JP3437436B2 - Magenta toner for developing electrostatic images and method of manufacturing the same - Google Patents

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 charge image formed by an image forming method such as an electrophotographic method and an electrostatic printing method, and a manufacturing method thereof.

More specifically, the present invention relates to a magenta toner for developing an electrostatic image for forming a full-color image, which has high image quality, excellent color reproducibility, and is stable in triboelectric charging, 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 having excellent color reproducibility without color unevenness as well as resolution and gradation have been obtained.

In a digital full-color copying machine, a color image original is color-separated with 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 consisting of a diameter is reproduced by using toners of each color of Y (yellow), M (magenta), C (cyan), and B (black) by utilizing the subtractive color mixing action at the time of heat and pressure fixing. A large amount of toner compared to the machine is transferred from the photoconductor through the intermediate transfer body,
Alternatively, it is necessary to transfer to a transfer material without intervention.

Among the color toners, the magenta toner is important for reproducing the flesh color, and since the flesh tone of a human image is a halftone, excellent developability is also required.

Quinacridone colorants, thioindigo colorants, xanthene colorants, monoazo colorants, perylene colorants, 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 xanthene-based dye is proposed in the publication, and a diketopyrrolopyrrole-based pigment is proposed in JP-A-2-210459.
No. 42383 proposes an anthraquinone dye.

Further, in order to control the transparency and color of the colorant, the pigment compound is not used alone, but it is disclosed in JP-A 1-222.
The use of quinacridone pigments in a mixed crystal state as in JP-A-62-291669 (corresponding U.S. Pat. No. 4,777,105), in which a pigment-pigment and a pigment-dye are blended as described in Japanese Patent No. Methods are also known.

These magenta colorants have good affinity with the binder resin and good light resistance, and although magenta toners having excellent triboelectrification characteristics and color tones can be obtained, they satisfy transparency but are more faithful to the original. In order to obtain such an image, a magenta toner having further improved color tone, saturation and electrophotographic characteristics has been desired.

[0010]

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

An object of the present invention is to provide a magenta toner for developing an electrostatic charge image, which can obtain an extremely clear magenta color with a high image density.

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

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

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

It is an object of the present invention 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, the magenta pigment being CI Pigment Red 122 ( C.
I. Pigment Red 122), C-I.
Pigment Red 202 (C.I. Pigment R
ed 202) and CI Pigment Violet 19 (CI Pigment Violet 1)
9) A magenta toner for developing an electrostatic charge image, which is the solid solution pigment.

Further, in the present invention, a polymerizable monomer, a magenta pigment and a polymerization initiator are mixed to prepare a polymerizable monomer composition, and the polymerizable monomer composition is dispersed in an aqueous medium. Magenta toner for producing particles of the polymerizable monomer composition, and for polymerizing the styrene monomer in the particles of the polymerizable monomer composition in an aqueous medium to produce a binder resin to produce magenta toner particles. Magenta toner particles contain a binder resin formed from a polymerizable monomer, and the magenta pigment is CI Pigment Red 122 (C.I.
Pigment Red 122), C.I. Pigment Red 202 (CI Pigment Red)
202) and CI Pigment Violet 1
9 (C.I. Pigment Violet 19) solid solution pigment, and a method for producing a magenta toner.

[0018]

BEST MODE FOR CARRYING OUT 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 a step of mixing at least three magenta pigments in a step prior to the dehydration step and the pigmentation step in the pigment production process, and then dehydrating and pigmenting. . Since the solid solution pigment used in the present invention is easily crushed, the pigment particles can be easily dispersed up to around the primary particle size.

As a 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. In particular, two types of substituted quinacridone pigments having the structures shown below and unsubstituted quinacridone pigments are used in combination from the viewpoint that the light resistance, the coloring power, the negative triboelectric charging property and the color mixing property are well balanced.

[0021]

[Outside 13]

C. I. Pigment Violet
No. 19 is easily changed in light resistance and coloring power depending on its crystal structure. I. Pigment Red 122 and C.I. I. Pigment Red 202 is stabilized by forming a solid solution with it. Furthermore, the hue of the solid solution is C.I. I. By changing the compounding ratio of Pigment Violet 19 and the condition setting at the time of crystallization, it is possible to widen the hue space of the solid solution without impairing the saturation and lightness 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 to contain let 19 in the following ratio.

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

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

If the value of A / C is less than 0.3, the tinting strength of the solid solution pigment is lowered and the image density of the magenta toner is lowered. When the value of A / C exceeds 5.0, the negative triboelectric charging property of the solid solution pigment is lowered and the positive triboelectric charging property is improved. Therefore, when the magenta toner has the negative triboelectric charging property, the negative triboelectric charging of the magenta toner is performed. And the fog is apt to occur. Further, when the value of A / C exceeds 5.0, 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 tends to deviate from the preferable range. Furthermore, if 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 lowered. A x C
When the value of / B exceeds 10.0, the negative triboelectrification property of the solid solution pigment decreases and the positive triboelectrification property is improved. Therefore, when the magenta toner has negative triboelectrification property, the negative triboelectrification property of the magenta toner is And the fogging is likely to occur, and the magenta toner is easily scattered from the developing device.

