JP4115495B2 - Toner and toner production method - Google Patents

Description

  The present invention relates to a toner for developing an electrostatic image in an image forming method such as electrophotography and electrostatic printing, or a method for producing a toner for forming a toner image in a toner jet type image forming method. The present invention relates to a method for producing toner for use in a fixing method in which a toner image formed with toner is heated and pressed and fixed on a print sheet such as a transfer material.

  In order to visualize an electric or magnetic latent image on a recording medium, there is an image forming method in which electrosensitive or magnetically sensitive fine particles such as toner are attracted to the latent image to form a visible image. A typical example is an electrophotographic method. For example, as described in the specification of Patent Document 1, many methods are known. In this electrophotographic method, a photoconductive substance is generally used to form an electrical latent image on a photoreceptor by various means, and then the latent image is developed with toner to form a toner image. If necessary, the toner image is transferred to a transfer material such as paper, and then the toner image is fixed on the transfer material using heating, pressurization, or solvent vapor to obtain a copy.

  In recent years, the above-described technology has been used in output means such as computers and word processors, so-called printers, because of its high print quality and quietness. Usually, toner used in printers and copiers is fine particles mainly composed of resin and magnetic material, carbon black, colorants such as dyes and pigments, and waxes, and usually has a particle size of 6 to 30 μm. It is a range. Toner is generally produced as a toner having a desired particle size by mixing and melting a colorant comprising a dye or a pigment in a thermoplastic resin, dispersing the colorant uniformly, then finely pulverizing and classifying. Has been. This method is relatively stable as a technology, and each material and each process can be managed relatively easily.

  On the other hand, a toner production method by a polymerization method, that is, a toner production method by a so-called suspension polymerization method has been proposed. These are described in Patent Documents 2 to 6, for example. In this method, a colorant such as a binder resin, a dye, and a pigment, for example, a magnetic material, carbon black, a charge control agent, a release agent such as wax and silicone oil, and the like should be included in the toner. Dissolve or disperse in a polymerizable monomer together with a polymerization initiator and a dispersant to form a polymerizable composition, disperse it in an aqueous continuous phase containing a dispersion stabilizer using a dispersing device, and form a fine particle dispersion. The dispersion is polymerized and solidified to obtain toner particles having a desired particle size and composition. Since this method does not include a pulverization process, it is expected to save energy, improve process yield, and reduce costs.

  As a method for improving the printing quality, a technique for reducing the particle diameter of the toner and reproducing the latent image finely and faithfully has been actively studied. However, if the particle diameter 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 that, a means for increasing the amount of the dye / pigment that is a colorant is generally used, but the pigment used in the toner colorant, especially the quinacridone pigment, is expensive and the production cost increases. There is. Therefore, in order to increase the coloring power of the dye / pigment itself and to improve the transparency of OHP, research on improving the dispersibility of the dye / pigment inside the toner has been actively conducted.

  In order to improve the dispersibility of the dye / pigment, it is generally important to make the dye / pigment and the resin easily compatible, and surface treatment of the dye / pigment is performed. Patent Documents 7 and 8 and the like are proposed to improve the dispersibility by performing a surface treatment of the dyed pigment. However, there is still room for improvement regarding the dispersibility of the pigment in the toner.

  In the case of the pulverized toner, it is necessary to adjust the treatment of the dye / pigment according to the composition of the binder resin, and there is a problem that a good dispersion state cannot be obtained if the matching between the two is inappropriate. .

  In the case of polymerized toners, surface treatment of dyes and pigments is often performed, but in many cases, hydrophobic treatment with a silane coupling agent or the like, or pigment dispersant, which is a polymer having a polar group, is adsorbed on the surface of the colorant It was intended to prevent the aggregation of the pigment.

However, when such a pigment dispersant is used, a certain degree of dispersion can be obtained, but re-aggregation of the pigment occurs in subsequent steps such as drying, molding, and polymerization reaction, or the polymerization method toner in an aqueous medium In the production of the toner, the presence of polar groups on the pigment surface may cause the pigment to float on the toner surface, resulting in a decrease in chargeability and environmental stability.
US Patent 2,297,691 Japanese Patent Publication No. 36-10231 Japanese Patent Publication No. 51-14895 JP-A-53-177735 JP-A-53-17736 JP-A-53-17737 JP 11-119461 A Japanese Patent No. 2800558

  Accordingly, an object of the present invention is to provide a toner that solves the above-described problems and a method for producing 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.

  Another object of the present invention is to provide a toner having no coloring agent floating on the toner surface and excellent in charging property and environmental stability, and a method for producing the toner.

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

（１）
（Ｒ_１とＲ_２のうち少なくとも一方が、置換基Ｘ_１（その他は水素）であり、その置換基Ｙ_１はオリゴマーまたはポリマーである。

(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.

）
で表されることを特徴とするトナーに関する。

)
It is related with the toner characterized by these.

  The present invention also provides 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):

（２）
（Ｒ_３とＲ_４のうち少なくとも一方が置換基Ｘ_２（その他は水素）であり、置換基Ｙ_２とＹ_３は、Ｈ、ＣＨ_３、オリゴマー及びポリマーからなるグループより選ばれる置換基である。

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

）
で表されることを特徴とするトナーに関する。

)
It is related with the toner characterized by these.

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

  According to the present invention, a toner in which a pigment is finely dispersed and excellent in coloring power and transparency can be provided. Further, in a method for producing a polymerized toner in an aqueous medium, a toner production method is provided, in which the colorant is prevented from rising on the toner surface, and the toner can be produced with excellent chargeability and environmental stability. can do.

