JP2003202697A - Toner and method of producing toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide toner excellent in coloring power and transparency by finely dispersing pigment in the toner, and a method of producing the toner. <P>SOLUTION: The toner incorporates at least binding resin, the pigment and a pigment dispersant, and the pigment dispersant is expressed by formula (1) or (2). <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner for developing an electrostatic charge image in an image forming method such as electrophotography and electrostatic printing, or for forming a toner image in a toner jet type image forming method. The present invention relates to a method for producing a toner, and more particularly to a method for producing a toner which is used in a fixing system in which a toner image formed of the toner is heated and pressed and fixed on a print sheet such as a transfer material.

[0002]

2. Description of the Related Art In order to visualize an electric or magnetic latent image on a recording medium, an electrostatic latent image such as toner is adsorbed on the latent image to form a visible image. There is a way. A typical example thereof is electrophotography, and a number of methods are known as described in, for example, US Pat. No. 2,297,691.
In this electrophotographic method, generally, a photoconductive material is used, an electric latent image is formed on a photoreceptor by various means, and then the latent image is developed with a toner to form a toner image. After the toner image is transferred to a transfer material such as paper, if necessary, the toner image is fixed on the transfer material by heating, pressurizing, or using solvent vapor to obtain a copy.

In recent years, the above-mentioned technology has been applied to high printing quality.
Due to its quietness, it has come to be used for output means such as computers and word processors, so-called printers. Usually, a toner used in a printer or a copying machine is a fine particle whose main components are a resin and a magnetic material, a carbon black, a coloring agent such as a dye and a pigment, and waxes, and the particle size thereof is usually 6 to 30 μm. It is a range. Toner is generally manufactured as a toner having a desired particle diameter by mixing and melting a coloring agent composed of a dye or pigment or a magnetic substance in a thermoplastic resin, uniformly dispersing the coloring agent, and then finely pulverizing and classifying the mixture. Has been done. This method is relatively stable as a technology, and management of each material and each process can be performed relatively easily.

On the other hand, a method for producing a toner by a polymerization method, that is, a method for producing a toner by a so-called suspension polymerization method has been proposed. These are disclosed, for example, in JP-B-36-10231, JP-B-51-14895, and JP-A-53-17.
7735, JP-A-53-17736, and JP-A-53-17737. In this method, a colorant such as a binder resin, a dye, or a pigment, for example, a magnetic material, carbon black, a charge control agent, a release agent such as wax or silicone oil, or the like, and a substance to be encapsulated in the toner are added as necessary. A polymerizable composition is dissolved or dispersed in a polymerizable monomer together with a polymerization initiator and a dispersant, and dispersed using a dispersion device in an aqueous continuous phase containing a dispersion stabilizer to obtain a dispersion of fine particles, By polymerizing and solidifying this dispersion, toner particles having a desired particle size and composition are obtained. Since this method has no crushing step, it is expected to save energy, improve the process yield, and reduce the cost.

As a method for improving the printing quality, a technique for reducing the particle diameter of the above-mentioned toner and reproducing the above-mentioned latent image finely and faithfully has been actively studied. However, when the particle size is reduced, the amount of toner per unit area is reduced, so that it is necessary to increase the coloring power per unit volume of toner in order to obtain a desired image density. As a means for this, a means for increasing the amount of the dye or pigment as a coloring agent is generally used. However, the pigment used as a toner colorant, particularly a quinacridone pigment, is expensive and the production cost is increased. There is. Therefore, in order to enhance the coloring power of the dye / pigment itself and improve the transparency of OHP, much research has been conducted on improving the dispersibility of the dye / pigment inside the toner.

In order to improve the dispersibility of the dye / pigment, it is generally important that the dye / pigment and the resin are easily compatible with each other, and the dye / pigment is surface-treated. As a proposal to improve the dispersibility by surface-treating a dye / pigment, Japanese Patent Application Laid-Open No. 11-119461 and Patent 2800 are proposed.
No. 558, etc. are mentioned. However, there is still room for improvement regarding the dispersibility of the pigment in the toner.

In the case of pulverized toner, it is necessary to adjust the treatment of dyes and pigments according to the composition of the binder resin, and if the matching of the two is inappropriate, a good dispersion state cannot be obtained. was there.

In the case of polymerized toners, the surface treatment of dyes and pigments is often carried out, but in many cases, hydrophobic treatment with a silane coupling agent or a pigment dispersant which is a polymer having a polar group is used as a coloring material. It was intended to prevent the aggregation of the pigment by adsorbing it on the surface.

However, when such a pigment dispersant is used, a certain degree of dispersion state can be obtained, but pigment reaggregation occurs in the subsequent steps such as drying, molding, polymerization reaction and the like. In the production of a polymerized toner, the presence of polar groups on the surface of the pigment may cause the pigment to float on the surface of the toner, resulting in a decrease in charging property and environmental stability.

[0010]

Therefore, the present invention is
An object of the present invention is to provide a toner that solves the above problems and a method for manufacturing the toner.

That is, an object of the present invention is to provide a toner excellent in coloring power and transparency and a method for producing the toner.

Another object of the present invention is to provide a toner in which the amount of pigment added to the toner is small and the cost is reduced, and a method for producing the toner.

It is another object of the present invention to provide a toner which does not cause a coloring agent to float on the surface of the toner and which is excellent in charging property and environmental stability, and a method for producing the toner.

[0014]

That is, the present invention is a toner containing at least a binder resin, a pigment and a pigment dispersant, wherein the pigment dispersant is represented by the following formula (1):

[Outside 21]

(1) (At least one of R ₁ and R ₂ is a substituent X ₁ (others are hydrogen), and the substituent Y ₁ is an oligomer or a polymer.

[0016]

[Outside 22]

And a toner represented by the formula (1).

The present invention also provides a toner containing at least a binder resin, a pigment and a pigment dispersant, wherein the pigment dispersant has the following formula (2).

[Outside 23]

(2) (At least one of R ₃ and R ₄ is a substituent X ₂ (other is hydrogen), and the substituents Y ₂ and Y ₃ are H, CH ₃ ,
It is a substituent selected from the group consisting of oligomers and polymers.

[0020]

[Outside 24]

And a toner represented by the formula (1).

The present invention also relates to a method for producing the above toner.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION The pigment dispersant according to the present invention comprises a quinacridone-based molecular skeleton which is easily adsorbed to a pigment which is a colorant, and an oligomer or polymer which has excellent affinity with a solvent and a resin which serves as a toner binder. Has a covalently bonded structure. Further, the pigment dispersant according to the present invention,
Since the above substituents X ₁ and X ₂ have an affinity with the polymerizable monomer used in the pigment dispersion step and the resin serving as the toner binder, The pigment dispersant is unlikely to be released and can be stably present.

The pigment dispersant that can be used in the present invention has the structure of formula (1) or (2), and at least one of R ₁ and R ₂ in formula (1) is the substituent X _1. , The number of the substituents X ₁ enhances the affinity with the solvent, but may hinder the adsorptive power to the pigment. Therefore, it is more preferable that one is the substituent X ₁ and the other is a hydrogen atom. preferable. Similarly in the formula (2), at least one of R ₃ and R ₄ is the substituent X ₂ , preferably one is the substituent X ₂ and the other is a hydrogen atom.

The substituent Y ₁ , which can be used in the present invention,
As Y ₂ and Y ₃ , a known oligomer or polymer substituent can be used, and in particular, a monomer selected from the group consisting of styrene, a styrene derivative, (meth) acrylic acid and a (meth) acrylic acid derivative is used. A vinyl polymer component or a polyester component contained as a monomer unit is effective, and it is necessary that it has excellent affinity with a solvent used in the pigment dispersion step and a resin serving as a toner binder. Specific examples of the oligomer or polymer constituting the substituents Y ₁ , Y ₂ and Y ₃ include polystyrene, poly-α-methylstyrene, polyacrylate, polymethacrylate, styrene-acrylic acid ester copolymer, styrene- Methacrylic acid ester copolymer, styrene-glycidyl acrylate copolymer,
Examples thereof include styrene-glycidyl methacrylate copolymer and polyester. The number average molecular weight of the substituents Y ₁ , Y ₂ and Y ₃ is preferably 500 to 100,000 (more preferably 500 to 30,000) in consideration of the solubility in the solvent used in the pigment dispersion step. The molecular weight distribution is preferably sharp. The molecular weight of the substituents Y ₁ , Y ₂ and Y ₃ can be controlled by adjusting the molecular weight of the oligomer or polymer used when introducing the oligomer or polymer as a substituent into the compound having a quinacridone skeleton.