The solid solution pigment is C.I. I. P
igment Red 122 0.50 to 0.85,
More preferably 0.5 to 0.80 part by weight is contained, and C.I.
I. Pigment Red 202 from 0.03 to 0.
35, more preferably 0.05 to 0.30 parts by weight, and C.I. I. Pigment Violet 19 is 0.06 to 0.40, more preferably 0.10 to 0.3.
It is preferable to contain 5 parts by weight.

The production of solid solution pigments is described, for example, in US Pat.
No. 60510, a method of simultaneously recrystallizing a solid solution component from sulfuric acid or a suitable solvent, followed by solvent treatment (after salt grinding), and German Patent Application Publication 12173.
The method of cyclizing the appropriately substituted diaminoterephthalic acid mixture described in JP-A No. 33 and then treating with a solvent can be mentioned.

The magenta toner particles of the present invention are prepared by mixing a polymerizable monomer such as a styrene monomer, optionally other vinyl monomer, a magenta solid solution pigment, a polar resin and a polymerization initiator to prepare 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 by

When the magenta toner particles are produced by such a manufacturing method, the magenta solid solution pigment is dispersed to near the primary particles when the polymerizable monomer composition is prepared. When a polar resin having an acid value of 3.0 to 20.0 mgKOH / g is used, reaggregation of particles of a 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 it does.

The polar resin used in the present invention is a re-aggregation of the solid solution pigment while being uniformly dispersed in the polymerizable monomer composition at the initial stage of polymerization of the polymerizable monomer in the particles of the polymerizable monomer composition. Of the polar resin has an acid value of 3.0 to 20.0 (mgKOH / mgKOH / mgKOH / mg).
It is preferably in the range of g).

If the acid value of the polar resin is less than 3.0 mgKOH / g, the polar resin and the solid solution pigment have a low affinity and are easily separated, so that the effect of suppressing re-aggregation is low, the coloring power is lowered, and the charging property is reduced. Is likely to occur. When the acid value of the polar resin exceeds 20.0 mgKOH / g, the dispersibility of the polar resin in the styrene monomer (nonpolar 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 suppression of reaggregation of the solid solution pigment,
The polar resin is contained in the magenta toner particles in an amount of 1 to 20% by weight, preferably 2.0 to 10.0 (wt%), and further satisfies the following formula (A) . Is more preferable.

[0035]

[Outside 14]

If the amount of the polar resin added is less than 1 wt%, the effect of the addition is small and the negative triboelectric chargeability of the toner is apt to deteriorate. If the amount of the polar resin added exceeds 20 wt%, the viscosity of the polymerizable monomer composition will increase, making granulation in an aqueous medium difficult and lowering the manufacturing stability.

Further, if the value of the above formula is less than 5, fog or toner scattering is likely to appear on the magenta toner.

When the value of the above formula exceeds 20, the fine powder component is liable to increase during the production of magenta toner particles by the polymerization method in an aqueous medium, which is not preferable.

The polar resin preferably does not contain an unsaturated group capable of reacting with the styrene monomer in the molecule. When a polar resin having a reactive unsaturated group is used, a cross-linking reaction occurs between the styrene monomer and the polar resin, and the color mixing property is deteriorated, which is not preferable.

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

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

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

In the present invention, styrene monomer o (m, p) -methylstyrene, m is used as the polymerizable monomer.
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, diethylaminoethyl (meth) acrylate; butadiene, isoprene, cyclohexene, Monomers such as (meth) acrylonitrile and acrylic acid amide may be added. Preferably, Publication Polymer Handbook Second Edition III-
The styrene monomer and other monomers are appropriately mixed and used so as to show 50 to 85 ° C. by calculation using the theoretical glass transition temperature (Tg) described in P139 to 192 (manufactured by John Wiley & Sons). If the theoretical glass transition temperature is less than 50 ° C, problems tend to occur in terms of toner storage stability and toner durability stability.
If the value exceeds 0, then in the case of full-color image formation, O
The transparency of the HP image is reduced.

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

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

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

If the maximum main peak value is less than 50 ° C., the self-aggregating force of the low softening point substance is weakened, and as a result, the high temperature offset property is weakened, which is not preferable as a magenta toner for forming a full-color image. On the other hand, if 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 the temperature range of 20 to 200 ° C. using, for example, DSC-7 manufactured by Perkin Elmer. The melting point of indium and zinc is used to correct the temperature of the device detection unit, and the heat of fusion of indium is used to correct the amount of heat. An aluminum pan was used as a sample and an empty pan was set as a control, and the temperature rising rate was 10 ° C./min. Measure with.

Considering the offset resistance and the durability of many sheets of magenta toner, the low softening point substance is contained in the toner particles in an amount of 5 to 5.
It is preferable that the content is 25% by weight.

The low softening point substance is preferably wax because it is easily melted at the time of heat and pressure fixing. Among them, the carbon number is 1
5 or more long-chain ester moieties

[0051]

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

Formula (1) R ₂ —COO—R ₃ [In the formula, 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 represent an organic group having 15 to 32 carbon atoms, and R ₅ represents an organic group having 2 to 200 carbon atoms. R ₄ and R ₆ are preferably alkyl groups, and R ₅
Is preferably an alkylene group.

