JP3382519B2 - 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 electrophotography and electrostatic printing.

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

[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 come to 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 a dot diameter of 20 μm to 70 μm corresponding to the original image is obtained. A latent image of Y (yellow), M (magenta), C (cyan),
A large amount of toner is transferred from the photoconductor to the intermediate transfer body, as compared with a black and white copying machine which reproduces by using the subtractive color mixing action at the time of heat and pressure fixing, using each color toner of B (black), or
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 and diketopyrrolopyrrole colorants have been known as magenta toner colorants.

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 for the time being, magenta toners having excellent triboelectrification characteristics and color tones can be obtained, but they satisfy transparency and are more faithful to the original. In order to obtain an image, a magenta toner having further improved color tone, saturation, and electrophotographic characteristics is 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.

It is an object of the present invention to provide a magenta toner for developing an electrostatic charge image, which can obtain extremely vivid colors with 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]

Specifically, the present invention is
A magenta toner for developing an electrostatic image comprising magenta toner particles containing at least a binder resin, a magenta pigment and a polar resin, wherein the binder resin is a styrene polymer, a styrene copolymer or a mixture thereof. The pigment is C.I. Eye. Pigment Red 122 (C.I.
I. Pigment Red 122) and C.I. Eye.
Pigment Violet 19 (CI Pigme
nt Violet 19) solid solution pigment or C.I. Eye. Pigment Red 202 (C.I. Pigme
nt Red 202) and C. Eye. Pigment Violet 19 (C.I. Pigment Viol
et 19) solid solution pigment, the polar resin having an acid value of 3 to
It relates to a magenta toner for developing an electrostatic charge image, which has a content of 20 mgKOH / g.

Further, the present invention is a method for producing a magenta toner having magenta toner particles, which comprises a styrene monomer, optionally other vinyl monomer, a magenta pigment,
A polarizable resin and a polymerization initiator are mixed to prepare a polymerizable monomer composition, and the polymerizable monomer composition is dispersed in an aqueous medium to produce particles of the polymerizable monomer composition, A method for producing magenta toner particles by polymerizing a styrene monomer in particles of a polymerizable monomer composition in a medium to produce a magenta toner particle, wherein the binder resin is a styrene polymer or a styrene copolymer. Or a mixture thereof, and the magenta pigment is C.I.
I. Pigment Red 122 and C.I. I. Pig
ment Violet 19 solid solution pigments or C.I.
I. Pigment Red 202 and C.I. I. Pig
mentViolet 19 and the polar resin has an acid value of 3 to 20 mgKOH / g.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION One of the features of the present invention is to include a specific solid solution pigment and a polar resin having a specific acid value in toner particles.

The solid solution pigment used in the present invention is generally obtained by a step of mixing two or more magenta pigments in a dehydration step in the pigment production process and a step before the pigmentation step, 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, from the viewpoints of excellent light resistance and excellent coloring power, a substituted quinacridone pigment having the structure shown below and an unsubstituted quinacridone pigment are used in combination.

Magenta solid solution pigment (1) : C.I. I. Pi
gment Red 122 and C.I. I. Pigment
Solid solution with Violet 19.

[0022]

[Outside 13]

Magenta solid solution pigment (2) : C.I. I. P
igment Red 202 and C.I. I. Pigmen
A solid solution with t Violet 19.

[0024]

[Outside 14]

C. I. Pigment Violet
Although the light resistance and the coloring power of 19 are likely to change depending on its crystal structure, they are stabilized by forming a solid solution. Furthermore, the hue of the solid solution is C.I. I. Pigment Viol
By changing the compounding ratio of et 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 brightness of the pigment.

In order to make the saturation and tinting strength of the solid solution pigment more preferable, the compounding ratio of the substituted quinacridone pigment and the unsubstituted quinacridone pigment in the solid solution pigment is 85:15.
It is preferably 30:70, more preferably 8
0:20 to 50:50 is preferable.

When the blending ratio of the substituted quinacridone pigment in the solid solution pigment exceeds 85:15, a fine secondary crystal structure of the substituted quinacridone alone tends to occur in the solid solution, so that the saturation tends to be slightly decreased.

When the compounding ratio of the substituted quinacridone pigment in the pigment is less than 30:70, on the contrary, a fine secondary crystal structure of the unsubstituted quinacridone alone occurs in the solid solution (for example, γ-type quinacridone is formed). ), The coloring power is slightly reduced.