The pigment dispersant according to the present invention has a structure in which a quinacridone-based molecular skeleton, which is easily adsorbed to a pigment as a colorant, and an oligomer or polymer excellent in affinity with a resin serving as a solvent and a toner binder are covalently bonded. Have. Further, since the pigment dispersing agent according to the present invention, the above substituents X ₁ and X ₂ have the affinity with the resin as a polymerizable monomer and a toner binder used in the pigment dispersion step, The release of the pigment dispersant in the polymerizable monomer or resin is unlikely to occur and can exist stably.

The pigment dispersant that can be used in the present invention has the structure of the formula (1) or (2), and at least one of R ₁ and R ₂ in the formula (1) is the substituent X _1. Since the number of X ₁ increases the affinity with the solvent, while it may inhibit the adsorptive power to the pigment, it is more preferable that one is a substituent X ₁ and the other is a hydrogen atom. Similarly in 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.

As the substituents Y ₁ , Y ₂ and Y ₃ that can be used in the present invention, known oligomer or polymer substituents can be used, and in particular, styrene, styrene derivatives, (meth) acrylic acid and (meth) acrylic. A vinyl polymer component or polyester component containing a monomer selected from the group consisting of acid derivatives as a monomer unit is effective, and has excellent affinity with the solvent used in the pigment dispersion step and the resin used as the toner binder. It is necessary to be. 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-acrylate copolymer, styrene- Examples include methacrylic acid ester copolymers, styrene-glycidyl acrylate copolymers, styrene-glycidyl methacrylate copolymers, and polyesters. The number average molecular weights of the substituents Y ₁ , Y ₂ and Y ₃ are preferably 500 to 100,000 (more preferably 500 to 30,000) in consideration of 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 more preferably 3 to 30 parts by mass when the toner is produced by a polymerization method. .

  In the production of the toner of the present invention, a known formulation, that is, an additive such as a pigment, a resin, other wax, or a charge control agent is used except that the pigment dispersant of formula (1) or (2) is contained. It is possible to use a known method as a manufacturing method. When the toner is manufactured by the pulverization method, the pigment dispersant is mixed with the binder resin, the pigment and other additives, and the mixture is melt-kneaded by applying heat and mechanical shearing force. After that, the toner is used. In the case of the pulverization method, it is also possible to prepare a toner by previously treating a pigment with a pigment dispersant and then melt-kneading the pigment. On the other hand, it is also possible to produce a toner by a polymerization method in which a polymerizable monomer is polymerized directly in an aqueous medium to obtain toner particles. The toner is obtained by a suspension polymerization method, an emulsion polymerization method, or an emulsion aggregation method. Obtainable. In the production method of the suspension polymerization toner, the pigment dispersant and, if necessary, the resin are dissolved in all or part of the polymerizable monomer, and the pigment powder is gradually added while stirring to sufficiently polymerize. The pigment dispersion paste obtained by applying mechanical shearing force with a dispersing machine such as a ball mill, paint shaker, dissolver, attritor, sand mill, high speed mill, etc. A pigment dispersion paste, a polymerization initiator, and the remaining polymerizable monomer are mixed to obtain a polymerizable monomer composition, which is added to an aqueous solvent containing a dispersion stabilizer and granulated, followed by a polymerization reaction. Toner particles can be obtained. In the case of the polymerization method, the pigment and the pigment dispersant can be added separately 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 or condensation polymerization monomer. Preferably, it is an addition polymerization monomer. Specifically, styrene: o-methyl styrene, m-methyl styrene, p-methyl styrene, p-methoxy styrene, p-phenyl styrene, p-chloro styrene, 3,4-dichloro styrene, p-ethyl styrene, 2 , 4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, p- Styrene derivatives such as n-dodecylstyrene; unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated polyenes such as butadiene and isoprene; halogens such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl iodide. Vinyl chlorides: vinyl acetate, vinyl propionate, vinyl benzoate Vinyl esters; methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylate-n-octyl, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, methacryl Α-methylene aliphatic carboxylic acid monoesters such as diethylaminoethyl acid; methyl acrylate, ethyl acrylate, acrylate-n-butyl, acrylate acrylate, propyl acrylate, acrylate-n-octyl, dodecyl acrylate, Acrylic acid esters such as 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate; vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl Vinyl ethers such as ethers; Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone; Vinyl Naphthalenes; (meth) acrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide can be mentioned.

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

  As the pigment that can be used in the present invention, known pigments can be used, and particularly preferably used for 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, and 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.

  In the present invention, the pigment is preferably added in an amount of 3 to 20 parts by mass per 100 parts by mass of the binder resin or polymerizable monomer.

  Examples of the polymerization initiator used in the method for producing the toner of the present invention include known polymerization initiators. 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-azobis (4-methoxy-2,4-dimethylvaleronitrile) Azo compounds such as: peroxides such as benzoyl peroxide and methyl ethyl ketone peroxide; nucleophiles such as alkali metals, metal hydroxides and Grignard reagents, proton acids, metal halides, and stable carbonium ions. The concentration of the polymerization initiator is preferably from 0.1 to 20 mass%, more preferably from 0.1 to 10 mass%, based on the polymerizable monomer.

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

  Further, in the present invention, for the purpose of imparting various characteristics, toner additives as shown below can also be used.

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

  It is also preferable to add an external additive 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 hydrophobic treatment are more preferable. As polishing agents, 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 A salt is preferably used. As the lubricant, fluorine 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 controllable particles, metal oxides such as tin oxide, titanium oxide, zinc oxide, silicon oxide and aluminum oxide, and carbon black are preferably used.