[0054]

[Outside 17] [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. R ₇ and R ₉ are preferably alkyl groups, and 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 represent an integer of 0 to 4, a + b is 4, and m and n are integers of 0 to 25. , M + n is 1
That is all. ] R ₁₀ and R ₁₁ are preferably alkyl groups.

[0056]

[Outside 19] [In the formula, 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, and c and d 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 alkyl groups.

The wax preferably used in the present invention is
Those having a hardness of 0.5 to 5.0 are preferable. The hardness of the wax is a value obtained by producing a cylindrical sample having a diameter of 20 mm and a thickness of 5 mm, and then measuring the Vickers hardness using, for example, a dynamic ultra-fine hardness meter (DUH-200) manufactured by Shimadzu Corporation. The measurement conditions are such that a load speed of 9.67 mm / sec and a load speed of 9.67 mm / sec are used for displacement of 10 μm, then the sample is held for 15 seconds, and the obtained dent shape is measured to determine the Vickers hardness. When the hardness of the wax 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 deteriorated. Since the self-cohesive force of itself is also small, the high temperature offset resistance decreases.

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 ester wax is preferably contained in the toner particles in an amount of 5 to 25 wt%. When 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 lowered.

The content of the ester wax is 25
If it exceeds wt%, the durability of many 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 that is colorless or light-colored, has a high charging speed for magenta toner, and can stably maintain a constant charge amount is preferable.

When the magenta toner particles are directly produced by a polymerization method, a charge control agent having no polymerization inhibitory property and less solubilized product in an aqueous medium is particularly preferable. Specific compounds include metal compounds such as salicylic acid, alkylsalicylic acid, dialkylsalicylic acid, naphthoic acid, or dicarboxylic acid as negative-charge controlling agents; sulfonic acids, polymeric compounds having carboxylic acid in the side chain, boron compounds,
Urea compounds, silicon compounds, currys arenes and the like can be mentioned.

Of these, metal compounds of aromatic hydroxycarboxylic acids are preferred because they are colorless or light-colored and have excellent negative chargeability controllability.

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, 1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,
Azo-based polymerization initiators such as 4-dimethylvaleronitrile and azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide,
Examples thereof include peroxide type polymerization initiators such as 2,4-dichlorobenzoyl peroxide and lauroyl peroxide.

The amount of the polymerization initiator added varies depending on the intended degree of polymerization, but is generally 0.
5 to 20% by weight is added. The polymerization initiators are slightly different depending on the type of polymerization method, but they may be used alone or in combination with reference to the 10-hour half-life temperature. If necessary, a crosslinking agent, a chain transfer agent, or a polymerization inhibitor may be further used to control the degree of polymerization.

The aqueous medium used for producing the magenta toner particles is, for example, tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, water as an inorganic dispersant. Magnesium oxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate,
Examples include bentonite, silica, and alumina. Examples of organic dispersants include polyvinyl alcohol, gelatin,
Examples include methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, and starch. These dispersants are 0.2 to 2.0 with respect to 100 parts by weight of the polymerizable monomer.
It is preferred to use parts by weight. The dispersant may be 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 products may be used as they are, but in order to obtain dispersed particles having a fine and uniform particle size, the inorganic compound should be formed in an aqueous medium under high speed stirring. Is also preferable. For example, in the case of tricalcium phosphate, a dispersant suitable for the suspension polymerization method can be obtained by mixing an aqueous sodium phosphate solution and an aqueous calcium chloride solution under high speed stirring. To make these dispersants finer, 0.001 to 0.1 part by weight of a surfactant may be used in combination. Specific examples thereof 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. Add magenta colorant, polar resin, low softening point substance and other additives to polymerizable monomer including styrene monomer and disperse with an attritor. Then add polymerization initiator and homogenize with homogenizer or ultrasonic disperser. A polymerizable monomer composition is prepared by dissolving or dispersing, and the polymerizable monomer composition is dispersed in an aqueous medium containing a dispersion stabilizer with a stirrer, a homomixer, a homogenizer, etc. to granulate.

Granulation is carried out by adjusting the stirring speed and time so that the droplet particles of the polymerizable monomer composition have a desired magenta toner particle size. After that, stirring may be performed to the extent that the particle state is maintained and the particles are prevented from settling due to the action of the dispersion stabilizer. The polymerization temperature of the polymerizable monomer is set to 40 ° C. or higher, generally 50 to 90 ° C. to carry out the polymerization. The temperature may be raised in the latter half of the polymerization reaction, and further, in order to remove unreacted polymerizable monomers and by-products that cause odor during toner image fixing, in the latter half of the reaction or after the reaction is partially completed. The aqueous medium may be distilled off from the reaction vessel. After the reaction is completed, 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 with respect to 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 or less.
It is preferably 0 to 150, particularly preferably 100 to 125.

In the present invention, SF-1 indicating the shape factor
Is, for example, Hitachi FE-SEM (S-800)
100 random toner images magnified at a magnification of 500 are randomly sampled, and the image information is, for example, an image analysis device (Luzex I manufactured by Nicore Co.) via an interface.
It is introduced into II) and analyzed, and the value calculated by the following formula is defined as shape factor SF-1.