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 a polymerizable monomer composition prepared by mixing a styrene monomer, optionally other vinyl monomer, a magenta solid solution pigment, a polar resin having an acid value of 3 to 20 mgKOH / g and a polymerization initiator. Adjust
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 to produce Preferably.

When the magenta toner particles are produced by such a manufacturing method, the magenta solid solution pigment is dispersed to near the primary particles and the acid value is 3 when the polymerizable monomer composition is prepared.
This is because the re-aggregation of particles of the magenta solid solution pigment having a nitrogen atom is suppressed by the polar resin of 20 mgKOH / g to 20 mgKOH / g, whereby the coloring power, lightness and chroma of the magenta toner particles are improved.

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. The acid value of the polar resin is in the range of 3 to 20 (KOHmg / g) in order to have both the function of suppressing the temperature and the function of stabilizing the particles of the polymerizable monomer composition in the aqueous medium. is important.

If the acid value of the polar resin is less than 3 KOHmg / g, the polar resin and the solid solution pigment have a low affinity and are easily separated from each other, so that the effect of suppressing re-aggregation is low and the coloring power and chargeability are lowered. Occurs. Acid value of polar resin is 20KOHm
When it exceeds g / g, the cohesiveness between the molecular chains of the polar resin becomes large, so that the dispersibility of the polar resin in the styrene monomer (non-polar liquid) decreases. Therefore, the stabilization of the particles of the polymerizable monomer composition by the polar resin in the aqueous medium decreases, and the manufacturing stability of the magenta toner particles decreases.

Considering suppression of reaggregation 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, and further contained so as to satisfy the following formula. Is more preferable.

[0035]

[Outside 15]

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 an unsaturated group is used, a cross-linking reaction occurs between the styrene monomer and the polar resin, and the color mixing property decreases, 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, a polymerizable monomer composition containing a styrene monomer may optionally contain o (m, p)
-Substituted styrene monomers such as methylstyrene, m (p) -ethylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate,
Butyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dimethyl (meth) acrylate A (meth) acrylic acid ester-based monomer such as aminoethyl or diethylaminoethyl (meth) acrylate; a monomer such as butadiene, isoprene, cyclohexene, (meth) acrylonitrile, or acrylic acid amide may be added. Preferably, Publication Polymer Handbook Second
Edition III-P139-192 (John Wiley & S
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 Ons. If the theoretical glass transition temperature is less than 50 ° C, problems easily occur from the viewpoint of storage stability of the toner and durability stability of the toner, while if it exceeds 85 ° C, the transparency of the OHP image in the case of full-color image formation is high. Sex decreases.

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 16] 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 17] [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 18] [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 19] [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 20] [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 21]

[0060]

[Outside 22]

[0061]

[Outside 23]

[0062]

[Outside 24]

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 coloring power 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 25] [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 26] (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.

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

Production Example 1 of solid solution pigment :

[0109]

[Outside 27] 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 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.
let 19) was prepared.

Crude 2,9-dimethylquinacridone 66
Parts by weight and crude quinacridone 34 parts by weight with water 600
Add to a container equipped with a condenser having a mixed solution consisting of 300 parts by weight of ethanol and 5 parts by weight, and
The mixture was heated to reflux while milling 9-dimethylquinacridone and quinacridone. After 5 hours, the solid solution pigment was filtered off, washed, dried and then pulverized to obtain a solid solution magenta pigment (1).

Production Example 2 of Solid Solution Pigment

[0114]

[Outside 29] 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.

Crude 3,10-dichloroquinacridone 2
0 part by weight and 80 parts by weight of crude unsubstituted quinacridone were 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 the mixture was mixed with 3,10-dichloroquinacridone and 5 parts for 5 hours. The mixture was heated to reflux while grinding the quinacridone. After 5 hours, the solid solution pigment was filtered off, washed, dried and then pulverized to obtain a solid solution magenta pigment (2).