The amount of the pigment dispersant used in the present invention is 2 to 100 parts by mass with respect to 100 parts by mass of the pigment, and 3 to 30 when the toner is produced by the polymerization method.
More preferably, it is parts by mass.

In the production of the toner of the present invention, a known formulation except that it contains the pigment dispersant represented by the formula (1) or (2), that is, addition of pigments, resins, other waxes and charge control agents. Agents can be used,
As a manufacturing method, a known method can be used. When the toner is manufactured by the pulverization method, a binder resin,
A pigment dispersant is mixed with a pigment and other additives, and heat and mechanical shearing forces are applied to melt and knead the mixture, and a pulverization step and a classification step are performed to obtain a toner. In the case of the pulverizing method, the pigment may be previously treated with a pigment dispersant, and the pigment may be melt-kneaded to produce a toner. On the other hand, it is also possible to produce a toner by a polymerization method in which a polymerizable monomer is directly polymerized in an aqueous medium to obtain toner particles, and the toner is prepared by a suspension polymerization method, an emulsion polymerization method, an emulsion aggregation method or the like. Obtainable. In the method for producing a suspension polymerization toner, in all or part of the polymerizable monomer, a pigment dispersant,
And, if necessary, melt the resin, gradually add the pigment powder while stirring to sufficiently blend with the polymerizable monomer, further ball mill, paint shaker, dissolver,
A pigment-dispersed paste obtained by applying mechanical shearing force with a disperser such as an attritor, a sand mill, or a high-speed mill is produced, and the obtained pigment-dispersed paste, a polymerization initiator, and the remaining polymerizable monomer. Can be mixed to obtain a polymerizable monomer composition, which can be added to an aqueous solvent containing a dispersion stabilizer for granulation and a polymerization reaction to obtain toner particles. In the case of the polymerization method, the pigment and the pigment dispersant may be separately added and mixed when the polymerizable monomer composition is produced.

The polymerizable monomer that can be used when the toner of the present invention is produced by a polymerization method is an addition polymerization type or condensation polymerization type monomer. Preferred are addition polymerization type monomers. Specifically, styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, p-
Methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn -Styrene derivatives such as hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene; unsaturated monoolefins such as ethylene, propylene, butylene, isobutylene Unsaturated polyenes such as butadiene and isoprene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl iodide; vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzenoate; methyl methacrylate , Ethyl methacrylate, propyl methacrylate, Methacrylic acid -n- octyl, dodecyl methacrylate, 2-ethylhexyl, stearyl methacrylate, phenyl methacrylate,
Α-methylene aliphatic carboxylic acid monoesters such as dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, -n-butyl acrylate, isobutyl acrylate,
Propyl acrylate, -n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate,
Acrylic esters such as phenyl acrylate; Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone; N-vinyl pyrrole, N
-N-vinyl compounds such as vinylcarbazole, N-vinylindole and N-vinylpyrrolidone; vinylnaphthalene compounds; and (meth) acrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide.

The binder resin used when the toner of the present invention is manufactured by the pulverization method is mainly determined by its affinity with the substituent X ₁ or X ₂ . For example,
Examples thereof include polystyrene, poly-α-methylstyrene, polyacrylic acid, polymethacrylic acid, polyacrylic acid ester, polymethacrylic acid ester, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, and polyester.

As the pigment that can be used in the present invention, known pigments can be used, and particularly preferred are colored pigments such as quinacridone pigments, carbon black and phthalocyanine pigments. For example, Pigment Violet 19, Pigment Red 122, Pigment Red 207, Pigment Red 206, Pigment Red 202, Pigment Black 6, Pigment Black 7, Pigment Black 8, Pigment Black 10,
Pigment Blue 16, Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 5, Pigment Blue 15: 6,
Pigment Green 7 and Pigment Green 36.

The amount of the pigment added in the present invention is preferably 3 to 20 parts by mass based on 100 parts by mass of the binder resin or the polymerizable monomer.

As the polymerization initiator used in the method for producing the toner of the present invention, known polymerization initiators can be mentioned. Specifically, 2,2-azobisisobutyronitrile, 2,2-azobis (2,4-dimethylvaleronitrile), 2,2-azobis (2-methylbutyronitrile), 1,1-azobis (Cyclohexane-1-carbonitrile), dimethyl-2,2-azobisisobutyrate, 4,4-azobis-4-cyanovaleric acid, 2,2-
Azo compounds such as azobis (4-methoxy-2,4-dimethylvaleronitrile); peroxides such as benzoyl peroxide and methyl ethyl ketone peroxide; nucleophiles such as alkali metals, metal hydroxides and Grignard reagents, protons Acids, metal halides, stable carbonium ions are mentioned. The concentration of the polymerization initiator is preferably 0.1 to 20% by mass, more preferably 0.1 to 10% by mass, based on the polymerizable monomer.

When the toner of the present invention is produced by a polymerization method, a chain transfer agent may be used, and known chain transfer agents may be mentioned.

Further, in the present invention, the following toner additives may be used for the purpose of imparting various characteristics.

To stabilize the triboelectric charging characteristics of the toner, the toner may contain a charge control agent. In this case, it is preferable to use a charge control agent that has a high charging speed of the toner and can stably maintain a constant charge amount. When the polymerization method is used for producing the toner particles, a charge control agent having no polymerization inhibitory property is particularly preferable. Specifically, as the negative charge control agent, metal compounds of salicylic acid, alkylsalicylic acid, dialkylsalicylic acid, naphthoic acid and dicarboxylic acid; sulfonic acid, polymer compounds having carboxylic acid in the side chain, boron compound, urea Compounds, silicon compounds, and carexarenes are preferred. The positive control agent is preferably a quaternary ammonium salt, a polymer type compound having the quaternary ammonium salt in its side chain, a guanidine compound, or an imidazole compound. It is preferable to add 0.5 to 10 parts by mass of these charge control agents to 100 parts by mass of the binder resin.

It is also preferable to add external additives such as a fluidity imparting agent, an abrasive, a lubricant, and charge control particles to the toner.
As the fluidity-imparting agent, metal oxides such as silicon oxide, aluminum oxide and titanium oxide are preferably used, and those subjected to a hydrophobic treatment are more preferable. Examples of the abrasive include metal oxides such as strontium titanate, cerium oxide, aluminum oxide, magnesium oxide and chromium oxide, nitrides such as silicon nitride, carbides such as silicon carbide, metals such as calcium sulfate, barium sulfate and calcium carbonate. Salt is preferably used. As a lubricant,
Fluorine-based resin powders such as vinylidene fluoride and polytetrafluoroethylene, and fatty acid metal salts such as zinc stearate and calcium stearate are preferably used. As the charge control particles, tin oxide, titanium oxide, zinc oxide, silicon oxide, metal oxides such as aluminum oxide,
Carbon black is preferably used.

These external additives are used in an amount of 0.1 to 10 parts by mass, preferably 0.1 to 100 parts by mass of the toner.
To 5 parts by weight are used. These additives may be used alone or in combination of two or more.

The toner of the present invention can be used as a one-component developer or can be mixed with a carrier and used as a two-component developer.

The methods for measuring various physical properties in the present invention will be collectively described below.

<Molecular Weight Distribution> The molecular weight distribution of the resin component contained in the toner of the present invention and the polymer composition (resin component) soluble in the polymerization solvent used in the present invention is measured by a GPC measuring device (HLC- 8120GPC Tosoh Corp.) was used and measured under the following measurement conditions. -Measurement conditions-Column: TSKgel HM-M (diameter 6.0 mm x 1
5 cm) in duplicate ・ Temperature: 40 ° C. ・ Flow rate: 0.6 ml / min ・ Detector: RI ・ Sample concentration: 10 μl of 0.1% sample For sample preparation, put the sample to be measured in THF After leaving it for an hour, shake it sufficiently (until the coalescence of the samples disappears) and let stand for another 12 hours. Then, the sample that has passed through the sample processing filter (pore size 0.45 μm) is used as a sample for GPC measurement. For the calibration curve, a molecular weight calibration curve prepared using a monodisperse polystyrene standard sample is used.