[0077]

[Outside 24] [Wherein MXLNG represents 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 toner particles.

Toner particles having a shape factor SF-1 of more than 150 are gradually changed from a spherical shape to an irregular shape, and the transfer efficiency is lowered accordingly. When using an intermediate transfer material to support various types of transfer materials,
Since the transfer process is performed substantially twice, the decrease in transfer efficiency leads to a decrease in toner utilization efficiency. Furthermore, in recent digital full-color copying machines and digital full-color printers, color image originals are preliminarily B (blue), G (green),
After color separation using an R (red) filter, a 20 to 70 μm dot latent image is formed on the photoconductor to form Y (yellow), M (magenta), C (cyan), B (black).
It is necessary to reproduce a multi-color image faithful to the original document or color information by utilizing the subtractive color mixing action using each color toner. At this time, a large amount of Y, M, C, and B toner is placed on the photosensitive member or the intermediate transfer member in accordance with the color information of the original or CRT, so that the color toners used in the present invention are extremely colored. High transferability is required. Therefore, a magenta toner having a large triboelectric charge amount and a toner particle shape factor SF-1 of 100 to 150 is preferable in order to maintain good transferability of the toner.

In order 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).
.About.8 .mu.m) 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, and a large amount of transfer residual toner is generated on the photosensitive member or the intermediate transfer member, which easily causes nonuniform unevenness of an image due to fog or transfer failure. When the weight average particle diameter of the toner exceeds 9 μm, resolution and dot reproducibility are deteriorated, and fusion to each member is likely to occur, and when the number variation coefficient of the toner exceeds 35%, the tendency is further increased. Get stronger.

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 for measuring GPC, the toner was previously used in a Soxhlet extractor with a solvent of toluene to 20 times.
After performing time extraction, distill off toluene with a rotary evaporator, and further wash or extract with an organic solvent (such as chloroform) that dissolves the low softening point substance such as a release agent but does not dissolve the resin component. After doing, THF
(Tetotahydrofuran) 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 Showa Denko A-801, 802, 803, 8
04, 805, 806, 807 are connected and the molecular weight distribution is measured using the calibration curve of standard polystyrene resin.

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

FIG. 1 is a schematic explanatory view of an apparatus for measuring the amount of triboelectric charge of toner. Prepare magenta toner to measure. 50 to 100 m of a mixture of a magenta toner (no external additive) and a carrier whose triboelectric charge amount is to be measured.
It is placed in a polyethylene bottle having a volume of 1 and shaken by hand for about 5 minutes to be triboelectrically charged. The carrier is a ferrite carrier coated with a silicone resin (average particle size 35 μm)
And the mixing weight ratio of the magenta toner and the carrier is 7:93.

Then, the mixture (toner and carrier) W ₀ (g: about 0.5-1.5 g) was put into a metal measuring container 2 having a 500 mesh screen 3 at the bottom, and a metal lid 4 was placed therein. do. At this time, weigh the entire measuring container 2 and W
₁ (g). Next, in the suction device 1 (at least the portion in contact with the measurement container 2 is insulative), suction is performed 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, the toner is suctioned sufficiently, preferably for 2 minutes to remove the toner by suction.

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

[0088]

[Outside 25] (V (volt) 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 indicates the weight of toner / carrier. Show ratio)

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

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

2 to 10 g of the resin sample was weighed in 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 0.1% mixed indicator of promethymol blue and phenol red, titration was performed with a previously evaluated 0.1N potassium hydroxide / ethanol solution, and the acid value was calculated according to the following calculation from the consumption amount of the alcohol potassium solution. Ask for.

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

Next, a method of evaluating the coloring power will be described.

93 parts by weight of a ferrite carrier coated with a silicone resin is mixed with 7 parts by weight of magenta toner to obtain a two-component developer. Using the obtained developer, the fixing temperature is made variable, and a toner image is transferred onto a transfer material by a modified Canon full-color copying machine (CLC500) without a fixing oil application mechanism to obtain a fixed image. At this time, the fixing conditions are as follows: a transfer material of 99 g / m ^{2 with} a gloss of 4 and a toner amount of 0.5 mg / c.
A magenta solid image of m ² is obtained, and the image has a glossiness of 10 to 10.
The fixing temperature is adjusted to 15. The image density of this single-color solid image is defined as the coloring power.

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

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

A two-component developer is prepared by mixing 93 parts by weight of an acrylic resin-coated ferrite carrier with 7 parts by weight of magenta toner. Canon full-color copying machine (CLC500) modified by using the obtained developer to make the fixing temperature variable, the surface material of the upper and lower rollers made of fluororesin, and omitting the fixing oil application mechanism.
With a modified machine, transfer the magenta toner image onto the transfer material,
Get a fixed image.

At this time, as fixing conditions, a transfer material having a gloss of 4 and a basis weight of 99 g / m ² was used, and a monochromatic solid image having a magenta toner amount of 0.5 to 0.7 mg / cm ² was obtained, and the image was transferred. The fixing temperature is adjusted so that the glossiness is 10 to 15. The density conditions are adjusted so that the grayscale can be reproduced as faithfully as possible in a full-color copy image using a Kodak grayscale and color patch as the original, and the maximum density of magenta (M) single-color copy becomes 1.1 or more. To adjust the concentration.