Example 1 A 0.1 M Na ₃ PO ₄ aqueous solution and a 1 M NOCaCl ₂ aqueous solution were prepared. In a four-necked flask equipped with a high-speed stirring device TK-Homomixer, 710 parts by weight of ion-exchanged water and 0.
450 parts by weight of a 1 mol-Na ₃ PO ₄ aqueous solution was added to adjust the rotation speed to 12,000 rotations, and the mixture was heated to 65 ° C.
68 parts by weight of a 1.0 mol-CaCl ₂ aqueous solution was gradually added to prepare an aqueous dispersion medium containing a minute sparingly water-soluble dispersant Ca ₃ (PO ₄ ) ₂ . 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-) Polymer of trimellitic acid; 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) ester wax (endothermic main peak value 64.4 ° C.) 15 parts by weight (ester compound (1 ) Is the main ingredient; 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 added to 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. 2 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile), which is a polymerization initiator, was added to the pigment dispersion liquid 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, the weight average diameter of the magenta toner particles measured by a Coulter counter is 6.2 μm, the number variation coefficient is 28%, and the shape factor S
F-1 was 107. The magenta toner particles obtained were styrene-n-butyl acrylate, copolymer about 2
It contained 00 parts by weight, 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 and about 15 parts by weight of an ester wax.

2 parts by weight of hydrophobized titanium oxide fine powder was externally added to 100 parts by weight of the obtained magenta toner particles to obtain a magenta toner. To 7 parts by weight of this toner, an acrylic resin-coated magnetic ferrite carrier 93 was added. Durability evaluation was performed by mixing two parts by weight and using a full-color copying machine CLC500 modified by Canon as a two-component developer. A stable, clear and good magenta image was obtained without lowering the developability even after running for 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 2.

Comparative Example 1 The colorant was C.I. I. Pigment Red 122 7
Magenta toner particles 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 magenta toner particles was 6.2 μm, the number variation coefficient was 58%, and the shape factor SF-1 was 109.

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.

Magenta toner was obtained by externally adding 2 parts by weight of hydrophobized titanium oxide fine powder to 100 parts by weight of the obtained magenta toner particles, and 93 parts by weight of an acrylic resin-coated ferrite carrier was added to 7 parts by weight of this toner. Was mixed and used as a two-component developer, and the durability was evaluated by a full-color copying machine CLC500 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
Magenta toner particles were produced in the same manner as in Example 1 except that the amount was changed to 7 parts by weight. The obtained magenta toner particles had a weight average particle diameter of 6.7 μm, a number variation coefficient of 49% and a shape factor SF-1 of 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.

Durability evaluation of the obtained magenta toner particles was carried out in the same manner as in Example 1. As a result, the electrification was lower than in Example 1 and therefore fog was generated from the beginning and the image quality was poor.

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
Magenta toner particles 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 magenta toner particles have a weight average particle diameter of 5.9 μm and a number variation coefficient of 56%.
The shape factor SF-1 was 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, OHP permeability,
In particular, the color reproducibility was poor.

Comparative Example 4 Saturated polyester resin (bisphenol A-phthalic anhydride-succinic acid); acid value 2 mgKOH / g; Mn = 45
00; peak molecular weight; 6500). Magenta toner particles were obtained in the same manner as in Example 1.

The weight average diameter of the obtained magenta toner particles is 6.2 μm, the number variation coefficient is 74%, and the shape factor S is
F-1 was 109.

When the durability of the obtained magenta toner particles was evaluated in the same manner as in Example 1, the chargeability was unstable as compared with Example 1, and fog occurred as the number of durable sheets increased.

Further, the coloring power, the color reproducibility and the OHP transparency were worse than in Example 1 because the colorant was not well dispersed in the magenta toner particles.

Comparative Example 5 Saturated polyester resin (terephthalic acid-propylene oxide modified bisphenol A-ethylene oxide modified bisphenol A-trimellitic acid polymer; acid value 2)
6 mg KOH / g, Mn = 8900, peak molecular weight; 1
Magenta toner particles were obtained in the same manner as in Example 1 except that (5000) was used.

The magenta toner particles obtained had a weight average particle diameter of 8.7 μm, a number variation coefficient of 54% and a shape factor SF.
-1 was 123.

When the durability of the obtained magenta toner particles was evaluated in the same manner as in Example 1, the charging property was unstable as compared with Example 1, and fog occurred.

In addition, the coloring power, color reproducibility and OHP transparency were inferior to those in Example 1 because the colorant was dispersed a little poorly.

Example 2 Magenta toner particles were treated in the same manner as in Example 1 except that the ester wax of Example 1 was changed to 7 parts by weight of alcohol-modified polypropylene wax (maximum endothermic peak value; 94 ° C.). Obtained.

The magenta toner particles thus obtained had a weight average diameter of 7.1 μm, a number variation coefficient of 33% and a shape factor SF.
-1 was 106.

When the obtained magenta toner particles were subjected to a durability test in the same manner as in Example 1, a clear and good magenta image having stable developability was obtained.

