158]

The magenta toner for developing an electrostatic image of the present invention can form a magenta image having a high image density, has a clear magenta color, has excellent transparency in a fixed image of an OHP sheet, and has a negative friction. It is also excellent in chargeability.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram of an apparatus for measuring a triboelectric charge amount of a toner.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Suction machine 2 Measuring container 8 Condenser 9 Electrometer

Claims (73)

[Claims] 1. A magenta toner for developing an electrostatic image having magenta toner particles containing at least a binder resin and a magenta pigment, wherein the magenta pigment is C.I. Pigment Red 122.
(CI Pigment Red 122), C.I.
Eye Pigment Red 202 (CI Pigmen)
t Red 202) and C.I. Pigment Violet 19 (CI Pigment Violet)
19) A magenta toner for developing an electrostatic charge image, which is the solid solution pigment according to 19). 2. The solid solution pigment is C.I. I. P
pigment red 122, C.I. I. Pigmen
t Red 202 and C.I. I. Pigment Vi
2. The magenta toner according to claim 1, containing olet 19 in the following ratio. 0.3 ≦ A / C ≦ 5.0 0.1 ≦ A × C / B ≦ 10.0 [where A is C.I. I. Pigment Red 12
2 shows the compounding weight of B. I. Pigment R
ed 202, wherein C is C.E. I. Pigm
ent Violet 19 is shown) 3. A solid solution pigment comprising C.I. I. P
and C.I. Red 122 in an amount of 0.50 to 0.85 parts by weight. I. Pigment Red 202
From 0.03 to 0.35 parts by weight, and C.I. I. Pigm
3. The magenta toner according to claim 1, comprising 0.06 to 0.40 parts by weight of ent Violet 19. 4. A solid solution pigment comprising C.I. I. P
i.g. Red 0.5 to 0.50 parts by weight of C.I. I. Pigment Red 202
And 0.05 to 0.30 parts by weight of C.I. I. Pigm
3. The magenta toner according to claim 1, comprising 0.10 to 0.35 parts by weight of ent Violet 19. 5. The magenta toner according to claim 1, wherein the magenta toner particles contain a styrene polymer, a styrene copolymer, or a mixture thereof, and a polar resin. 6. The magenta toner particles comprise a binder resin 65 to 65.
98% by weight, 1 to 15% by weight of a magenta pigment and an acid value of 3.
6. The magenta toner according to claim 1, comprising 1 to 20% by weight of a polar resin of 0 to 20.0 mgKOH / g. 7. The magenta toner particles comprise a polar resin of 2.
7. The magenta toner according to claim 6, comprising 0 to 10.0% by weight. 8. The magenta toner according to claim 5, wherein the magenta toner particles contain a magenta pigment and a polar resin having an acid value of 3.0 to 20.0 mgKOH / g so as to satisfy the following formula. . [Outside 1] 9. The magenta toner according to claim 5, wherein the polar resin is a saturated polyester resin. 10. The magenta toner according to claim 9, wherein the saturated polyester resin has a number average molecular weight of 2.500 to 10,000. 11. The magenta toner according to claim 5, wherein the polar resin is an epoxy resin. 12. The epoxy resin has a number average molecular weight of 2.50.
The magenta toner according to claim 11, wherein the number is from 0 to 10.000. 13. The magenta toner according to claim 5, wherein the polar resin is a styrene-acrylic acid copolymer. 14. The styrene-acrylic acid copolymer has a number average molecular weight of 2.500 to 10,000.
3 magenta toner. 15. The magenta toner according to claim 1, wherein the magenta toner particles contain a low softening point substance having an endothermic main peak in a DSC endothermic curve at 55 to 130 ° C. 16. The magenta toner according to claim 15, wherein the magenta toner particles contain 5 to 25% by weight of a low softening point substance. 17. The magenta toner according to claim 15, wherein the low softening point substance is a wax. 18. The low-softening point substance is a long-chain ester moiety having 15 or more carbon atoms. 19. An ester compound having the formula: wherein R ₁ represents an organic group having 15 or more carbon atoms.