Then, with a modified full-color copying machine, the lightness L on a solid image with a magenta (M) color image density of 1.2
*, The color reproducibility is evaluated by the saturation C *, and the image quality uniformity is evaluated by the highlight image with the image density of 0.2.

The evaluation was carried out in five stages, and when the color reproduction range E of the image of Comparative Example 1 was defined by the following formula and the value was set to 100, the color reproduction range: E = ((lightness L *) ² × (color Degree C *) ² )
^It was evaluated that ^1/2 E> 110 = A 105 <E ≦ 110 = B 90 <E ≦ 105 = C 80 <E ≦ 90 = D E ≦ 80 = E.

Comparative Example 1 is also applied to the uniformity of highlight areas.
It is evaluated by the relative evaluation by visual inspection in five stages of A, B, C, D and E, where B is B.

Next, a transparency image (OHP)
The evaluation method for transparency is described below.

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

Commercial full-color copying machine (CLC500;
Using a modified machine manufactured by Canon Inc., the unfixed toner image having gradation is obtained by developing and transferring at a developing contract of 320 V on a transparency sheet in an environment of temperature 23 ° C./humidity 65% RH. . The obtained unfixed toner image was fixed with an external fixing device (without oil coating function; roller diameter 40 mm) in which the surface of the fixing roller was formed of a fluororesin at a fixing temperature of 180 ° and a fixing process speed of 30 mm / sec. Get a fixed image.

The image density of the obtained fixed image is 0.4 to 0.
When the transmittance T% of 6 (halftone part) was measured and the transmittance of Comparative Example 1 was 100, T%> 110 = A 100 <T% ≦ 110 = B 90 <T% ≦ 105 = The relative value was evaluated as C 80 <T% ≤ 90 = D T% ≤ 80 = E.

The transmittance was measured by Shimadzu self-spectrophotometer UV.
2200 (manufactured by Shimadzu Corporation) was used for 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]

EXAMPLES The present invention will be described more specifically by showing examples below.

Production Example 1 of solid solution pigment :

[0109]

[Outside 26] The compound represented by the formula (3) was cyclized in phosphoric acid to produce 2,9-dimethylquinacridone. Phosphoric acid with 2,9-dimethylquinacridone is dispersed in water, then 2,9-dimethylquinacridone is filtered off and crude 2,9-dimethylquinacridone (CI Pigmen) moistened with water is obtained.
t Red 122) was prepared.

Separately, the following formula

[0111]

[Outside 27] The compound represented by the formula (3) was cyclized in phosphoric acid to produce 3,10-dichloroquinacridone. Phosphoric acid with 3,10-dichloroquinacridone is dispersed in water and then 3,10
The crude 3,10-dichloroquinacridone (C.I. Pig.
ment Red 202) was prepared.

Separately, the following formula

[0113]

[Outside 28] The compound represented by the formula (3) was cyclized in phosphoric acid to produce an unsubstituted quinacridone. Phosphoric acid with quinacridone is dispersed in water, then the quinacridone is filtered off and the crude quinacridone (CI Pigment Vi) wet with water is removed.
olet 19).

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 mixed solution of 600 parts by weight of water and 300 parts by weight of ethanol, and during a period of 6 hours 2,9. -Dimethylquinacridone, 3,
The mixture was heated to reflux while milling 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.
70, the value of B is 0.10. The value of C is 0.2
0, A / C is 3.50, and A × C / B is 1.
It was 40.

Production Examples 2 and 3 of solid solution pigments , except that the compounding 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.
Got

[0117]

[Table 1]

Production Example (a) of Solid Solution Pigment (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 mixed with water. 600 parts by weight and ethanol 300
The mixture was added to a container equipped with a condenser having a mixture of 1 part by weight, and the mixture was heated to reflux while grinding 9,9-dimethylquinacridone and quinacridone for 5 hours. After 5 hours, the solid solution pigment was filtered off, washed, dried and then pulverized 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 a crude unsubstituted quinacridone were mixed with 600 parts of water. Parts by weight and ethanol 300
The mixture was added to a container equipped with a condenser having a mixture of 1 part by weight, and the mixture was heated to reflux while grinding 3,10-dichloroquinacridone and quinacridone for 5 hours. After 5 hours, the solid solution pigment was filtered, washed, dried and then pulverized to obtain a solid solution magenta pigment (b).

Example 1 A 0.1M Na ₃ PO ₄ aqueous solution and a 1M NOCaCl ₂ aqueous solution were prepared. In a four-necked flask equipped with a high speed stirrer TK- homomixer was added and 0.1 mol -Na ₃ PO ₄ aqueous solution 450 parts by weight of ion-exchanged water 710 parts by weight to adjust the rotational speed to the rotational 12.000, It was heated to 65 ° C. 68 parts by weight of 1.0 mol-CaCl ₂ aqueous solution was gradually added to the mixture to form a fine soft water-soluble dispersant Ca ₃ (PO ₄ ).
_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) Polymer of bisphenol A-trimellitic acid; acid value = 15 mg KO
H / g, Mn = 4500; peak molecular weight = 6000) 2 parts by weight of metal compound of dialkyl salicylic acid (negative charge control agent) 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 for 3 hours using an attritor to prepare a pigment dispersion.