<Measurement Method of Amount of Triboelectrification> Appropriate mixing amount (2 to 15% by mass) when the toner and the carrier are made into a developer
And mix for 180 seconds with a Turbula mixer. This mixed powder (developer) has an opening of 20 μm at the bottom.
It is put in a metal container equipped with a (635 mesh) conductive screen, sucked by a suction device, and the triboelectric charge amount is obtained from the difference in weight before and after suction and the potential accumulated in the capacitor connected to the container. At this time, the suction pressure is 250 mmHg. By this method, the triboelectric charge amount is calculated using the following formula. Q (μC / g) = (C × V) / (W1-W2) (W1 is the mass before suction, W2 is the mass after suction, C is the capacity of the capacitor, and V is the capacity of the capacitor. <Measurement of toner particle size> 0.1-0.1 ml of surfactant (alkylbenzene sulfonate) is added to 100-150 ml of electrolyte solution.
5 ml is added, and 2 to 20 mg of the measurement sample is added thereto. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment for 1 to 3 minutes by an ultrasonic disperser, and a Coulter counter multisizer with an aperture of 100 μm is used to obtain a particle diameter of 2 to 40.
A particle size distribution based on volume is measured for particles of μm, and the number average particle size and the weight average particle size are calculated from the results.

[0042]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to the examples. In addition,
All parts used in the examples are parts by mass.

Production Example 1-1 of Pigment Dispersant An acid-polystyrene-modified quinacridone (formula (1) -1) was synthesized by the method shown below. (1) Synthesis of 2-carboxyquinacridone 1,4-cyclohexanedione-2,5-dicarboxylic acid dimethy
l ester 4.56 parts (0.020 mol part), methyl
4-aminobenzoate 3.78 parts (0.025 mol part),
2.33 parts (0.025 mol parts) of aniline, methano-
50 parts of concentrated hydrochloric acid and 0.47 part of concentrated hydrochloric acid were charged into a 100 ml reaction vessel and reacted at 50 ° C. for 5 hours. The reaction mixture was cooled to room temperature, 1.8 parts of 10% NaOH aqueous solution was added, and 10
Stir for minutes. The crystals were filtered and washed with hot methanol.
After the crystals are dried, they are purified by a silica gel column to obtain the compound of formula (1-a)
Got The structure of formula (1-a) is a nuclear magnetic resonance spectrum,
It was identified by IR spectrum, elemental analysis and mass spectrometry.

[0044]

[Outside 25]

(1-a) 1.0 part (0.0023) of the compound represented by the formula (1-a)
mol part), ethanol 7.7 parts, 85% KOH1.2
4 parts (0.0188 mol part), 3.73 parts of water, m-nitr
30 parts of obenzene sulfonic acid sodium salt 0.92 parts
It was charged in a ml reaction vessel and heated under reflux for 20 hours. The solvent was distilled off from the reaction mixture, 20 ml of water was added to the residue, and the mixture was filtered. The filtrate was charged into a 50 ml reaction vessel and heated to 80 ° C. To this, 5.36 parts of 10% hydrochloric acid was added, and the mixture was stirred for 8 hours
Stirred at 0 ° C.

After filtering the precipitated crystals, the crystals were washed twice with hot water and dried to obtain the formula (1-b). The structure of formula (1-b) was identified by nuclear magnetic resonance spectrum, IR spectrum, elemental analysis, and mass spectrometry.

[0047]

[Outside 26]

(1-b) 0.39 parts (0.000995 mol) of the compound of the formula (2)
Part), 4 parts of polyphosphoric acid were charged into a 10 ml reaction vessel, and 1
The reaction was carried out at 10 ° C for 22 hours. The reaction mixture was poured into water, and the precipitated crystals were filtered. After washing with water and drying, the formula (1
-C) was obtained. The structure of formula (1-c) was identified by nuclear magnetic resonance spectrum, IR spectrum, elemental analysis, and mass spectrometry.

[0049]

[Outside 27]

(1-c) (3) Synthesis of acid chlorinated quinacridone derivative Carboxylated quinacridone (formula (1-c)) 4.0
Parts, 40 ml of toluene and 12 ml of thionyl chloride were charged into a reaction vessel, and then 0.2 ml of pyridine was added dropwise,
Refluxed for hours. The reaction product was concentrated by an evaporator to obtain acid chlorinated quinacridone.

(4) Synthesis of acid-polystyrene modified quinacridone Polystyrene (Mn = 4120, Mw = 5022) 25
Parts, nitrobenzene 80 ml, aluminum chloride 8.0
Parts were placed in a reaction vessel and stirred at room temperature for 4 hours, then 4.0 parts of acid chlorinated quinacridone was added, and the mixture was stirred at room temperature for 6 hours. The reaction product was diluted with 100 ml of THF and then added dropwise to 2 liters of methanol for reprecipitation purification. Further, washing and filtration were repeated with methanol, and vacuum drying was performed at room temperature for 12 hours to obtain an acid-polystyrene modified quinacridone (formula (1) -1). The IR spectrum, elemental analysis, and molecular weight measurement of this final product revealed that one styrene modified with acid styrene was modified with one quinacridone skeleton.

[0052]

[Outside 28]

1- (1) (R ₁ : substituent X ₁ , R ₂ : hydrogen, Y ₁ : polystyrene

[Outside 29]

Production Example 1-2 of Pigment Dispersant In the production of the above pigment dispersant 1- (1), the molecular weight of polystyrene used for modification is Mn = 20100, Mw =
The following pigment dispersant 1- (2) was produced in the same manner except that the amount was changed to 81800.

[0055]

[Outside 30]

1- (2) (R ₁ : substituent X ₁ , R ₂ : hydrogen, Y ₁ : polystyrene

[Outside 31]

Production Example 1-3 of Pigment Dispersant In the production of the above pigment dispersant 1- (1), polystyrene used for modification is styrene-n-butyl acrylate copolymer (ST / BA = 80/20, Mn = 376
2, the following pigment dispersant 1- (3) was produced in the same manner except that Mw = 4743) was changed.

[0058]

[Outside 32]

1- (3) (R ₁ : substituent X ₁ , R ₂ : hydrogen, substituent Y ₁ : styrene-n-butyl acrylate copolymer)

[Outside 33]

) Production Example of Pigment Dispersant 1-4 In the production of the above pigment dispersant 1- (1), the molecular weight of polystyrene used for modification is Mn = 28200, Mw =
The following pigment dispersant 1- (4) was produced in the same manner except that the amount was changed to 40510.

[0061]

[Outside 34]

1- (4) (R ₁ : substituent X ₁ , R ₂ : hydrogen, substituent Y ₁ : polystyrene

[Outside 35]

) Production of resin 60 parts of styrene, 25 parts of n-butyl acrylate, 15 parts of monobutyl maleate, 0.5 part of divinylbenzene,
Solution 1 was prepared by mixing 1.2 parts of benzoylperoxide, and solution 2 was prepared by dissolving 0.12 parts of partially saponified polyvinyl alcohol in 170 parts of water. The solutions 1 and 2 thus obtained were vigorously stirred to prepare a suspension dispersion. Next, the suspension dispersion obtained above was added to a reactor in which 300 parts of water was charged and the atmosphere was replaced with nitrogen.
Suspension polymerization was carried out at 5 ° C. for 8 hours. After the reaction was completed, it was washed with water and dehydrated and dried to obtain a resin (1).

Example 1 Resin (1) 100 parts Pigment Dispersant 1- (2) 4 parts Quinacridone (CI Pigment Violet 19) 6 parts Chromium complex (charge control agent) 4 parts The above materials were well mixed with a blender and then kneaded with a twin-screw kneading extruder set at 150 ° C. The obtained kneaded product was cooled, coarsely pulverized by a cutter mill, then finely pulverized by a fine pulverizer using a jet stream, and the finely pulverized powder obtained was classified by a fixed wall type air classifier. A classified powder was produced. Furthermore, using the multi-division classifier utilizing the Coanda effect (Nippon Mining Industry elbow jet classifier), the classified powder obtained above was strictly classified at the same time to remove ultrafine powder and coarse powder, thereby giving a magenta color. Toner was obtained.

The particle size of the obtained toner was measured with a Coulter counter to find that it had a weight average particle size of 8.4 μm. When the cross section of the toner particles was observed by a transmission electron microscope (TEM) by a dyeing ultrathin section method, it was confirmed that pigment particles of about 50 nm were finely dispersed in the resin layer.