Since the colorant was slightly poorly dispersed as compared with Example 1, the coloring power, the color reproducibility and the OHP transmissivity were slightly deteriorated, but they were at a practically acceptable level.

Example 3 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 were obtained in the same manner as in Example 1, except that the peak molecular weight was changed to 700;

The magenta toner particles thus obtained had a weight average particle diameter of 6.4 μm, a number variation coefficient of 30% and a shape factor SF.
-1 was 120.

When the obtained magenta toner particles were evaluated for durability in the same manner as in Example 1, a clear and good magenta image having stable developability was obtained.

The color reproducibility was slightly deteriorated because the dispersion of the colorant was slightly worse than in Example 1, but it was at a level where there was no practical problem.

Example 4 The saturated polyester resin of Example 1 was replaced with an epoxy resin (a polymer of bisphenol A-epichlorohydrin-phthalic anhydride-triethylenetetramine; acid value = 3 mgKOH /
g; Mn = 2800; peak molecular weight; 7500) Magenta toner particles were obtained in the same manner as in Example 1 except that the amount was changed to 5 parts by weight.

The obtained magenta toner had a weight average diameter of 5.9 μm, a number variation coefficient of 33% and a shape factor SF.
-1 was 109.

The durability evaluation of the obtained magenta toner particles was carried out in the same manner as in Example 1. As a result, the fog was slightly generated as compared with Example 1 due to its slightly lower charging property, but the developability was stable at a practical level. A clear and good magenta image was obtained.

Compared with Example 1, the amount of toner scattering due to the transfer was slightly larger, so that the highlight reproducibility was slightly deteriorated, but it was at a level where there was no practical problem.

Example 5 Magenta toner particles were obtained in the same manner as in Example 1 except that the solid solution magenta pigment (2) was used instead of the pigment of Example 1.

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

When the obtained magenta toner particles were evaluated for durability in the same manner as in Example 1, a clear and good magenta image having stable developing property was obtained.

Compared with Example 1, the colorant in the magenta toner particles contained a large amount of coarse particles, so that the color reproducibility and the coloring power were slightly deteriorated, but they were at a level where there was no practical problem.

The formulations of the above Examples and Comparative Examples are shown in Table 1, and the evaluation results of each toner are shown in Table 2.

[0159]

[Table 1]

[0160]

[Table 2]

[0161]

As described above, according to the present invention,
By using a solid solution pigment of a specific type of quinacridone pigment and a polar resin having an acid value in a specific range, it is possible to obtain excellent triboelectric chargeability and obtain an extremely vivid color, and
A magenta toner for developing an electrostatic charge image having excellent P transparency and manufacturing stability was obtained.

[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 (58) Fields investigated (Int.Cl. ⁷ , DB name) G03G 9/08

Claims (69)