1 g of the pigment dispersion was mixed with 9 g of styrene monomer.
A solid solution magenta pigment (1) was obtained by conducting a sedimentation test by diluting with
No sedimentation was observed and it was confirmed that the solid solution magenta pigment (1) had good dispersibility. To the pigment dispersion, 2 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile), which is a polymerization initiator, was added to prepare a polymerizable monomer crude product. The polymerizable monomer crude product was put into an aqueous dispersion medium and granulated for 15 minutes while maintaining the rotation speed of the high-speed stirrer at 12,000 rpm. After that, the stirrer of the propeller stirring blade was changed from the high-speed stirrer, 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. and the polymerization was continued for 4 hours in total for 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 with a Coulter counter is 6.3 μm.
And the number variation coefficient is 24%, and the shape factor SF-1 is 106
Met. The magenta toner particles (1) thus obtained were 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, about 2 parts by weight of a metal compound of dialkylsalicylic acid. Parts and about 15 parts by weight of ester wax.

Magenta Toner Particles (1) 100 Obtained
2 parts by weight of hydrophobized titanium oxide fine powder was externally added to 1 part by weight to obtain a magenta toner. To 7 parts by weight of this toner,
93 parts by weight of a magnetic ferrite carrier coated with an acrylic resin was mixed and the durability was evaluated as a two-component developer by a full color copying machine CLC500 modified by Canon. A stable, clear and good magenta image was obtained without lowering the developability even after running 20,000 sheets under the conditions of room temperature and normal humidity (23 ° C., 60%).

The coloring power was also good and the OHP transparency was excellent. The results are shown in Table 3.

Comparative Example 1 The colorant was C.I. I. Pigment Red 122 7
Comparative magenta toner particles (1) were obtained in the same manner as in Example 1 except that the amount was changed to parts by weight. The weight average diameter of the obtained comparative magenta toner particles (1) was 6.2.
In μm, the number variation coefficient is 58% and the shape factor SF-1 is 10
It was 9.

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

Obtained Comparative Magenta Toner Particles (1) 1
2 parts by weight of hydrophobized titanium oxide fine powder was externally added to 00 parts by weight to obtain a magenta toner. To 7 parts by weight of this toner,
Acrylic resin coated ferrite carrier 9
Durability evaluation was carried out by mixing 3 parts by weight and using it as a two-component developer with a full-color copying machine CL500 modified by Canon. When 20,000 sheets were subjected to durability under normal temperature and normal humidity, a magenta image with fog on the non-image area was obtained because of low chargeability.

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

Comparative Example 2 The colorant 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) had a weight average particle size of 6.7.
μm, the number variation coefficient is 49%, and the shape factor 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, and C.I. I. Pigment V
iolet 19 has settled.

The obtained comparative magenta toner particles (2) were evaluated for durability in the same manner as in Example 1. As a result, the electrification was lower than that in Example 1, so that fog was generated from the beginning and the image quality was poor. Met.

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

Comparative Example 3 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 prepared 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 diameter of 5.9 μm, a number variation coefficient of 56% and a shape factor SF-1 of 113.

A magenta pigment used in the same manner as in Example 1 was subjected to a sedimentation test. As a result, the magenta pigment sedimented in about 10 hours.

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

Further, since the dispersibility of the colorant in the toner particles is worse than that in Example 1, the coloring power and 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 magenta toner particles (a) thus obtained were 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.

Magenta toner was obtained in the same manner as in Example 1, a two-component type developer was prepared, and evaluated in the same manner as in Example 1. The results are shown in Table 3.

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 in place of the solid solution magenta pigment (1).

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

Magenta toner was obtained in the same manner as in Example 1, and a two-component type developer was prepared, and evaluated in the same manner as in Example 1. The results are shown in Table 3.

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 in place of the solid solution magenta pigment (1). The weight average particle diameter of the magenta toner particles (2) was 6.6 μm, the variation coefficient was 32%, and the shape factor SF-1 was 109.

Magenta toner was obtained in the same manner as in Example 1, and a two-component type developer was prepared, and evaluated in the same manner as in Example 1. The results are shown in Table 3.

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 in place of the solid solution magenta pigment (1). The weight average diameter of the magenta toner particles (3) was 6.2 μm, the variation coefficient was 27%, and the shape factor SF-1 was 108.

Magenta toner was obtained in the same manner as in Example 1, and a two-component type developer was prepared, and evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0147]

[0148]

[0149]

Example 4 The saturated polyester resin of Example 1 was converted into a styrene-acrylic resin (styrene-methacrylic acid-methacrylic acid methyl ester copolymer; acid value = 12 mg KOH / g; Mn = 6).
Magenta toner particles ( 4 ) were obtained in the same manner as in Example 1, except that the peak molecular weight was changed to 700;

The magenta toner particles ( 4 ) thus obtained had a weight average diameter of 7.4 μm, a number variation coefficient of 31% and a shape factor SF-1 of 106.