BET was added to 100 parts of the obtained toner.
0.8 part of hydrophobic silica having a specific surface area of 200 m ² / g according to the method was externally added. To 7 parts of this toner, 93 parts of a ferrite carrier having an average particle diameter of 45 μm, which was surface-coated with a styrene-methyl acrylate copolymer, was mixed to obtain a developer.

Under normal temperature and normal humidity environment (temperature 25 ° C / humidity 60%
RH), the amount of charge of 0.1 g of the obtained developer was measured by the blow-off method and found to be -17.4 μC / g. Using this developer, an image output test was conducted by a Canon full-color copying machine CLC-500 modified machine under normal temperature and normal humidity environment. The development condition is development contrast 3
It was performed at 00V. The obtained image had an appropriate amount of applied toner, a high density, good reproducibility of fine lines, and a high quality image was obtained. This evaluation was carried out at low temperature and low humidity (15 ° C / 15
% RH) and high temperature and high humidity (30 ° C./75% RH), no fog occurs in any environment, the density change is small, and the toner has good charging characteristics. I understood. Further, when an image was similarly formed on the OHP sheet and projection was performed, a magenta-color projected image with high transparency was obtained.

Example 2 Resin (1) 100 parts Quinacridone (CI Pigment Violet 19) 30 parts Pigment Dispersant 1- (2) 20 parts The powder was crushed so as to pass through a sieve having an opening of 1 mm to obtain a masterbatch (1). Then, 80 parts of resin (1), 30 parts of the masterbatch (1), 4 parts of chromium complex (charge control agent), the above materials were mixed well with a blender in the same manner as in Example 1,
It was kneaded by a twin-screw kneading extruder set at 150 ° C. The obtained kneaded product was cooled, pulverized and classified in the same manner as in Example 1 to obtain a magenta toner.

The particle size of the obtained toner was measured with a Coulter counter to find that it had a weight average particle size of 8.4 μm. When the cross section of the toner particles was observed by a transmission electron microscope (TEM) by a dyeing ultrathin section method, it was confirmed that pigment particles of about 45 nm were finely dispersed in the resin layer.

Using the toner thus obtained, a developer was prepared in the same manner as in Example 1, and the charge amount was measured in the same manner as in Example 1. The charge amount was -18.6 μC / g. Using this developer, the full-color copying machine CL made by Canon is used as in the first embodiment.
When an image output test was performed using a C-500 modified machine,
It was found that, under any of the environments, fogging did not occur, the change in density was small, and the toner had good charging characteristics. Further, when an image was similarly formed on the OHP sheet and projection was performed, a magenta-color projected image with high transparency was obtained.

Example 3 340 parts styrene monomer 4 parts pigment dispersant of formula (1) -1 4 parts quinacridone (CI Pigment Violet 19) after premixing well in a container, Was maintained at 20 ° C. or lower and dispersed by a bead mill for about 5 hours to prepare a pigment dispersion paste a. The obtained pigment-dispersed paste a was uniformly applied onto a glass plate using a wire bar and naturally dried, and then the gloss value was measured and found to be 110, showing good smoothness. Further, when SEM observation was performed on the aluminum foil similarly coated, it was found that the particle diameter was about 55 nm, and the pigment was finely dispersed.

To 710 parts of ion-exchanged water, 450 parts of 0.1 mol / liter-Na ₃ PO ₄ aqueous solution was added, and after heating to 60 ° C., 11,000 rpm using a TK type homomixer (manufactured by Tokushu Kika Kogyo). It was stirred at. 70 parts of 1.0 mol / liter-CaCl ₂ aqueous solution was gradually added to this,
A dispersion medium containing Ca ₃ (PO ₄ ) ₂ was obtained. Pigment dispersion paste a 182 parts 2-Ethylhexyl acrylate 30 parts Paraffin wax (mp 75 ° C) 60 parts Styrene-methacrylic acid-methyl methacrylate copolymer 5 parts Di-tert-butylsalicylic acid Metal compound 3 parts These are heated to 60 ° C, dissolved and dispersed, and further 60
While maintaining at 0 ° C., 10 parts of a polymerization initiator 2,2′-azobisisobutyronitrile was added and dissolved to prepare a polymerizable monomer composition.

The above monomer composition was added to the dispersion medium prepared in the 2 liter flask of the homomixer. 6
100 at 0 ° C under nitrogen atmosphere using TK homomixer
The mixture was stirred at 00 rpm for 20 minutes to granulate the monomer composition. Then, the mixture was reacted at 60 ° C. for 3 hours while stirring with a paddle stirring blade, and then polymerized at 80 ° C. for 10 hours. After the completion of the polymerization reaction, the reaction product was cooled, hydrochloric acid was added, and Ca ₃ (P
O ₄ ) ₂ was dissolved, filtered, washed with water and dried to obtain a polymerized toner.

The particle size of the obtained toner was measured with a Coulter counter to find that it had a weight average particle size of 8.2 μm. When the surface of the toner was observed with an electron scanning microscope (SEM), no pigment particles were observed. Further, when TEM observation was performed in the same manner as in Example 1, the surface layer portion mainly composed of styrene-acrylic resin and the central portion mainly composed of wax were separated, and a capsule structure was confirmed. It was also confirmed that pigment particles of about 55 nm were finely dispersed in the styrene-acrylic resin layer.

Using the toner thus obtained, a developer was prepared in the same manner as in Example 1 and the charge amount was measured in the same manner as in Example 1 to find that it was -17.6 μC / g. Using this developer, an image was reproduced in the same manner as in Example 1 using a full color copying machine CLC-500 modified by Canon. The obtained image had an appropriate amount of applied toner, a high density, good reproducibility of fine lines, and a high quality image was obtained. This evaluation
Low temperature and low humidity (15 ℃ / 15%), high temperature and high humidity (30 ℃ / 75%)
%), It was found that fogging did not occur in any environment, the change in density was small, and the toner exhibited good charging characteristics. When an image was similarly printed on the OHP sheet and projected on the OHP sheet, a highly transparent magenta-color projected image was obtained.

Example 4 320 parts of styrene monomer 80 parts of n-butyl acrylate 4 parts of pigment dispersant of formula (1) -3 4 parts of quinacridone (CI Pigment Violet 19) in a container After premixing well, it was dispersed in a bead mill for about 5 hours while maintaining it at 20 ° C. or lower to prepare a pigment dispersion paste b.

The obtained pigment-dispersed paste b was uniformly applied onto a glass plate using a wire bar and naturally dried, and then the gloss value was measured and found to be 112, showing good smoothness. Further, when SEM observation was performed on the aluminum foil similarly coated, it was found that the particle diameter was about 55 nm, and the pigment was finely dispersed. Pigment dispersion paste b 212 parts Paraffin wax (mp 75 ° C.) 60 parts Styrene-methacrylic acid copolymer (95: 5, Mw 50,000) 5 parts Di-tert-butylsalicylic acid metal compound, mixture did. While maintaining at 60 ℃, starter 2,2 '
10 parts of azobis (2,4-dimethylvaleronitrile) was added and dissolved to prepare a monomer composition.

In a dispersion medium prepared in the same manner as in Example 3,
The above monomer composition was added. 20 at 10,000 rpm using a TK homomixer in a nitrogen atmosphere at 60 ° C.
After stirring for a minute, the monomer composition was granulated. After that, the mixture was stirred for 1 hour at 60 ° C while stirring with a paddle stirring blade, and then at 80 ° C.
And reacted for 12 hours. After the completion of the polymerization reaction, the reaction product was cooled, hydrochloric acid was added to dissolve Ca ₃ (PO ₄ ) ₂ , and the polymerized toner was obtained by filtering, washing with water and drying.

The particle size of the obtained toner was measured with a Coulter counter to find that it had a weight average particle size of 8.4 μm. When the toner surface was observed by SEM in the same manner as in Example 3, pigment particles were not observed as in Example 3. Furthermore, when the cross section of the particles was observed by TEM as in Example 3, the same capsule structure as in Example 3 was confirmed, and it was found that pigment particles of about 55 nm were finely dispersed in the styrene-acrylic resin layer. confirmed.