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

  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 described together 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 determined by the GPC measuring device (HLC-8120 GPC Tosoh Corp.) ) Was measured under the following measurement conditions.
・ Measurement conditions ・ Column: TSKgelHM-M (diameter: 6.0 mm × 15 cm), duplex: Temperature: 40 ° C.
・ Flow rate: 0.6ml / min
・ Detector: RI
・ Sample concentration: 10 μl of 0.1% sample
The sample is prepared by placing the sample to be measured in THF and allowing it to stand for several hours, and then shake it sufficiently (until the samples are united together) and let stand for another 12 hours. And let what passed the sample processing filter (pore size 0.45 micrometer) be a sample for GPC measurement. The calibration curve uses a molecular weight calibration curve created with a monodisperse polystyrene standard sample.

<Measurement method of triboelectric charge>
When the toner and the carrier are made into a developer, the toner and the carrier are mixed so that an appropriate mixing amount (2 to 15% by mass) is obtained, and then mixed for 180 seconds with a turbula mixer. The mixed powder (developer) is placed in a metal container having a conductive screen with a mesh opening of 20 μm (635 mesh) at the bottom, and sucked with a suction machine, and the weight difference between before and after suction and a capacitor connected to the container The triboelectric charge amount is obtained from the electric potential accumulated in. 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 potential accumulated in the capacitor.)

<Toner particle size measurement>
0.1 to 5 ml of a surfactant (alkylbenzene sulfonate) is added to 100 to 150 ml of the electrolyte solution, and 2 to 20 mg of a measurement sample is added thereto. The electrolytic solution in which the sample is suspended is dispersed for 1 to 3 minutes using an ultrasonic disperser, and a particle having a particle diameter of 2 to 40 μm is used as a reference, using a 100 μm aperture with a Coulter counter multisizer. The particle size distribution is measured, and the number average particle size and the weight average particle size are calculated from the results.

  The present invention will be described below with reference to examples, but the present invention is not limited to the examples. In addition, all the parts used in an Example show a mass part.

[Production Example 1-1 of Pigment Dispersant]
The acid-polystyrene modified quinacridone (formula (1) -1) was synthesized by the method shown below.

(1) Synthesis of 2-carboxyquinacridone 1,4-cyclohexandione-2,5-dicarboxylic acid dimethyl ester 4.56 parts (0.020 mol part), methyl 4-aminobenzoate 3.78 parts (0.025 mol part), aniline 2.33 parts (0.025 mol part), 50 parts of methanol 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 the mixture was stirred for 10 minutes. The crystals were filtered and washed with hot methanol. The crystals were dried and purified on a silica gel column to give formula (1-a). The structure of the formula (1-a) was identified by nuclear magnetic resonance spectrum, IR spectrum, elemental analysis, and mass spectrometry.

（１−ａ）

(1-a)

  1.0 part (0.0023 mol part) of the compound represented by formula (1-a), 7.7 parts of ethanol, 1.24 parts (0.0188 mol part) of 85% KOH, 3.73 parts of water, m -0.92 part of nitrobenzene sulfonicacid sodium salt was charged into a 30 ml reaction vessel and heated to reflux for 20 hours. The reaction mixture was evaporated, 20 ml of water was added to the residue and filtered. The filtrate was charged into a 50 ml reaction vessel and heated to 80 ° C. To this was added 5.36 parts of 10% hydrochloric acid, and the mixture was stirred at 80 ° C. for 18 hours.

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

（１−ｂ）

(1-b)

  0.39 part (0.000995 mol part) of the compound of the formula (2) and 4 parts of polyphosphoric acid were charged into a 10 ml reaction vessel and reacted at 110 ° C. for 22 hours. The reaction mixture was poured into water, and the precipitated crystals were filtered. Washing with water and drying yielded formula (1-c). The structure of the formula (1-c) was identified by nuclear magnetic resonance spectrum, IR spectrum, elemental analysis, and mass spectrometry.

（１−ｃ）

(1-c)

(3) Synthesis of acid chlorinated quinacridone derivative 4.0 parts of carboxylated quinacridone (formula (1-c)), 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 and refluxed for 10 hours. Went. The reaction product was concentrated by an evaporator to obtain acid chlorinated quinacridone.

(4) Synthesis of acid-polystyrene-modified quinacridone 25 parts of polystyrene (Mn = 4120, Mw = 5022), 80 ml of nitrobenzene and 8.0 parts of aluminum chloride were charged into a reaction vessel and stirred at room temperature for 4 hours, and then acid chlorinated quinacridone. 4.0 parts was added and 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. Furthermore, washing and filtration were repeated with methanol, and vacuum drying was performed at room temperature for 12 hours to obtain acid-polystyrene-modified quinacridone (formula (1) -1). When the IR spectrum, elemental analysis, and molecular weight measurement of this final product were performed, it was found that one acid polystyrene modification was made per one quinacridone skeleton.

１−（１）
（Ｒ_１：置換基Ｘ_１、Ｒ_２：水素、Ｙ_１：ポリスチレン

1- (1)
(R ₁ : Substituent X ₁ , R ₂ : Hydrogen, Y ₁ : Polystyrene

）

)

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

１−（２）
（Ｒ_１：置換基Ｘ_１、Ｒ_２：水素、Ｙ_１：ポリスチレン

1- (2)
(R ₁ : Substituent X ₁ , R ₂ : Hydrogen, Y ₁ : Polystyrene

）

)

[Production Example 1-3 of Pigment Dispersant]
In the production of the pigment dispersant 1- (1), the polystyrene used for modification is changed to a styrene-n-butyl acrylate copolymer (ST / BA = 80/20, Mn = 3762, Mw = 4743). Similarly, the following pigment dispersant 1- (3) was produced.