The magenta toner particles ( 4 ) thus obtained were evaluated for durability in the same manner as in Example 1. As a result, a clear and good magenta image having stable developability was obtained.

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

The magenta toner particles ( 5 ) thus obtained had a weight average diameter of 4.9 μm, a number variation coefficient of 42% and a shape factor SF-1 of 111.

The magenta toner particles ( 5 ) thus obtained were evaluated for durability in the same manner as in Example 1. As a result, although somewhat fogged due to a lower chargeability than in Example 1, development was carried out at a practical level. A clear and good magenta image having stable properties was obtained.

[0156]

[Table 2]

[0157]

[Table 3]

[0158]

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

[Brief description of drawings]

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

[Explanation of symbols]

1 suction machine 2 measuring vessels 8 capacitors 9 electrometer

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI G03G 9/08 346 384 (56) References JP 62-291669 (JP, A) JP 9-50150 (JP, A) ) JP-A-9-43909 (JP, A) JP-A-8-328341 (JP, A) JP-A-8-297376 (JP, A) JP-A-4-190246 (JP, A) JP-A-2- 123373 (JP, A) JP-A-1-224777 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03G 9/08

Claims (51)

(57) [Claims] 1. A magenta toner for developing an electrostatic charge image, comprising magenta toner particles containing at least a binder resin and a magenta pigment, the magenta pigment being CI Pigment Red 122.
(C.I. Pigment Red 122), C.I. Pigment Red 202 (C.I. Pigment)
Red 202) and CI Pigment Violet 19 (CI Pigment Violet 1)
A magenta toner for developing electrostatic images, which is the solid solution pigment of 9). 2. The solid solution pigment comprises C.I. I. P
igment Red122, C.I. I. Pigment
Red 202 and C.I. I. PigmentVideo
The magenta toner according to claim 1, which contains t19 in the following ratio. 0.3 ≦ A / C ≦ 5.0 0.1 ≦ A × C / B ≦ 10.0 [wherein A is C.I. I. Pigment Red122
The blending weight of C.I. I. Pigment Re
The blending weight of d202 is shown, and C is C.I. I. Pigmen
t shows the blending weight of Violet 19] 3. The solid solution pigment is C.I. I. P
IGMENT Red 122 in an amount of 0.50 to 0.85 parts by weight, and C.I. I. Pigment Red 202 in an amount of 0.03 to 0.35 parts by weight, and C.I. I. Pigme
The magenta toner according to claim 1, which contains 0.06 to 0.40 parts by weight of nt Violet 19. 4. The solid solution pigment comprises C.I. I. P
IGMENT Red 122 in an amount of 0.55 to 0.80 parts by weight, and C.I. I. Pigment Red 202 is contained in an amount of 0.05 to 0.30 parts by weight, and C.I. I. Pigme
The magenta toner according to claim 1, which contains 0.10 to 0.35 part by weight of nt 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 are made of a binder resin 65 to
98% by weight, 1 to 15% by weight of magenta pigment and an acid value of 3.
The magenta toner according to claim 1, which contains 1 to 20% by weight of a polar resin of 0 to 20.0 mgKOH / g. 7. The magenta toner particle comprises a polar resin of 2.
The magenta toner according to claim 6, which contains 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. . [Outer 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, which is 0 to 10,000. 13. The magenta toner according to claim 5, wherein the polar resin is a styrene-acrylic acid copolymer. 14. Styrene - acrylic acid copolymer has a number average molecular weight of 2, 500 to, claim 1 is 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 of 55 to 130 ° C. in a DSC endothermic curve. 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 wax. 18. The low softening point substance is a long-chain ester portion having 15 or more carbon atoms. (In the formula, R ₁ is a number 15 or more organic groups carbon) to claim 15 containing an ester compound having 17
One of the magenta toners. 19. The low softening point substance has the following formula (1) R ₂ —COO—R ₃ (1) [wherein, R ₂ and R ₃ represent a saturated hydrocarbon group having 15 to 45 carbon atoms]. ] The magenta toner according to any one of claims 15 to 18, containing an ester compound represented by 20. The magenta toner according to claim 19, wherein R ₂ and R ₃ are alkyl groups. 21. The magenta toner particles have a shape factor SF.
-1 is 100 to 150 or the magenta toner of claims 1 to 20. 22. The magenta toner particles have a shape factor SF.
-1 is 100 to 125 or the magenta toner of claims 1 to 20. 23. 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 to polymerize the styrene monomer. one of the magenta toner of claims 1 to 22 has the generated polymerized magenta toner particles. 24. A polymerized magenta toner, wherein the polymerizable monomer composition further contains an acrylic acid ester monomer or a methacrylic acid ester monomer, and contains a styrene copolymer produced by polymerization of the monomer in an aqueous medium. 24. The magenta toner of claim 23 having particles. 25. The magenta toner particles, any of a magenta toner according to claim 1 to 24 weight average particle diameter of 3～9Myuemu. 26. 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. A method for producing a magenta toner in which particles of a monomer composition are produced, and a styrene monomer in particles of a polymerizable monomer composition is produced in an aqueous medium to produce 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 CI Pigment Red 122.