Using the toner thus obtained, a developer was prepared in the same manner as in Example 1. The charge amount was -18.4 μC / g.
Met. Using this developer, an image was reproduced in the same manner as in Example 1 by using a CLC-500 modified full-color copying machine manufactured by Canon. The obtained image had an appropriate amount of applied toner, a high density, good reproducibility of fine lines, and a high quality image was obtained. This evaluation is performed at low temperature and low humidity (15 ° C / 15
%), High temperature and high humidity (30 ° C / 75%),
It was found that no fog was generated in any of the environments, the change in density was small, and the toner exhibited good charging characteristics. In addition, when an image was similarly printed on the OHP sheet and projected with OHP, a magenta-color projected image with high transparency was obtained.

Example 5: 320 parts of styrene monomer, 80 parts of n-butyl acrylate, 5 parts of pigment dispersant of the formula (1) -4, and 20 parts of carbon black (Special Black 4 manufactured by Degussa) in a container. After premixing, it was dispersed for about 5 hours with a bead mill while maintaining it at 20 ° C. or lower to prepare a pigment dispersion paste c.

The pigment dispersion paste c thus obtained was uniformly applied onto a glass plate using a wire bar, and naturally dried, and then the gloss value was measured and found to be 115, indicating good smoothness. Further, SEM observation of an aluminum foil similarly applied revealed that the particle size was about 30 to 60 nm, and that the pigment was finely dispersed. Pigment dispersion paste c 212 parts Paraffin wax (mp 75 ° C.) 60 parts Styrene-methacrylic acid copolymer (95: 5, Mw 50,000) 5 parts Di-tert-butylsalicylic acid metal compound 3 parts Is heated to 60 ° C, dissolved and dispersed, and then 60
The initiator 2,2'-azobis (2,4
-Dimethylvaleronitrile) 10 parts was added and dissolved to prepare a monomer composition.

In the dispersion medium prepared in the same manner as in Example 3,
The above monomer composition was added. 20 at 10,000 rpm using a TK homomixer in a nitrogen atmosphere at 60 ° C.
After stirring for a minute, the monomer composition was granulated. After that, the mixture was stirred for 1 hour at 60 ° C while stirring with a paddle stirring blade, and then at 80 ° C.
And reacted for 12 hours. After completion of the polymerization reaction, the reaction product is cooled, hydrochloric acid is added to dissolve Ca ₃ (PO ₄ ) ₂ ,
A polymerized toner was obtained by filtering, washing with water and drying.

The particle size of the obtained toner was measured with a Coulter counter to find that it had a weight average particle size of 8.1 μm. When the toner surface was observed by SEM in the same manner as in Example 3, pigment particles were not observed as in Example 3. Further, when the cross section of the particles was observed by TEM as in Example 3, the same capsule structure as in Example 3 was confirmed, and the styrene-acrylic resin layer had a thickness of about 40 to 60.
It was confirmed that the nm pigment particles were uniformly dispersed.

Using the toner thus obtained, a developer was prepared in the same manner as in Example 1. The charge amount was -19.8 μC / g.
Met. Using this developer, an image was reproduced in the same manner as in Example 1 by using a CLC-500 modified full-color copying machine manufactured by Canon. The obtained image had an appropriate amount of applied toner, a high density, good reproducibility of fine lines, and a high quality image was obtained. This evaluation was carried out at low temperature and low humidity (15 ° C / 15
%), High temperature and high humidity (30 ° C / 75%),
It was found that in both cases, fogging did not occur, the change in density was small, and the toner exhibited good charging characteristics.

Example 6-Styrene monomer 200 parts-n-butyl acrylate 50 parts-Carbon black (Special Black 4 manufactured by Degussa) 12.5 parts-Formula (1) -4 pigment dispersant 3.2 parts- After well premixing styrene-methacrylic acid copolymer (95: 5, Mw 50,000) 6.3 parts and di-tert-butylsalicylic acid metal compound 3.8 parts in a container, it was kept at 20 ° C. or lower. The beads were dispersed as they were for about 5 hours.

While heating 220 parts of the above dispersion liquid to 60 ° C. and stirring, paraffin wax (mp 75 ° C.) 60
Parts and an initiator 2,2′-azobis (2,4-dimethylvaleronitrile) 10 parts were added and dissolved to prepare a monomer composition.

In the dispersion medium prepared in the same manner as in Example 3,
The above monomer composition was added. 20 at 10,000 rpm using a TK homomixer in a nitrogen atmosphere at 60 ° C.
After stirring for a minute, the monomer composition was granulated. After that, the mixture was stirred for 1 hour at 60 ° C while stirring with a paddle stirring blade, and then at 80 ° C.
And reacted for 12 hours. After completion of the polymerization reaction, the reaction product is cooled, hydrochloric acid is added to dissolve Ca ₃ (PO ₄ ) ₂ ,
A polymerized toner was obtained by filtering, washing with water and drying.

The particle size of the obtained toner was measured with a Coulter counter to find that it had a weight average particle size of 8.5 μm. When the toner surface was observed by SEM in the same manner as in Example 3, pigment particles were not observed as in Example 3. Further, when the cross section of the particles was observed by TEM as in Example 3, the same capsule structure as in Example 3 was confirmed, and the styrene-acrylic resin layer had a thickness of about 40-80.
It was confirmed that the nm pigment particles were uniformly dispersed.

Using the toner thus obtained, a developer was prepared in the same manner as in Example 1. The charge amount was -17.0 μC / g.
Met. Using this developer, an image was reproduced in the same manner as in Example 1 by using a CLC-500 modified full-color copying machine manufactured by Canon. The obtained image had an appropriate amount of applied toner, a high density, good reproducibility of fine lines, and a high quality image was obtained. This evaluation was carried out at low temperature and low humidity (15 ° C / 15
%), High temperature and high humidity (30 ° C / 75%),
It was found that in both cases, fogging did not occur, the change in density was small, and the toner exhibited good charging characteristics. [Comparative Example 1] 320 parts of styrene monomer, 80 parts of n-butyl acrylate, 20 parts of quinacridone (CI Pigment Violet 19) were well premixed in a container, and then bead mill while keeping it at 20 ° C or lower. And dispersed for about 5 hours to prepare a pigment dispersion paste d.

The pigment dispersion paste d thus obtained was coated on a glass plate in the same manner as in Example 3, and the gloss value was measured to be 7
It was 0 and smoothness was not obtained. Further, SEM observation of the product coated on an aluminum foil in the same manner as in Example 3 revealed that the particle size was from coarse particles of about 220 nm to fine powder of about 55 nm, and the dispersion of the particle size distribution due to the aggregation of the pigments was remarkable. It was Pigment dispersion paste d 212 parts Paraffin wax (mp 75 ° C.) 60 parts Styrene-methacrylic acid copolymer (95: 5, Mw 50,000) 5 parts Di-tert-butylsalicylic acid metal compound 3 parts Was heated to 60 ° C., dissolved and dispersed, and an initiator was further added to obtain a monomer composition. Granulation, polymerization, washing and drying were carried out in the same manner as in Example 3 to obtain a polymerized toner.

The particle size of the obtained toner was measured with a Coulter counter to find that it had a weight average particle size of 8.1 μm. When the toner surface was observed by SEM in the same manner as in Example 3, pigment particles were not observed as in Example 3. Furthermore, when the cross section of the particles was observed by TEM as in Example 3, the same capsule structure as in Example 3 was confirmed, and the styrene-acrylic resin layer had a thickness of 50 to 200.
Needle-shaped pigment particles of about nm were dispersed. It was also observed that many pigment particles were present at the interface between the wax and the styrene acrylic resin.

Using the toner thus obtained, a developer was prepared in the same manner as in Example 1. The charge amount was −20.6 μC / g.
Met. Using this developer, an image was reproduced in the same manner as in Example 1 by using a CLC-500 modified full-color copying machine manufactured by Canon. The obtained image has an appropriate amount of applied toner, good reproducibility of fine lines, low temperature and low humidity (15 ° C /
15%) and a high temperature and high humidity (30 ° C./75%) environment, no fog was found in any of them, and it was found that the toner exhibited good charging characteristics. But OH
When an image was similarly printed on the P sheet and projected by OHP, the projected image was slightly inferior in transparency to Example 3, and the saturation was not obtained as in Example 3.

[Comparative Example 2] Pigment dispersant (Azisper PB711: manufactured by Ajinomoto Co., Inc. (graft polymer obtained by reacting a polyepoxy compound with a carboxyl group-containing linear polymer and an organic amino compound)) 4 parts Styrene monomer 320 Parts, n-butyl acrylate 80 parts, quinacridone (CI Pigment Violet 19: 3) 20 parts well premixed in a container, then dispersed in a bead mill for about 5 hours while keeping it at 20 ° C. or lower, A pigment dispersion paste e was produced.