１−（３）
（Ｒ_１：置換基Ｘ_１、Ｒ_２：水素、置換基Ｙ_１：スチレン−ｎ−ブチルアクリレート共重合体

1- (3)
(R ₁ : Substituent X ₁ , R ₂ : Hydrogen, Substituent Y ₁ : Styrene-n-butyl acrylate copolymer

）

)

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

１−（４）
（Ｒ_１：置換基Ｘ_１、Ｒ_２：水素、置換基Ｙ_１：ポリスチレン

1- (4)
(R ₁ : Substituent X ₁ , R ₂ : Hydrogen, Substituent Y ₁ : Polystyrene

）

)

[Production of resin]
60 parts of styrene, 25 parts of n-butyl acrylate, 15 parts of monobutyl maleate, 0.5 part of divinylbenzene and 1.2 parts of benzoyl peroxide were mixed to prepare solution 1, and polyvinyl alcohol was added to 170 parts of water. A solution obtained by dissolving 0.12 part of partially saponified product is designated as Solution 2. The suspensions 1 and 2 thus obtained were vigorously stirred to prepare a suspension dispersion. Next, the suspension dispersion obtained above was added to a reactor purged with nitrogen by adding 300 parts of water, and suspension polymerization was carried out at a reaction temperature of 75 ° C. for 8 hours. After completion of the reaction, it was washed with water and dehydrated to obtain 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 may be mixed in a blender Then, the mixture was kneaded with a twin-screw kneading extruder set at 150 ° C. The obtained kneaded product is cooled, coarsely pulverized by a cutter mill, finely pulverized using a fine pulverizer using a jet stream, and the obtained finely pulverized powder is classified by a fixed wall type air classifier. A classified powder was prepared. Further, the classified powder obtained above is subjected to a magenta color by strictly classifying and removing ultrafine powder and coarse powder at the same time using a multi-division classifier using the Coanda effect (elbow jet classifier manufactured by Nittetsu Mining). A toner was obtained.

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

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

  When the charge amount of 0.1 g of the obtained developer was measured by a blow-off method in a normal temperature and humidity environment (temperature 25 ° C./humidity 60% RH), it was −17.4 μC / g. Using this developer, an image output test was conducted with a Canon full-color copier CLC-500 modified machine at room temperature and humidity. The development conditions were a development contrast of 300V. The obtained image had an appropriate amount of applied toner, high density, good reproducibility of fine lines, and a high quality image was obtained. This evaluation was also performed at low temperature and low humidity (15 ° C./15% RH) and high temperature and high humidity (30 ° C./75% RH). Was found to have good charging characteristics. Further, when an image was similarly formed on the OHP sheet and projected, a highly transparent magenta projection image was obtained.

[Example 2]
・ Resin (1) 100 parts ・ Quinacridone (CI Pigment Violet 19) 30 parts ・ Pigment Dispersant 1- (2) 20 parts These are kneaded with two rolls and passed through a sieve having an opening of 1 mm. The mixture was pulverized to obtain a master batch (1). next,
-Resin (1) 80 parts-Masterbatch (1) 30 parts-Chromium complex (charge control agent) 4 parts The above materials are mixed well in a blender in the same manner as in Example 1 and biaxial kneading set at 150 ° C. It knead | mixed with the extruder. The obtained kneaded product was cooled, pulverized and classified in the same manner as in Example 1 to obtain a magenta toner.

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

  Using the obtained toner, 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, it was −18.6 μC / g. Using this developer, an image output test was conducted with a Canon full color copier CLC-500 remodeled machine in the same manner as in Example 1. As a result, no fogging occurred, and there was little change in density in any environment. It was found that the toner has good charging characteristics. Further, when an image was similarly formed on the OHP sheet and projected, a highly transparent magenta projection image was obtained.

[Example 3]
• 340 parts of styrene monomer • 4 parts of pigment dispersant of formula (1) -1 • 20 parts of quinacridone (CI Pigment Violet 19) well premixed in a container, then keep it below 20 ° C. Dispersion was carried out with a bead mill for about 5 hours to prepare pigment dispersion paste a. The obtained pigment dispersion paste a was uniformly applied on a glass plate using a wire bar, naturally dried, and measured for a gloss value of 110, indicating good smoothness. Further, when the same coating on the aluminum foil was observed by SEM, the particle size was about 55 nm, and it was found that the pigment was finely dispersed.

450 parts of 0.1 mol / liter-Na ₃ PO ₄ aqueous solution was put into 710 parts of ion-exchanged water, heated to 60 ° C., and then stirred at 11000 rpm using a TK homomixer (manufactured by Special Machine Industries). did. To this, 70 parts of a 1.0 mol / liter-CaCl ₂ aqueous solution was gradually added to obtain a dispersion medium containing Ca ₃ (PO ₄ ) ₂ .
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 3 parts of metal compound These were heated to 60 ° C., dissolved and dispersed, and further maintained at 60 ° C., while adding 10 parts of a polymerization initiator 2,2′-azobisisobutyronitrile to dissolve and polymerize. A functional monomer composition was prepared.

The monomer composition was charged into a dispersion medium prepared in a 2-liter flask of the homomixer. The monomer composition was granulated by stirring at 10000 rpm for 20 minutes using a TK homomixer in a nitrogen atmosphere at 60 ° C. Thereafter, 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 completion of the polymerization reaction, the reaction product was cooled, hydrochloric acid was added to dissolve Ca ₃ (PO ₄ ) ₂ , filtered, washed with water and dried to obtain a polymerized toner.