Any of the magenta toners. 19. The low softening point substance is represented by the following formula (1): R ₂ —COO—R ₃ (1) wherein R ₂ and R _{3 each} represent a saturated hydrocarbon group having 15 to 45 carbon atoms. The magenta toner according to any one of claims 15 to 18, comprising an ester compound represented by the following formula: 20. The magenta toner according to claim 19, wherein R ₂ and R ₃ are an alkyl group. 21. The low softening point substance is represented by the following formula (2): [In the formula, R ₄ and R ₆ each represent an organic group having 15 to 32 carbon atoms, and R ₅ represents an organic group having 2 to 20 carbon atoms. ]
The magenta toner according to any one of claims 15 to 18, comprising an ester compound represented by the following formula: (22) R ₄ and R ₆ are alkyl groups;
23. The magenta toner according to claim 22, wherein ₅ is an alkylene group. 23. The low-softening point substance is represented by the following formula (3): [In the formula, R ₇ and R ₉ represent an organic group having 15 to 32 carbon atoms, and R ₈ represents an organic group having 2 to 20 carbon atoms. ]
The magenta toner according to any one of claims 15 to 18, comprising an ester compound represented by the following formula: 24. R ₇ and R _{9 each} represent an alkyl group;
24. The magenta toner according to claim 23, wherein ₈ represents an alkylene group. 25. The low softening point substance is represented by the following formula (4): [Wherein, R ₁₀ and R ₁₁ represent an organic group having 15 to 40 carbon atoms, a and b each represent an integer of 0 to 4, a + b is 4, m and n are each an integer of 0 to 25, , M + n is 1
The magenta toner according to any one of claims 15 to 18, comprising an ester compound represented by the following formula: 26. The magenta toner according to claim 25, wherein R ₁₀ and R ₁₁ are alkyl groups. 27. The low softening point substance is represented by the following formula (5): [Wherein, R ₁₂ and R ₁₃ represent an organic group having 15 to 40 carbon atoms, R ₁₄ represents a hydrogen atom or an organic group having 1 to 40 carbon atoms, c and d each represent an integer of 0 to 3, c + d is 1 to 3, and z is an integer of 1 to 3. The magenta toner according to any one of claims 15 to 18, comprising an ester compound represented by the following formula: 28. The magenta toner according to claim 27, wherein R ₁₂ , R ₁₃ and R ₁₄ are an alkyl group. 29. The magenta toner particles have a shape factor SF
The magenta toner according to any one of claims 1 to 28, wherein -1 is 100 to 150. 30. The magenta toner particles have a shape factor SF
The magenta toner according to any one of claims 1 to 28, wherein -1 is 100 to 125. 31. The magenta toner according to claim 1, wherein the magenta toner particles have negative triboelectrification and contain 0.5 to 10% by weight of a negative charge control agent. 32. The magenta toner according to claim 31, wherein the negative charge control agent is a metal compound of an aromatic hydroxycarboxylic acid. 33. Magenta toner particles are obtained by granulating a polymerizable monomer composition containing at least a styrene monomer, a magenta pigment, a polar resin and a polymerization initiator in an aqueous medium, and polymerizing the styrene monomer. The magenta toner according to any one of claims 1 to 32, comprising the produced polymerized magenta toner particles. 34. The polymerizable monomer composition further contains an acrylate ester monomer or a methacrylate ester monomer, and a styrene copolymer produced by polymerization of the monomer in an aqueous medium is used to form polymerized magenta toner particles. 34. The magenta toner of claim 33. 35. The magenta toner according to claim 1, wherein the magenta toner particles have a weight average particle diameter of 3 to 9 μm. 36. The magenta toner according to claim 1, wherein the magenta toner particles have a weight average particle diameter of 3 to 8 μm. 37. A polymerizable monomer composition is prepared by mixing a polymerizable monomer, a magenta pigment and a polymerization initiator, and the polymerizable monomer composition is dispersed in an aqueous medium to form a polymerizable monomer. A method for producing a magenta toner, wherein particles of a monomer composition are produced, and a styrene monomer in the particles of the polymerizable monomer composition is polymerized in an aqueous medium to form a binder resin to produce magenta toner particles. The magenta toner particles contain a binder resin formed from a polymerizable monomer, and the magenta pigment is C.I.