(C.I. Pigment Red 122), C.I. Pigment Red 202 (C.I. Pigment)
Red 202) and CI Pigment Violet 19 (CI Pigment Violet 1)
9. A method for producing a magenta toner, which is the solid solution pigment of 9). 27. The solid solution pigment is C.I. I.
Pigment Red 122, C.I. I. Pigmen
t Red 202 and C.I. I. Pigment Vio
27. The method for producing a magenta toner according to claim 26 , wherein the magenta toner contains let19 in the following ratio. 0.3 ≦ A / C ≦ 5.0 0.1 ≦ A × C / B ≦ 10.0 [wherein A is C.I. I. Pigment Red122
The blending weight of C.I. I. Pigment Re
The blending weight of d202 is shown, and C is C.I. I. Pigmen
The compounding weight of tViolet19 is shown. ] 28. polymerizable monomer, a manufacturing method of a magenta toner according to claim 26 or 27 which is a styrene monomer. 29. binder resin, styrene polymer, claim contains a styrene copolymer or a mixture thereof 2
A method for producing a magenta toner according to any one of 6 to 28 . 30. A polymerizable monomer composition further method of making any of a magenta toner according to claim 26 or 29 contains a polar resin. 31. The solid solution pigment comprises C.I. I.
Pigment Red 122 in an amount of 0.50 to 0.85 parts by weight, and C.I. I. Pigment Red 202 in an amount of 0.03 to 0.35 parts by weight, and C.I. I. Pigme
any of the processes for preparation of the magenta toner according to claim 26 or 30 nt Violet 19 contains 0.06 to 0.40 parts by weight. 32. The solid solution pigment comprises C.I. I.
Pigment Red 122 in an amount of 0.55 to 0.80 parts by weight, and C.I. I. Pigment Red 202 is contained in an amount of 0.05 to 0.30 parts by weight, and C.I. I. Pigme
any of the processes for preparation of the magenta toner according to claim 26 or 30 nt Violet 19 contains 0.10 to 0.35 parts by weight. 33. The magenta toner particles, styrene polymers, styrene copolymer or a mixture thereof, any of a magenta toner according to claim 26 or 32 containing a polar resin. 34. The magenta toner particles are made of a binder resin 65.
98 wt%, any of the processes for preparation of the magenta toner according to claim 26 or 33 containing from 1 to 15 wt% magenta pigment and a polar resin from 1 to 20 wt%. 35. The method for producing a magenta toner according to claim 34 , wherein the magenta toner particles contain a polar resin in an amount of 2.0 to 10.0% by weight. 36. The magenta toner particles, to claim 33 containing the polar resin of the magenta pigment and acid 3.0 to 20.0 mg KOH / g so as to satisfy the following formula
35. The method for producing a magenta toner according to 35 . [Outside 3] 37. polar resin production method of any of the magenta toner according to claim 33 or 36 is a saturated polyester resin. 38. The method for producing a magenta toner according to claim 37 , wherein the saturated polyester resin has a number average molecular weight of 2,500 to 10,000. 39. The polar resin is an epoxy resin.
33. The method for producing a magenta toner according to any one of 33 to 35 . 40. The epoxy resin has a number average molecular weight of 2 , 50.
40. The method for producing a magenta toner according to claim 39 , wherein the amount is 0 to 10,000. 41. A polar resin is a styrene - method of any one magenta toner according to claim 33 to 36 acrylic acid copolymer. 42. A styrene - acrylate copolymer has a number average molecular weight of 2, 500 to, claim 4 is 000
1. The method for producing a magenta toner according to any one of 1 . 43. The magenta toner particles, any of the processes for preparation of the magenta toner of the DSC endothermic 26 to claim endothermic main peak contains a low softening point material fifty-five to one hundred thirty ° C. in curve 42. 44. The method for producing magenta toner according to claim 43, wherein the magenta toner particles contain 5 to 25% by weight of a low softening point substance. 45. The low softening point substance is a wax.
43 or 44, the method for producing a magenta toner. 46. The low softening point substance is a long-chain ester portion having 15 or more carbon atoms. (Wherein, R ₁ is showing a number 15 or more organic groups carbon) claims 43 to 45 containing an ester compound having a
1. A method for manufacturing a magenta toner according to any one of 1. 47. The low softening point substance is represented by the following formula (1) R ₂ —COO—R ₃ (1) [wherein, R ₂ and R ₃ represent a saturated hydrocarbon group having 15 to 45 carbon atoms]. ] The method for producing a magenta toner according to any one of claims 43 to 45 , which comprises an ester compound represented by the above. 48. The method for producing a magenta toner according to claim 47 , wherein R ₂ and R ₃ are alkyl groups. 49. The magenta toner particles have a shape factor SF.
Method of any one magenta toner according to claim 26 or 48 -1 is 100 to 150. 50. The magenta toner particles have a shape factor SF.
Method of any one magenta toner according to claim 26 or 48 -1 is 100 to 125. 51. The magenta toner particles, any of the processes for preparation of the magenta toner according to claim 26 to 50 weight average particle diameter of 3～9Myuemu.