  When the particle diameter of the obtained toner was measured with a Coulter counter, it had a weight average diameter of 8.2 μm. When the toner surface was observed with an electron scanning microscope (SEM), pigment particles were not observed. Further, when TEM observation was performed in the same manner as in Example 1, it was divided into a surface layer part mainly composed of styrene-acrylic resin and a center part mainly composed of wax, and a capsule structure was confirmed. It was also confirmed that about 55 nm pigment particles were finely dispersed in the styrene-acrylic resin layer.

  Using the obtained toner, 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, it was −17.6 μC / g. Using this developer, images were produced in the same manner as in Example 1 using a Canon full-color copying machine CLC-500 remodeled machine. The obtained image had an appropriate amount of applied toner, high density, good reproducibility of fine lines, and a high quality image was obtained. When this evaluation was carried out at low temperature and low humidity (15 ° C./15%) and high temperature and high humidity (30 ° C./75%), there was no fogging, there was little change in density, and the toner was good. It was found that it showed charging characteristics. Further, when an image was similarly formed on an OHP sheet and projected by OHP, a highly transparent magenta color projection 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 • 20 parts of quinacridone (CI Pigment Violet 19) While maintaining the temperature at 20 ° C. or lower, the mixture was dispersed with a bead mill for about 5 hours to prepare a pigment dispersion paste b.

The obtained pigment dispersion paste b was uniformly coated on a glass plate using a wire bar, naturally dried, and then the gloss value was measured to be 112, indicating good smoothness. Further, when the same coating on the aluminum foil was observed by SEM, the particle size was about 55 nm, and it was found that 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 and did. Further, while maintaining at 60 ° C., 10 parts of initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was added and dissolved to prepare a monomer composition.

The monomer composition was charged into a dispersion medium prepared in the same manner as in Example 3. The monomer composition was granulated by stirring at 60 ° C. for 20 minutes at 10,000 rpm using a TK homomixer in a nitrogen atmosphere. Thereafter, the mixture was reacted at 60 ° C. for 1 hour while stirring with a paddle stirring blade, and then reacted at 80 ° C. for 12 hours. After completion of the polymerization reaction, the reaction product was cooled, hydrochloric acid was added to dissolve Ca ₃ (PO ₄ ) ₂ , filtered, washed with water and dried to obtain a polymerized toner.

  When the particle size of the obtained toner was measured with a Coulter counter, it had a weight average particle size of 8.4 μm. When the toner surface was observed by SEM as in Example 3, no pigment particles were observed as in Example 3. Further, when the cross section of the particles was observed with TEM in the same manner as in Example 3, the same capsule structure as in Example 3 was confirmed, and about 55 nm pigment particles were finely dispersed in the styrene-acrylic resin layer. confirmed.

  When a developer was prepared using the obtained toner in the same manner as in Example 1, the charge amount was −18.4 μC / g. Using this developer, an image was produced in the same manner as in Example 1 using a Canon full color copier CLC-500 remodeling machine. The obtained image had an appropriate amount of applied toner, high density, good reproducibility of fine lines, and a high quality image was obtained. When this evaluation was carried out at low temperature and low humidity (15 ° C./15%) and high temperature and high humidity (30 ° C./75%), there was no fogging, there was little change in density, and the toner was good. It was found that it showed charging characteristics. Further, when an image was similarly formed on the OHP sheet and projected on the OHP, a highly transparent magenta projection image was obtained.

[Example 5]
-320 parts of styrene monomer-80 parts of n-butyl acrylate-5 parts of pigment dispersant of formula (1) -4-20 parts of carbon black (Special Black 4 manufactured by Degussa) Dispersing with a bead mill for about 5 hours while maintaining the temperature below ℃, pigment dispersion paste c was prepared.

The obtained pigment dispersion paste c was uniformly coated on a glass plate using a wire bar, naturally dried and then measured for a gloss value of 115, indicating good smoothness. Further, when the same coating on the aluminum foil was observed with an SEM, the particle size was about 30 to 60 nm, and it was found 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 The monomer was heated to 60 ° C., dissolved and dispersed, and further maintained at 60 ° C., and 10 parts of initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was added to dissolve the monomer. A composition was prepared.

The monomer composition was charged into a dispersion medium prepared in the same manner as in Example 3. The monomer composition was granulated by stirring at 60 ° C. for 20 minutes at 10,000 rpm using a TK homomixer in a nitrogen atmosphere. Thereafter, the mixture was reacted at 60 ° C. for 1 hour while stirring with a paddle stirring blade, and then reacted at 80 ° C. for 12 hours. After completion of the polymerization reaction, the reaction product was cooled, hydrochloric acid was added to dissolve Ca ₃ (PO ₄ ) ₂ , filtered, washed with water and dried to obtain a polymerized toner.

  When the particle size of the obtained toner was measured with a Coulter counter, it had a weight average particle size of 8.1 μm. When the toner surface was observed by SEM as in Example 3, no pigment particles were 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 about 40 to 60 nm of pigment particles were uniformly finely dispersed in the styrene-acrylic resin layer. It was confirmed that

  When a developer was produced using the obtained toner in the same manner as in Example 1, the charge amount was −19.8 μC / g. Using this developer, an image was produced in the same manner as in Example 1 using a Canon full color copier CLC-500 remodeling machine. The obtained image had an appropriate amount of applied toner, high density, good reproducibility of fine lines, and a high quality image was obtained. When this evaluation was performed at low temperature and low humidity (15 ° C./15%) and high temperature and high humidity (30 ° C./75%), no fogging occurred, there was little change in density, and the toner showed good charging characteristics. I found out.