The obtained pigment-dispersed paste e was uniformly applied on a glass plate using a wire bar and naturally dried, and then the gloss value was measured to be 112, showing good smoothness. Further, when SEM observation was performed on the aluminum foil similarly coated, it was found that the particle diameter was about 55 nm, and the pigment was finely dispersed. Pigment dispersion paste 212 parts Paraffin wax (mp 75 ° C.) 60 parts Styrene-methacrylic acid copolymer (95: 5, Mw 50,000) 5 parts Di-tert-butylsalicylic acid metal compound 3 parts Was heated to 60 ° C., dissolved and dispersed, and an initiator was further added to obtain a monomer composition. Granulation, polymerization, washing and drying were carried out in the same manner as in Example 3 to obtain a polymerized toner.

The particle size of the obtained toner was measured with a Coulter counter to find that it had a weight average particle size of 8.1 μm. When the surface of the toner was observed by SEM in the same manner as in Example 3, many pigment particles having a particle diameter of about 55 nm were observed. Furthermore, as in Example 3, the cross section of the particles was TE
When observed with M, the same capsule structure as in Example 3 was confirmed, and the styrene-acrylic resin layer contained pigment particles having a particle size of about 50 to 150 nm in a slightly cohesive manner, and the wax and binder were It was found that many pigments also existed at the interface of.

Using the toner thus obtained, a developer was prepared in the same manner as in Example 1. The charge amount was -12.0 μC / g.
Met. Using this developer, an image was reproduced in the same manner as in Example 1 by using a CLC-500 modified full-color copying machine manufactured by Canon. The obtained image had a proper amount of applied toner, but some fog occurred. Further, under high temperature and high humidity (30 ° C./75%) environment, fog was observed to be worse, and it was revealed that the toner had inferior environmental characteristics as compared with the toner of Example 3. On the other hand, when the image was printed on the OHP sheet, a magenta projection image slightly less transparent than that of Example 3 was obtained.

[0098]   [Comparative Example 3] ・ Resin (1) 100 parts ・ Quinacridone (PigmentViolet19) 6 parts ・ Chromium complex (charge control agent) 4 parts The above materials are kneaded, pulverized and classified in the same manner as in Example 1 to obtain a magenta toner. Obtained.

The particle diameter of the obtained toner was measured with a Coulter counter to find that it had a weight average diameter of 8.1 μm. When the cross section of the particles was observed by TEM in the same manner as in Example 1, it was found that the styrene-n-butyl methacrylate resin layer had pigment particles with a particle size of about 50 to 200 nm slightly coagulated. all right.

Using the toner thus obtained, a developer was prepared in the same manner as in Example 1. The charge amount was -16.2 μC / g.
Met. Using this developer, a full-color copying machine CLC-500 manufactured by Canon Inc. was used in the same manner as in Example 1,
When an image was printed on the OHP sheet, a magenta projection image slightly less transparent than that in Example 1 was obtained.

[0101]

[Table 1]

Each of the environmental stability, fog and permeability in the table was evaluated according to the following criteria. The same criteria were used for the evaluation of the examples described below.

[Environmental Stability of Charge Amount] Evaluation was performed according to the evaluation criteria shown in the following formula. The sample used was left in each environment for 24 hours. A: (charge amount under high temperature and high humidity)-(charge amount under low temperature and low humidity) <15 (μC / g) B: 15 ≤ (charge amount under high temperature and high humidity)-(charge amount under low temperature and low humidity) < 25 C: 25 ≤ (charge amount under high temperature and high humidity)-(charge amount under low temperature and low humidity) [Fog] Fogging density under high temperature and high humidity Tokyo Denshoku Densitometer TC-6DS Fogging density (%) = (Reflection density of fog on transfer paper)
-(Reflection density of unused transfer paper) A: 1.0% or less B: 1.0% to 2.0% C: over 2.0% [OHP sheet permeability] Fixed image on OHP sheet (toner paste) An amount of 0.7 mg / cm ² ) is used as a transmission image with an overhead projector (OHP: 9550 manufactured by 3M), and L * and c * of the image projected on the white wall are applied to a spectral radiance meter (PR650 manufactured by Photo Research). And measure
The colorimetric index of the projected image was evaluated as p = (95-L *) / c *. A (good): 0.50 ≦ p <0.60 B (possible): 0.60 ≦ p <0.65 C (bad): 0.65 ≦ p Production Example 2-1 of Pigment Dispersant Shown below. A styrene-glycidyl methacrylate copolymer-modified quinacridone (formula (2) -1) was synthesized by the method.

Quinacridone (C.I. Pigment Violet 1
9) 0.31 part, potassium tert-butoxide 0.11 part, dimethy
l sulfoxide 5.0 parts, styrene-glycidyl methacrylate copolymer (number average molecular weight Mn = 14606, weight average molecular weight Mw = 16700, epoxy equivalent 462 g / mo
l) 6.0 parts of the solution was added to a 50 ml reaction container, and the reaction was carried out at 60 ° C. for 5 hours in an oil bath. After cooling the reaction mixture,
Take it out to a 100 ml beaker, add 50 ml of the reaction solution washed with 50 ml of xylene, and add 0.5 m.
2.0 ml of ol / HCl aqueous solution was added with stirring.
The resulting mixture was added dropwise to 400 ml of methanol for reprecipitation purification. Furthermore, 200 ml of water and 20 ml of methanol
After washing and filtering with 0 ml, it was dried under reduced pressure for 12 hours at room temperature to obtain 2.6 parts of styrene-glycidyl methacrylate copolymer-modified quinacridone (formula 2- (1)). The IR spectrum, elemental analysis, and molecular weight measurement of this final product showed that the average per quinacridone skeleton was 1.
It was found that 30 styrene-glycidyl methacrylate copolymers were modified.

[0105]

[Outside 36]

2- (1) (At least one of the substituents R ₃ and R ₄ is the substituent X ₂ , and the total amount of the dispersant is 65% of the total of R ₃ and R _4.
Was the substituent X ₂ . The rest is hydrogen and the substituent X ₂
Substituents Y ₂ and Y ₃ are styrene-glycidyl methacrylate copolymer (St / glycidyl methacrylate = 80/20)

[Outside 37]

) Production Example 2-2 of Pigment Dispersant In the production of the above pigment dispersant 2- (1), the production conditions of the styrene-glycidyl methacrylate copolymer were changed to use styrene-glycidyl methacrylate for modification. The molecular weight of the copolymer is Mn = 30812, Mw = 37051
In the same manner except that the following pigment dispersant 2-
(2) was produced.

[0108]

[Outside 38]

2- (2) (At least one of the substituents R ₃ and R ₄ is the substituent X ₂ , and the total amount of R ₃ and R ₄ is 61% of the total amount of the dispersant.
Was the substituent X ₂ . The rest is hydrogen and the substituent X ₂
Substituents Y ₂ and Y ₃ are styrene-glycidyl methacrylate copolymer (80/20)

[Outside 39]

) Production Example 2-3 of Pigment Dispersant In the production of the above pigment dispersant 2- (1), the production conditions of the styrene-glycidyl methacrylate copolymer are changed to use styrene-glycidyl methacrylate for modification. The molecular weight of the copolymer is Mn = 16202, Mw = 19244
In the same manner except that the following pigment dispersant 2-
(3) was produced.

[0111]

[Outside 40]

B-3 (at least one of the substituents R ₃ and R ₄ is the substituent X ₂ and the total amount of the dispersant is 55% of R ₃ and R _4).
Was the substituent X ₂ . The rest is hydrogen and the substituent X ₂
Substituents Y ₂ and Y ₃ are styrene-glycidyl methacrylate copolymer (80/20)

[Outside 41]

[Example 7] 100 parts of the resin (1) used in Example 1 4 parts of the pigment dispersant of the formula 2- (1) 4 parts quinacridone (CI Pigment Violet 19) 6 parts chromium Complex (charge control agent) 4 parts The above materials were kneaded, pulverized and classified in the same manner as in Toner Preparation Example 1 to obtain magenta resin fine powder.