(57) [Claims] 1. A magenta toner for developing an electrostatic image comprising magenta toner particles containing at least a binder resin, a magenta pigment and a polar resin, wherein the binder resin is a styrene polymer, a styrene copolymer or a mixture thereof. And the magenta pigment is C.I. Eye. Pigment red
122 (CI Pigment Red 122) and C.I. Eye. Pigment Violet 19 (C.I.
I. Pigment Violet 19) solid solution pigment or C.I. Eye. Pigment Red 202 (C.I.
I. Pigment Red 202) and C.I. Eye.
Pigment Violet 19 (CI Pigme
nt Violet 19) solid solution pigment, wherein the polar resin has an acid value of 3 to 20 mgKOH / g. 2. The solid solution pigment is C.I. I. Pigment
Red 122 and C.I. I. Pigment Violet
The magenta toner according to claim 1, wherein the compounding weight ratio to t 19 is 85:15 to 30:70. 3. The solid solution pigment is C.I. I. Pigment
Red 202 and C.I. I. Pigment Viol
The blending weight ratio with et 19 is 85:15 to 30:70.
The magenta toner according to claim 1 or 2. 4. The magenta toner particles are made of a binder resin 65 to 65.
4. The magenta toner according to claim 1, which contains 98% by weight, 1 to 15% by weight of a magenta pigment, and 1 to 20% by weight of a polar resin. 5. The magenta toner particles include a polar resin of 2.
The magenta toner according to any one of claims 1 to 4, containing 0 to 10.0% by weight. 6. The magenta toner according to claim 1, wherein the magenta toner particles contain a magenta pigment and a polar resin so as to satisfy the following formula (A). [Outer 1] 7. The magenta toner particles have a polar resin content of 2.0.
The magenta toner according to claim 1, wherein the magenta toner is contained in an amount of ˜10.0% by weight. 8. The magenta toner according to claim 1, wherein the polar resin is a saturated polyester resin. 9. The magenta toner according to claim 8, wherein the saturated polyester resin has a number average molecular weight of 2,500 to 10,000. 10. The magenta toner according to claim 1, wherein the polar resin is an epoxy resin. 11. The epoxy resin has a number average molecular weight of 2,5.
11. The magenta toner according to claim 10, which is from 00 to 10,000. 12. The magenta toner according to claim 1, wherein the polar resin is a styrene-acrylic acid copolymer. 13. The styrene-acrylic acid copolymer has a number average molecular weight of 2,500 to 10,000.
2 magenta toner. 14. 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. 15. The magenta toner according to claim 14, wherein the magenta toner particles contain 5 to 25% by weight of a low softening point substance. 16. The magenta toner according to claim 14, wherein the low softening point substance is wax. 17. The low softening point substance is a long-chain ester portion having 15 or more carbon atoms. 17. An ester compound containing (wherein R ₁ represents an organic group having 15 or more carbon atoms).
One of the magenta toners. 18. The low softening point substance contains an ester compound represented by the following formula (1).
One of the magenta toners. R ₂ —COO—R ₃ (1) [In the formula, R ₂ and R ₃ represent a saturated hydrocarbon group having 15 to 45 carbon atoms. ] 19. The magenta toner according to claim 18, wherein R ₂ and R ₃ are alkyl groups. 20. The magenta toner according to claim 14, wherein the low softening point substance contains an ester compound represented by the following formula (2). [Outside 3] [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 20 carbon atoms. ] 21. R ₄ and R ₆ are alkyl groups, and R
The magenta toner according to claim 20, wherein ₅ is an alkylene group. 22. The magenta toner according to claim 14, wherein the low softening point substance contains an ester compound represented by the following formula (3). [Outside 4] [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. ] 23. R ₇ and R ₉ represent an alkyl group, and R ₇
The magenta toner according to claim 22, wherein ₈ represents an alkylene group. 24. The low softening point substance contains an ester compound represented by the following formula (4).
One of the magenta toners. [Outside 5] [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. ] 25. The magenta toner according to claim 24, wherein R ₁₀ and R ₁₁ are alkyl groups. 26. The low softening point substance contains an ester compound represented by the following formula (5).
One of the magenta toners. [Outside 6] [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, 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. ] 27. The magenta toner according to claim 26, wherein R ₁₂ , R ₁₃ and R ₁₄ are alkyl groups. 28. The magenta toner particles have a shape factor SF.
28. The magenta toner according to claim 1, wherein -1 is 100 to 150. 29. The magenta toner particles have a shape factor SF.
28. The magenta toner according to claim 1, wherein-is 100 to 125. 30. The magenta toner particles contain 0.5 to 10% by weight of a negative chargeability control agent.
Magenta toner of any of 9. 31. The magenta toner according to claim 30, wherein the negative charge control agent is a metal compound of aromatic hydroxycarboxylic acid. 32. The 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 31, containing the produced polymerized magenta toner particles. 33. The polymerizable monomer composition further contains an acrylic acid ester monomer or a methacrylic acid ester monomer, wherein the polymerized magenta toner particles are a styrene copolymer produced by polymerization of the monomer in an aqueous medium. The magenta toner according to claim 32, wherein the magenta toner contains the magenta toner. 34. The magenta toner according to claim 1, wherein the magenta toner particles have a weight average particle diameter of 3 to 9 μm. 35. The magenta toner according to claim 1, wherein the magenta toner particles have a weight average particle diameter of 3 to 8 μm. 36. A method for producing a magenta toner having magenta toner particles, which comprises mixing a styrene monomer, optionally other vinyl monomer, a magenta pigment, a polar resin and a polymerization initiator to prepare a polymerizable monomer composition. Then, 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. The binder resin is a styrene polymer, a styrene copolymer, or a mixture thereof, and the magenta pigment is C.I. I. Pigment Red 1