[Example 6]
Styrene monomer 200 parts n-butyl acrylate 50 parts Carbon black (Special Black 4 Degussa) 12.5 parts Formula (1) -4 pigment dispersant 3.2 parts Styrene-methacrylic acid copolymer ( 95: 5, Mw 50,000) 6.3 parts. Di-tert-butylsalicylic acid metal compound 3.8 parts was well premixed in a container and then dispersed in a bead mill for about 5 hours while keeping it at 20 ° C or lower. .

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

The monomer composition was charged into a dispersion medium prepared in the same manner as in Example 3. The monomer composition was granulated by stirring at 60 ° C. for 20 minutes at 10,000 rpm using a TK homomixer in a nitrogen atmosphere. Thereafter, the mixture was reacted at 60 ° C. for 1 hour while stirring with a paddle stirring blade, and then reacted at 80 ° C. for 12 hours. After completion of the polymerization reaction, the reaction product was cooled, hydrochloric acid was added to dissolve Ca ₃ (PO ₄ ) ₂ , filtered, washed with water and dried to obtain a polymerized toner.

  When the particle diameter of the obtained toner was measured with a Coulter counter, it had a weight average diameter of 8.5 μm. When the toner surface was observed by SEM as in Example 3, no pigment particles were observed as in Example 3. Furthermore, when the cross section of the particles was observed with TEM in the same manner as in Example 3, the same capsule structure as in Example 3 was confirmed, and about 40 to 80 nm of pigment particles were uniformly finely dispersed in the styrene-acrylic resin layer. It was confirmed that

  When a developer was produced using the obtained toner in the same manner as in Example 1, the charge amount was −17.0 μC / g. Using this developer, an image was produced in the same manner as in Example 1 using a Canon full color copier CLC-500 remodeling machine. The obtained image had an appropriate amount of applied toner, high density, good reproducibility of fine lines, and a high quality image was obtained. When this evaluation was performed at low temperature and low humidity (15 ° C./15%) and high temperature and high humidity (30 ° C./75%), no fogging occurred, there was little change in density, and the toner showed good charging characteristics. I found out.

[Comparative Example 1]
-320 parts of styrene monomer-80 parts of n-butyl acrylate-20 parts of quinacridone (CI Pigment Violet 19) After premixing well in a container, it is dispersed in a bead mill for about 5 hours while keeping it at 20 ° C or lower. Thus, a pigment dispersion paste d was prepared.

The obtained pigment dispersion paste d was applied onto a glass plate in the same manner as in Example 3, and the gloss value was measured to be 70, indicating that no smoothness was obtained. In addition, when the SEM observation was performed on the aluminum foil applied in the same manner as in Example 3, the particle size ranged from coarse particles of about 220 nm to fine particles of about 55 nm, and the variation in particle size distribution due to pigment aggregation 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-butyl salicylic acid metal compound 3 parts Was heated to 60 ° C., dissolved and dispersed, and further an initiator was added to obtain a monomer composition. In the same manner as in Example 3, a polymerized toner was obtained through granulation, polymerization, washing and drying.

  When the particle size of the obtained toner was measured with a Coulter counter, it had a weight average particle size of 8.1 μm. When the toner surface was observed by SEM as in Example 3, no pigment particles were 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 needle-like pigment particles of about 50 to 200 nm were dispersed in the styrene-acrylic resin layer. It was. It was also observed that many pigment particles were present at the interface between the wax and the styrene acrylic resin.

  When a developer was prepared using the obtained toner in the same manner as in Example 1, the charge amount was -20.6 μC / g. Using this developer, an image was produced in the same manner as in Example 1 using a Canon full color copier CLC-500 remodeling machine. The obtained image has an appropriate amount of applied toner, good reproducibility of fine lines, and was performed under low temperature and low humidity (15 ° C / 15%) and high temperature and high humidity (30 ° C / 75%). As a result, it was found that the toner exhibits good charging characteristics. However, when an image was similarly formed on the OHP sheet and projected on the OHP, a projection image slightly inferior in transparency compared to Example 3 was obtained, and saturation was not obtained as in Example 3.

[Comparative Example 2]
Pigment dispersant (Ajisper PB711: manufactured by Ajinomoto Co., Inc. (grafted polymer obtained by reacting a polyepoxy compound with a linear polymer having a carboxyl group and an organic amino compound) 4 parts styrene monomer 320 parts n-butyl acrylate 80 parts Quinacridone (CI Pigment Violet 19: 3) After 20 parts were well premixed in a container, the mixture was dispersed in a bead mill for about 5 hours while being kept at 20 ° C. or lower to prepare a pigment dispersion paste e.

The obtained pigment dispersion paste e was uniformly coated on a glass plate using a wire bar, naturally dried, and then measured for gloss value. As a result, it was 112, which showed good smoothness. Further, when the same coating on the aluminum foil was observed by SEM, the particle size was about 55 nm, and it was found that the pigment was finely dispersed.
-Pigment dispersion paste e 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 further an initiator was added to obtain a monomer composition. In the same manner as in Example 3, a polymerized toner was obtained through granulation, polymerization, washing and drying.

  When the particle size of the obtained toner was measured with a Coulter counter, 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. Further, when the cross section of the particles was observed by TEM in the same manner as in Example 3, the same capsule structure as in Example 3 was confirmed, and pigment particles having a particle size of about 50 to 150 nm were slightly agglomerated in the styrene-acrylic resin layer. It was found that there were many pigments at the interface between the wax and the binder.

  When a developer was prepared using the obtained toner in the same manner as in Example 1, the charge amount was -12.0 μC / g. Using this developer, an image was produced in the same manner as in Example 1 using a Canon full color copier CLC-500 remodeling machine. The obtained image had an appropriate amount of applied toner, but some fogging occurred. In addition, fogging was observed to deteriorate under a high temperature and high humidity (30 ° C./75%) environment, and it became clear that the environmental characteristics of the toner were inferior to the toner of Example 3. On the other hand, when the image was put on the OHP sheet, a magenta projection image slightly inferior in transparency as compared with Example 3 was obtained.