(CI Pigment Red 122), C.I.
Eye Pigment Red 202 (CI Pigmen)
t Red 202) and C.I. Pigment Violet 19 (CI Pigment Violet)
(19) A method for producing a magenta toner, which is a solid solution pigment. 38. A solid solution pigment comprising C.I. I.
Pigment Red 122, C.I. I. Pigme
nt Red 202 and C.I. I. Pigment V
An iolet 19 is contained in the following ratio.
A method for producing a magenta toner. 0.3 ≦ A / C ≦ 5.0 0.1 ≦ A × C / B ≦ 10.0 [where A is C.I. I. Pigment Red 12
2 shows the compounding weight of B. I. Pigment R
ed 202, wherein C is C.E. I. Pigm
ent Violet 19 is shown. ] 39. The method for producing a magenta toner according to claim 37, wherein the polymerizable monomer is a styrene monomer. 40. The binder resin according to claim 3, wherein the binder resin contains a styrene polymer, a styrene copolymer or a mixture thereof.
39. The method for producing a magenta toner according to any one of 7 to 39. 41. The method for producing a magenta toner according to claim 37, wherein the polymerizable monomer composition further contains a polar resin. 42. The solid solution pigment is C.I. I.
Pigment Red 122 from 0.50 to 0.85
Parts by weight, and C.I. I. Pigment Red 20
2 in an amount of 0.03 to 0.35 parts by weight, and C.I. I. Pig
42. The method for producing a magenta toner according to any one of claims 37 to 41, comprising 0.06 to 0.40 parts by weight of Ment Violet 19. 43. The solid solution pigment is C.I. I.
Pigment Red 122 from 0.55 to 0.80
Parts by weight, and C.I. I. Pigment Red 20
2 in an amount of 0.05 to 0.30 parts by weight, and C.I. I. Pig
The method for producing a magenta toner according to any one of claims 37 to 41, wherein 0.1 to 0.35 parts by weight of the Ment Violet 19 is contained. 44. The magenta toner according to claim 37, wherein the magenta toner particles contain a styrene polymer, a styrene copolymer or a mixture thereof, and a polar resin. 45. The magenta toner particles comprise a binder resin 65.
The method for producing a magenta toner according to any one of claims 37 to 44, wherein the method comprises from about 98% by weight to about 98% by weight of the magenta pigment, and from 1 to 20% by weight of the polar resin. 46. The method for producing a magenta toner according to claim 45, wherein the magenta toner particles contain 2.0 to 10.0% by weight of a polar resin. 47. The magenta toner according to claim 44, wherein the magenta toner particles contain a magenta pigment and a polar resin having an acid value of 3.0 to 20.0 mgKOH / g so as to satisfy the following formula. Manufacturing method. [Outside 7] 48. The method for producing a magenta toner according to claim 44, wherein the polar resin is a saturated polyester resin. 49. The method for producing a magenta toner according to claim 48, wherein the saturated polyester resin has a number average molecular weight of 2.500 to 10,000. 50. The method for producing a magenta toner according to claim 44, wherein the polar resin is an epoxy resin. 51. The epoxy resin has a number average molecular weight of 2.50.
The method for producing a magenta toner according to claim 50, wherein the number is from 0 to 10.000. 52. The method for producing a magenta toner according to claim 44, wherein the polar resin is a styrene-acrylic acid copolymer. 53. The styrene-acrylic acid copolymer has a number average molecular weight of 2.500 to 10,000.