The particle size of the obtained toner was measured with a Coulter counter to find that it had a weight average particle size of 8.6 μm. When the cross section of the toner particles was observed by a transmission electron microscope (TEM) by a dyeing ultrathin section method, it was confirmed that pigment particles of about 50 nm were finely dispersed in the resin layer.

A developer was prepared in the same manner as in Example 1 by using the obtained toner, and the result was -18.4 μC / g. Canon full color copier C using this developer
Images were reproduced in the same manner as in Example 1 using a modified LC-500 machine. The obtained image had a proper amount of applied toner, a high density, a good reproducibility of fine lines, and a high quality image was obtained. This evaluation is based on low temperature and low humidity (15 ° C / 15%),
When it was carried out at high temperature and high humidity (30 ° C./75%), it was found that no fog occurred and there was little change in density, and the toner showed good charging characteristics. Also, OH
When an image was similarly printed on the P sheet and projected with OHP, a highly transparent magenta color projected image was obtained.

Example 8 Resin (1) 100 parts Quinacridone (CI Pigment Violet 19) 30 parts Pigment Dispersant 2- (2) 20 parts These were kneaded with a double roll, The powder was crushed so as to pass through a sieve having an opening of 1 mm to obtain a masterbatch (2). Next, 80 parts of resin (1), 30 parts of the masterbatch (2), 4 parts of chromium complex (charge control agent), the above materials were mixed well with a blender in the same manner as in Example 1,
It was kneaded by a twin-screw kneading extruder set at 150 ° C. The obtained kneaded product was cooled, pulverized and classified in the same manner as in Example 1 to obtain a magenta toner.

The particle diameter of the obtained toner was measured with a Coulter counter to find that it had a weight average particle diameter of 8.1 μm. When the cross section of the toner particles was observed by a transmission electron microscope (TEM) by a dyeing ultrathin section method, it was confirmed that pigment particles of about 45 nm were finely dispersed in the resin layer.

When a developer was prepared in the same manner as in Example 1, the result was -17.6 μC / g. An image similar to that in Example 1 was formed using this developer. The obtained image had a proper amount of applied toner, a high density, good reproducibility of fine lines, and was a high-quality image. When this evaluation was conducted at low temperature and low humidity (15 ° C / 15%) and high temperature and high humidity (30 ° C / 75%), no fog was generated, the density change was small, and the toner showed good charging characteristics. I found out. In addition, when an image was similarly printed on the OHP sheet and projected with OHP, a magenta-color projected image with high transparency was obtained.

Example 9 340 parts styrene monomer 4 parts pigment dispersant of formula 2- (1) 4 parts quinacridone (CI Pigment Violet 19) well premixed in a container, Was dispersed in a bead mill for about 5 hours while maintaining 20 ° C. or lower to prepare a pigment dispersion paste f. The obtained pigment-dispersed paste f was uniformly applied onto a glass plate using a wire bar and naturally dried, and then the gloss value was measured and found to be 109, indicating good smoothness. Further, when SEM observation was performed on the aluminum foil similarly coated, it was found that the particle diameter was about 55 nm, and the pigment was finely dispersed. Pigment dispersion paste f 182 parts 2-Ethylhexyl acrylate 30 parts Paraffin wax (mp 75 ° C) 60 parts Styrene-methacrylic acid-methyl methacrylate copolymer 5 parts Di-tert-butylsalicylic acid Metal compound 3 parts These are heated to 60 ° C, dissolved and dispersed, and further 60
While maintaining at 0 ° C., 10 parts of an initiator 2,2′-azobisisobutyronitrile was added and dissolved to prepare a monomer composition.

In the dispersion medium prepared in the same manner as in Example 3,
The above monomer composition was added. 20 at 10,000 rpm using a TK homomixer in a nitrogen atmosphere at 60 ° C.
After stirring for a minute, the monomer composition was granulated. After that, the mixture was reacted at 60 ° C for 3 hours while stirring with a paddle stirring blade, and then at 80 ° C.
It was polymerized for 10 hours. After the completion of the polymerization reaction, the reaction product was cooled, hydrochloric acid was added to dissolve Ca ₃ (PO ₄ ) ₂ , and the polymerized toner was obtained by filtering, washing with water and drying.

The particle diameter of the obtained toner was measured with a Coulter counter to find that it had a weight average particle diameter of 8.1 μm. When the surface of the toner was observed with an electron scanning microscope (SEM), no pigment particles were observed. Furthermore, when TEM observation was performed in the same manner as in Example 3, the surface layer portion mainly composed of styrene-acrylic resin and the central portion mainly composed of wax were separated, and a capsule structure was confirmed. It was also confirmed that pigment particles of about 55 nm were uniformly finely dispersed in the styrene-acrylic resin layer.

A developer was prepared in the same manner as in Example 1, and the charge amount was measured in the same manner as in Example 1. As a result, -19.8 μC /
It was g. Using this developer, an image was reproduced in the same manner as in Example 1 using a full color copying machine CLC-500 modified by Canon. The obtained image had an appropriate amount of applied toner, a high density, good reproducibility of fine lines, and a high quality image was obtained. This evaluation was carried out at low temperature and low humidity (15 ° C / 15
%), High temperature and high humidity (30 ° C / 75%),
It was found that in both cases, fogging did not occur, the change in density was small, and the toner exhibited good charging characteristics. In addition, when an image was similarly printed on the OHP sheet and projected with OHP, a magenta projected image with high transparency was obtained.

Example 10 • 320 parts of styrene monomer • 80 parts of n-butyl acrylate • 4 parts of pigment dispersant of formula 2- (3) • 20 parts of quinacridone (Pigment Violet 19) well premixed in a container While maintaining it at 20 ° C. or lower, it was dispersed by a bead mill for about 5 hours to prepare a pigment dispersion paste g.

The obtained pigment-dispersed paste g was uniformly applied onto a glass plate using a wire bar and naturally dried, and then the gloss value was measured and found to be 113, showing good smoothness. Further, when SEM observation was performed on the aluminum foil similarly coated, it was found that the particle diameter was about 55 nm, and the pigment was finely dispersed. Pigment dispersion paste g 212 parts Paraffin wax (mp 75 ° C.) 60 parts Styrene-methacrylic acid copolymer (95: 5, Mw 50,000) 5 parts Di-tert-butylsalicylic acid metal compound 3 parts Is heated to 60 ° C, dissolved and dispersed, and then 60
The initiator 2,2'-azobis (2,4
-Dimethylvaleronitrile) 10 parts was added and dissolved to prepare a monomer composition.

In a dispersion medium prepared in the same manner as in Example 3,
The above monomer composition was added. 20 at 10,000 rpm using a TK homomixer in a nitrogen atmosphere at 60 ° C.
After stirring for a minute, the monomer composition was granulated. After that, the mixture was stirred for 1 hour at 60 ° C while stirring with a paddle stirring blade, and then at 80 ° C.
And reacted for 12 hours. After the completion of the polymerization reaction, the reaction product was cooled, hydrochloric acid was added to dissolve Ca ₃ (PO ₄ ) ₂ , and the polymerized toner was obtained by filtering, washing with water and drying.

The particle size of the obtained toner was measured with a Coulter counter to find that it had a weight average particle size of 8.2 μm. When the toner surface was observed by SEM in the same manner as in Example 3, pigment particles were not observed as in Example 3. Furthermore, when the cross section of the particles was observed by TEM as in Example 3, the same capsule structure as in Example 2 was confirmed, and it was found that pigment particles of about 55 nm were finely dispersed in the styrene-acrylic resin layer. confirmed.

When a developer was prepared in the same manner as in Example 1, the charge amount was -19.0 μC / g. Using this developer, an image was reproduced in the same manner as in Example 1 by using a CLC-500 modified full-color copying machine manufactured by Canon. The obtained image has an appropriate amount of applied toner, high density,
The fine line reproducibility was also good, and a high quality image was obtained. This evaluation is based on low temperature low humidity (15 ° C / 15%), high temperature high humidity (30 ° C)
/ 75%), no fog was generated, the density change was small, and the toner showed good charging characteristics. In addition, when an image was similarly printed on the OHP sheet and projected with OHP, a magenta-color projected image with high transparency was obtained.

Example 11 200 parts of styrene monomer 50 parts of n-butyl acrylate 12.5 parts of quinacridone (Pigment Violet 19) 1 part of pigment dispersant of formula (2) -2 2.5 parts of styrene-methacrylic acid After thoroughly premixing 6.3 parts of the copolymer (95: 5, Mw 50,000) and 3.8 parts of the metal compound of di-tert-butylsalicylic acid in a container, while keeping it at 20 ° C. or lower, it was about to be mixed with a bead mill. Dispersed for 5 hours.