[Comparative Example 3]
-Resin (1) 100 parts-Quinacridone (PigmentViolet 19) 6 parts-Chromium complex (charge control agent) 4 parts-The above materials were kneaded, pulverized and classified in the same manner as in Example 1 to obtain a magenta toner.

  When the particle size of the obtained toner was measured with a Coulter counter, it had a weight average particle size 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 pigment particles having a particle size of about 50 to 200 nm were present in a slightly cohesive manner in the styrene-n-butyl methacrylate resin layer. all right.

  When a developer was prepared using the obtained toner in the same manner as in Example 1, the charge amount was -16.2 μC / g. Using this developer, a Canon full-color copying machine CLC-500 remodeled machine was used to output an image on an OHP sheet in the same manner as in Example 1. As a result, the magenta color was slightly inferior in transparency compared to Example 1. Projection images were obtained.

  Each evaluation of environmental stability, fogging and permeability in the table was performed according to the following criteria. In addition, also about the below-mentioned Example, it evaluated by the same reference | standard.

[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]
Densitometer TC-6DS manufactured by Tokyo Denshoku under high temperature and high humidity
Fog density (%) = (reflection density of the fogging part 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]
The fixed image on the OHP sheet (toner paste amount 0.7 mg / cm ² ) was made into a transmission image with an overhead projector (OHP: 9550 manufactured by 3M), and L * and c * of the image projected on the white wall surface were spectral radiance. It was measured with a meter (PR650 manufactured by Photo Research) and evaluated as a colorimetric index p = (95−L *) / c * of the projected image.
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]
A styrene-glycidyl methacrylate copolymer-modified quinacridone (formula (2) -1) was synthesized by the following method.

  0.31 part of quinacridone (CI Pigment Violet 19), 0.11 part of potassium tert-butoxide, 5.0 parts of dimethyl sulfoxide, styrene-glycidyl methacrylate copolymer (number average molecular weight Mn = 14606, weight average molecular weight Mw) = 16700, epoxy equivalent 462 g / mol) 6.0 parts of solution was added to a 50 ml reaction vessel, and the reaction was carried out in an oil bath at 60 ° C. for 5 hours. After cooling the reaction mixture, the reaction mixture was taken out into a 100 ml beaker, and a 50 ml reaction vessel was washed with 50 ml of xylene, and 2.0 ml of 0.5 mol / HCl aqueous solution was added with stirring. The obtained mixture was added dropwise to 400 ml of methanol to perform reprecipitation purification. Further, after washing and filtering with 200 ml of water and 200 ml of methanol, vacuum drying was performed at room temperature for 12 hours to obtain 2.6 parts of a styrene-glycidyl methacrylate copolymer-modified quinacridone (Formula 2- (1)). The IR spectrum, elemental analysis, and molecular weight measurement of this final product revealed that an average of 1.30 styrene-glycidyl methacrylate copolymer modifications were made per quinacridone skeleton.

２−（１）
（置換基Ｒ_３、Ｒ_４の少なくとも一方は置換基Ｘ_２であり、分散剤全体としては、Ｒ_３及びＲ_４の合計の６５％が置換基Ｘ_２であった。残りは水素であり、置換基Ｘ_２中の置換基Ｙ_２及びＹ_３は、スチレン−メタクリル酸グリシジル共重合体（Ｓｔ／メタクリル酸グリシジル＝８０／２０）

2- (1)
(At least one of the substituents R ₃ and R ₄ is the substituent X ₂ , and as a whole dispersant, 65% of the total of R ₃ and R ₄ was the substituent X _{2. The} rest is hydrogen. The substituents Y ₂ and Y ₃ in the substituent X ₂ are styrene-glycidyl methacrylate copolymer (St / glycidyl methacrylate = 80/20).

）

)

[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, and the molecular weight of the styrene-glycidyl methacrylate copolymer used for modification was Mn = 30812, Mw = 37051. The following pigment dispersant 2- (2) was produced in the same manner except changing to

２−（２）
（置換基Ｒ_３、Ｒ_４少なくとも一方は置換基Ｘ_２であり、分散剤全体としては、Ｒ_３及びＲ_４の合計の６１％が置換基Ｘ_２であった。残りは水素であり、置換基Ｘ_２中の置換基Ｙ_２及びＹ_３はスチレン−メタクリル酸グリシジル共重合体（８０／２０）

2- (2)
(At least one of the substituents R ₃ and R ₄ is the substituent X ₂ , and as a whole dispersant, 61% of the total of R ₃ and R ₄ was the substituent X ₂ . The substituents Y ₂ and Y ₃ in the group X ₂ are styrene-glycidyl methacrylate copolymer (80/20).

）

)

[Production Example 2-3 of Pigment Dispersant]
In the production of the pigment dispersant 2- (1), the production conditions of the styrene-glycidyl methacrylate copolymer were changed, and the molecular weight of the styrene-glycidyl methacrylate copolymer used for modification was Mn = 16202, Mw = 19244. The following pigment dispersant 2- (3) was produced in the same manner except changing to

Ｂ−３
（置換基Ｒ_３、Ｒ_４少なくとも一方は置換基Ｘ_２であり、分散剤全体としては、Ｒ_３及びＲ_４の合計の５５％が置換基Ｘ_２であった。残りは水素であり、置換基Ｘ_２中の置換基Ｙ_２及びＹ_３はスチレン−メタクリル酸グリシジル共重合体（８０／２０）

B-3
(At least one of the substituents R ₃ and R ₄ is the substituent X ₂ , and as a whole dispersant, 55% of the total of R ₃ and R ₄ was the substituent X ₂ . The substituents Y ₂ and Y ₃ in the group X ₂ are styrene-glycidyl methacrylate copolymer (80/20).