2. The method for producing a magenta toner according to any one of 2. 54. The method for producing a magenta toner according to any one of claims 37 to 53, wherein the magenta toner particles contain a low softening point substance having an endothermic main peak in a DSC endothermic curve at 55 to 130 ° C. 55. The method for producing a magenta toner according to claim 54, wherein the magenta toner particles contain 5 to 25% by weight of a low softening point substance. 56. The method for producing a magenta toner according to claim 54, wherein the low softening point substance is a wax. 57. The low softening point substance is a long chain ester moiety having 15 or more carbon atoms. 57. An ester compound having the formula: wherein R ₁ represents an organic group having 15 or more carbon atoms.
The method for producing a magenta toner of any one of the above. 58. The low softening point substance is represented by the following formula (1): R ₂ —COO—R ₃ (1) wherein R ₂ and R _{3 each} represent a saturated hydrocarbon group having 15 to 45 carbon atoms. The method for producing a magenta toner according to any one of claims 54 to 56, comprising an ester compound represented by the following formula: 59. The method for producing a magenta toner according to claim 58, wherein R ₂ and R ₃ are alkyl groups. 60. The low-softening point substance is represented by the following formula (2): [In the formula, R ₄ and R ₆ each represent an organic group having 15 to 32 carbon atoms, and R ₅ represents an organic group having 2 to 20 carbon atoms. The method for producing a magenta toner according to any one of claims 54 to 56, comprising an ester compound represented by the following formula: 61. A compound according to claim 61, wherein R ₄ and R ₆ are alkyl groups,
_The method for producing a magenta toner according to claim 60, wherein ₅ is an alkylene group. 62. A low softening point substance represented by the following formula (3): [In the formula, R ₇ and R ₉ each represent an organic group having 15 to 32 carbon atoms, and R ₈ represents an organic group having 2 to 20 carbon atoms. The method for producing a magenta toner according to any one of claims 54 to 56, comprising an ester compound represented by the following formula: 63. R ₇ and R _{9 each} represent an alkyl group;
63. The method for producing a magenta toner according to claim 62, wherein ₈ represents an alkylene group. 64. The low-softening point substance is represented by the following formula (4): [Wherein, R ₁₀ and R ₁₁ represent an organic group having 15 to 40 carbon atoms, a and b each represent an integer of 0 to 4, a + b is 4, m and n are each an integer of 0 to 25, , M + n is 1
The method for producing a magenta toner according to any one of claims 54 to 56, comprising an ester compound represented by the following. 65. The method for producing a magenta toner according to claim 64, wherein R ₁₀ and R ₁₁ are alkyl groups. 66. The low softening point substance is represented by the following formula (5): [Wherein, R ₁₂ and R ₁₃ represent an organic group having 15 to 40 carbon atoms, R ₁₄ represents a hydrogen atom or an organic group having 1 to 40 carbon atoms, c and d each represent an integer of 0 to 3, c + d is 1 to 3 and z is an integer of 1 to 3]. The method for producing a magenta toner according to any one of claims 54 to 56, comprising: 67. The method for producing a magenta toner according to claim 66, wherein R ₁₂ , R ₁₃ and R ₁₄ are alkyl groups. 68. The magenta toner particles have a shape factor SF
68. The method for producing a magenta toner according to claim 37, wherein -1 is 100 to 150. 69. The magenta toner particles have a shape factor SF
The method for producing a magenta toner according to any one of claims 37 to 67, wherein -1 is 100 to 125. 70. The method for producing a magenta toner according to claim 37, wherein the magenta toner particles have negative triboelectricity and contain 0.5 to 10% by weight of a negative charge control agent. 71. The method for producing a magenta toner according to claim 70, wherein the negative charge control agent is a metal compound of an aromatic hydroxycarboxylic acid. 72. The method for producing a magenta toner according to claim 37, wherein the magenta toner particles have a weight average particle diameter of 3 to 9 μm. 73. The method for producing a magenta toner according to any one of claims 37 to 71, wherein the magenta toner particles have a weight average particle size of 3 to 8 μm.