22 and C.I. I. Pigment Violet 19 solid solution pigment or C.I. I. Pigment Red 20
2 and C.I. I. Pigment Violet 19 is a solid solution, and the polar resin has an acid value of 3 to 20 mgKOH / g. 37. The method according to claim 36, wherein the polymerizable monomer composition is prepared by adding a polymerization initiator after the styrene monomer, the solid solution pigment and the polar resin are mixed. 38. The method according to claim 36 or 37, wherein the magenta toner particles are prepared by a suspension polymerization method. 39. The solid solution pigment is C.I. I. Pigment
Red 122 and C.I. I. Pigment Viol
The blending weight ratio with et 19 is 85:15 to 30:70.
39. The manufacturing method according to claim 36, wherein 40. The solid solution pigment is C.I. I. Pigmen
t Red 202 and C.I. I. Pigment Vio
The blending weight ratio with let 19 is 85:15 to 30: 7.
39. The manufacturing method according to claim 36, wherein the manufacturing method is 0. 41. The magenta toner particles are made of a binder resin 65.
40 to 98% by weight, a magenta pigment 1 to 15% by weight, and a polar resin 1 to 20% by weight. 42. The method according to claim 41, wherein the magenta toner particles contain a polar resin in an amount of 2.0 to 10.0% by weight. 43. The method according to claim 36, wherein the magenta toner particles contain a magenta pigment and a polar resin so as to satisfy the following formula (A). [Outside 7] 44. The method according to claim 36, wherein the polar resin is a saturated polyester resin. 45. The method according to claim 44, wherein the saturated polyester resin has a number average molecular weight of 2,500 to 10,000. 46. The method according to claim 36, wherein the polar resin is an epoxy resin. 47. The epoxy resin has a number average molecular weight of 2,5.
47. The method according to claim 46, wherein the production method is 00 to 10,000. 48. The method according to claim 36, wherein the polar resin is a styrene-acrylic acid copolymer. 49. The styrene-acrylic acid copolymer has a number average molecular weight of 2,500 to 10,000.
Manufacturing method of 8. 50. The polymerizable monomer composition further comprises DSC.
The production method according to any one of claims 36 to 49, which contains a low softening point substance having an endothermic main peak in an endothermic curve of 55 to 130 ° C. 51. The method according to claim 50, wherein the polymerizable monomer composition contains the low softening point substance in an amount of 5 to 25% by weight. 52. The method according to claim 50 or 51, wherein the low softening point substance is wax. 53. The low softening point substance is a long-chain ester portion having 15 or more carbon atoms. 53. An ester compound having (wherein R ₁ represents an organic group having 15 or more carbon atoms) 53.
One of the manufacturing method of. 54. The low softening point substance contains an ester compound represented by the following formula (1):
One of the manufacturing method of. R ₂ —COO—R ₃ (1) [In the formula, R ₂ and R ₃ represent a saturated hydrocarbon group having 15 to 45 carbon atoms. ] 55. The method according to claim 54, wherein R ₂ and R ₃ are alkyl groups. 56. The method according to claim 50, wherein the low softening point substance contains an ester compound represented by the following formula (2). [Outside 9] [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 20 carbon atoms] 57. R ₄ and R ₆ are alkyl groups, R
57. The production method according to claim 56, wherein ₅ is an alkylene group. 58. The method according to any one of claims 50 to 52, wherein the low softening point substance contains an ester compound represented by the following formula (3). [Outside 10] [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. ] 59. R ₇ and R ₉ represent an alkyl group, and R ₇
59. The production method according to claim 58, wherein ₈ represents an alkylene group. 60. The low softening point substance contains an ester compound represented by the following formula (4).
One of the manufacturing method of. [Outside 11] [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. ] 61. The method according to claim 60, wherein R ₁₀ and R ₁₁ are alkyl groups. 62. The low softening point substance contains an ester compound represented by the following formula (5):
One of the manufacturing method of. [Outside 12] [In the formula, 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, 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. ] 63. The method according to claim 62, wherein R ₁₂ , R ₁₃ and R ₁₄ are alkyl groups. 64. The magenta toner particles have a shape factor SF.
64. The manufacturing method according to claim 36, wherein -1 is 100 to 150. 65. The magenta toner particles have a shape factor SF.
The manufacturing method according to any one of claims 36 to 63, wherein-is 100 to 125. 66. The method according to claim 36, wherein the polymerizable monomer composition contains 0.5 to 10% by weight of a negative chargeability control agent. 67. The method according to claim 66, wherein the negative charge control agent is a metal compound of aromatic hydroxycarboxylic acid. 68. The method according to claim 36, wherein the magenta toner particles have a weight average particle diameter of 3 to 9 μm. 69. The method according to claim 36, wherein the magenta toner particles have a weight average particle diameter of 3 to 8 μm.