While heating 220 parts of the above dispersion liquid to 60 ° C. and stirring, paraffin wax (mp 75 ° C.) 60
Parts and an initiator 2,2′-azobis (2,4-dimethylvaleronitrile) 10 parts were added and dissolved to prepare a monomer composition.

In a dispersion medium prepared in the same manner as in Example 3,
The above monomer composition was added. 20 at 10,000 rpm using a TK homomixer in a nitrogen atmosphere at 60 ° C.
After stirring for a minute, the monomer composition was granulated. After that, the mixture was stirred for 1 hour at 60 ° C while stirring with a paddle stirring blade, and then at 80 ° C.
And reacted for 12 hours. After completion of the polymerization reaction, the reaction product is cooled, hydrochloric acid is added to dissolve Ca ₃ (PO ₄ ) ₂ ,
A polymerized toner was obtained by filtering, washing with water and drying.

The particle diameter of the obtained toner was measured with a Coulter counter to find that it had a weight average particle diameter of 8.5 μm. When the toner surface was observed by SEM in the same manner as in Example 3, pigment particles were not observed as in Example 3. Further, when the cross section of the particles was observed by TEM as in Example 3, the same capsule structure as in Example 3 was confirmed, and the styrene-acrylic resin layer had about 55 to 70.
It was confirmed that the nm pigment particles were uniformly dispersed.

A developer was prepared in the same manner as in Example 1 by using the obtained toner. The charge amount was −20.5 μC / g.
Met. Using this developer, an image was reproduced in the same manner as in Example 1 by using a CLC-500 modified full-color copying machine manufactured by Canon. The obtained image had an appropriate amount of applied toner, a high density, good reproducibility of fine lines, and a high quality image was obtained. This evaluation was carried out at low temperature and low humidity (15 ° C / 15
%), High temperature and high humidity (30 ° C / 75%),
It was found that in both cases, fogging did not occur, the change in density was small, and the toner exhibited good charging characteristics.

[0133]

[Table 2]

[0134]

According to the present invention, it is possible to provide a toner in which a pigment is finely dispersed and which is excellent in coloring power and transparency. Furthermore, in a method for producing a polymerized toner in an aqueous medium, a method for producing a toner is provided, in which a colorant is prevented from floating on the toner surface, and a toner excellent in charging property and environmental stability can be produced. can do.

Claims (18)

[Claims] 1. A toner containing at least a binder resin, a pigment and a pigment dispersant, wherein the pigment dispersant is represented by the following formula (1). [Outer 1] (1) (At least one of R ₁ and R ₂ is a substituent X ₁ (others are hydrogen), and the substituent Y ₁ is an oligomer or a polymer. ) 2. The substituent Y ₁ of the pigment dispersant is styrene,
A vinyl polymer component or a polyester component containing a monomer selected from the group consisting of a styrene derivative, (meth) acrylic acid and a (meth) acrylic acid derivative as a monomer unit.
The toner according to. 3. The toner according to claim 1, wherein the content of the pigment dispersant is 2 to 100 parts by mass with respect to 100 parts by mass of the pigment. 4. A method for producing a toner by melt-kneading a mixture containing at least a binder resin, a pigment and a pigment dispersant, pulverizing the obtained kneaded product, and classifying the mixture to produce a toner. Is represented by the following formula (1). [Outside 3] (1) (At least one of R ₁ and R ₂ is a substituent X ₁ (others are hydrogen), and the substituent Y ₁ is an oligomer or a polymer. ) 5. A production method for producing a toner by melt-kneading a mixture containing at least a binder resin and a pigment treated with a pigment dispersant, crushing the obtained kneaded product, and classifying the mixture. A method for producing a toner, wherein the pigment dispersant is represented by the following formula (1). [Outside 5] (1) (At least one of R ₁ and R ₂ is a substituent X ₁ (others are hydrogen), and the substituent Y ₁ is an oligomer or a polymer. ) 6. A method for producing a toner, comprising preparing a polymerizable monomer composition containing at least a polymerizable monomer and a pigment, polymerizing the polymerizable monomer in the composition to prepare a toner. A method for producing a toner, wherein the pigment is surface-treated with a pigment dispersant represented by the following formula (1) before being added to the polymerizable monomer composition. . [Outside 7] (1) (At least one of R ₁ and R ₂ is a substituent X ₁ (other is hydrogen), and the substituent Y ₁ is an oligomer or a polymer. ) 7. The method for producing a toner according to claim 6, wherein the toner is produced by suspension polymerization. 8. A toner for preparing a toner by preparing a polymerizable monomer composition containing at least a polymerizable monomer, a pigment and a pigment dispersant, and polymerizing the polymerizable monomer in the composition. The method for producing a toner, wherein the pigment dispersant is represented by the following formula (1). [Outside 9] (1) (At least one of R ₁ and R ₂ is a substituent X ₁ (others are hydrogen), and the substituent Y ₁ is an oligomer or a polymer. ) 9. The method for producing a toner according to claim 8, wherein the toner is produced by suspension polymerization. 10. A toner containing at least a binder resin, a pigment and a pigment dispersant, wherein the pigment dispersant is represented by the following formula (2). [Outside 11] (2) (At least one of R ₃ and R ₄ is a substituent X ₂ (others are hydrogen), and the substituents Y ₂ and Y ₃ are H, CH ₃ ,
It is a substituent selected from the group consisting of oligomers and polymers. [Outside 12] ) 11. The substituents Y ₂ and Y _{3 of the} pigment dispersant are
A vinyl polymer component containing a monomer selected from the group consisting of styrene, styrene derivatives, (meth) acrylic acid and (meth) acrylic acid ester as a monomer unit, or a polyester component. 10. The toner according to item 10. 12. The toner according to claim 10, wherein the content of the pigment dispersant is 2 to 100 parts by mass with respect to 100 parts by mass of the pigment. 13. A production method for producing a toner by melt-kneading a mixture containing at least a binder resin, a pigment and a pigment dispersant, pulverizing the obtained kneaded product and classifying the mixture.
The method for producing a toner, wherein the pigment dispersant is represented by the following formula (2). [Outside 13] (2) (At least one of R ₃ and R ₄ is a substituent X ₂ (others are hydrogen), and the substituents Y ₂ and Y ₃ are H, CH ₃ ,
It is a substituent selected from the group consisting of oligomers and polymers. [Outside 14] ) 14. A production method for producing a toner by melt-kneading a mixture containing at least a binder resin and a pigment treated with a pigment dispersant, crushing the obtained kneaded product, and classifying the mixture. A method for producing a toner, wherein the pigment dispersant is represented by the following formula (2). [Outside 15] (2) (At least one of R ₃ and R ₄ is a substituent X ₂ (others are hydrogen), and the substituents Y ₂ and Y ₃ are H, CH ₃ ,
It is a substituent selected from the group consisting of oligomers and polymers. [Outside 16] ) 15. A method for producing a toner, comprising producing a polymerizable monomer composition containing at least a polymerizable monomer and a pigment, polymerizing the polymerizable monomer in the composition to produce a toner. The method for producing a toner, wherein the pigment is surface-treated with a pigment dispersant represented by the following formula (2) before being added to the polymerizable monomer composition. . [Outside 17] (2) (At least one of R ₃ and R ₄ is a substituent X ₂ (others are hydrogen), and the substituents Y ₂ and Y ₃ are H, CH ₃ ,
It is a substituent selected from the group consisting of oligomers and polymers. [Outside 18] ) 16. The method for producing a toner according to claim 15, wherein the toner is produced by suspension polymerization. 17. A toner for producing a toner by producing a polymerizable monomer composition containing at least a polymerizable monomer, a pigment and a pigment dispersant, and polymerizing the polymerizable monomer in the composition. And a pigment dispersant represented by the following formula (2):
A method for producing a toner, wherein: [Outside 19] (2) (At least one of R ₃ and R ₄ is a substituent X ₂ (others are hydrogen), and the substituents Y ₂ and Y ₃ are H, CH ₃ ,
It is a substituent selected from the group consisting of oligomers and polymers. [Outside 20] ) 18. The method for producing a toner according to claim 17, wherein the toner is produced by suspension polymerization.