）

)

[Example 7]
-Resin used in Example 1 (1) 100 parts-Pigment dispersant of formula 2- (1) 4 parts-Quinacridone (CI Pigment Violet 19) 6 parts-Chromium complex (charge control agent) 4 parts The material was kneaded, pulverized, and classified in the same manner as in Toner Preparation Example 1 to obtain a magenta resin fine powder.

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

  Using the obtained toner, a developer was produced in the same manner as in Example 1, and the result was −18.4 μC / g. Using this developer, an image was produced in the same manner as in Example 1 using a Canon full color copier CLC-500 remodeling machine. The obtained image had an appropriate amount of applied toner, high density, good reproducibility of fine lines, and a high quality image was obtained. When this evaluation was performed at low temperature and low humidity (15 ° C./15%) and high temperature and high humidity (30 ° C./75%), no fogging occurred, there was little change in density, and the toner showed good charging characteristics. I found out. Further, when an image was similarly formed on the OHP sheet and projected on the OHP, a highly transparent magenta projection image was obtained.

[Example 8]
・ Resin (1) 100 parts ・ Quinacridone (CI Pigment Violet 19) 30 parts ・ Pigment dispersant 2- (2) 20 parts These are kneaded with two rolls so as to pass through a sieve having an opening of 1 mm. The mixture was pulverized to obtain a master batch (2). next,
-Resin (1) 80 parts-Masterbatch (2) 30 parts-Chromium complex (charge control agent) 4 parts The above materials are mixed well in a blender as in Example 1, and biaxial kneading set at 150 ° C. It knead | mixed with the extruder. The obtained kneaded product was cooled, pulverized and classified in the same manner as in Example 1 to obtain a magenta toner.

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

  When a developer was produced in the same manner as in Example 1, it was -17.6 μC / g. Using this developer, the same image was produced as in Example 1. The obtained image was a high quality image with an appropriate amount of applied toner, high density, good reproducibility of fine lines. When this evaluation was performed at low temperature and low humidity (15 ° C./15%) and high temperature and high humidity (30 ° C./75%), no fogging occurred, there was little change in density, and the toner showed good charging characteristics. I found out. Further, when an image was similarly formed on the OHP sheet and projected on the OHP, a highly transparent magenta projection image was obtained.

[Example 9]
-340 parts of styrene monomer-4 parts of pigment dispersant of formula 2- (1)-20 parts of quinacridone (CI Pigment Violet 19) is well premixed in a container and then kept at 20 ° C or below The pigment dispersion paste f was prepared by dispersing with a bead mill for about 5 hours. The obtained pigment dispersion paste f was uniformly coated on a glass plate using a wire bar, naturally dried, and then its gloss value was measured to be 109, which showed good smoothness. Further, when the same coating on the aluminum foil was observed by SEM, the particle size was about 55 nm, and it was found that 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 3 parts of metal compound These were heated to 60 ° C., dissolved and dispersed, and further maintained at 60 ° C., and 10 parts of initiator 2,2′-azobisisobutyronitrile was added and dissolved, A body composition was prepared.

The monomer composition was charged into a dispersion medium prepared in the same manner as in Example 3. The monomer composition was granulated by stirring at 60 ° C. for 20 minutes at 10,000 rpm using a TK homomixer in a nitrogen atmosphere. Thereafter, 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 completion of the polymerization reaction, the reaction product was cooled, hydrochloric acid was added to dissolve Ca ₃ (PO ₄ ) ₂ , filtered, washed with water and dried to obtain a polymerized toner.

  When the particle size of the obtained toner was measured with a Coulter counter, it had a weight average particle size of 8.1 μm. When the toner surface was observed with an electron scanning microscope (SEM), pigment particles were not observed. Further, when TEM observation was performed in the same manner as in Example 3, it was divided into a surface layer part mainly composed of styrene-acrylic resin and a center part mainly composed of wax, and a capsule structure was confirmed. It was also confirmed that about 55 nm pigment particles 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, it was -19.8 μC / g. Using this developer, images were produced in the same manner as in Example 1 using a Canon full-color copying machine CLC-500 remodeled machine. The obtained image had an appropriate amount of applied toner, high density, good reproducibility of fine lines, and a high quality image was obtained. When this evaluation was performed at low temperature and low humidity (15 ° C./15%) and high temperature and high humidity (30 ° C./75%), no fogging occurred, there was little change in density, and the toner showed good charging characteristics. I found out. Further, when an image was similarly formed on the OHP sheet and projected with OHP, a highly transparent magenta projection image 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) are well premixed in a container and then kept at 20 ° C. or lower. The pigment dispersion paste g was prepared by dispersing for about 5 hours in a bead mill.

The obtained pigment dispersion paste g was uniformly coated on a glass plate using a wire bar, naturally dried, and then its gloss value was measured to be 113, which showed good smoothness. Further, when the same coating on the aluminum foil was observed by SEM, the particle size was about 55 nm, and it was found that 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 The monomer was heated to 60 ° C., dissolved and dispersed, and further maintained at 60 ° C., and 10 parts of initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was added to dissolve the monomer. A composition was prepared.

The monomer composition was charged into a dispersion medium prepared in the same manner as in Example 3. The monomer composition was granulated by stirring at 60 ° C. for 20 minutes at 10,000 rpm using a TK homomixer in a nitrogen atmosphere. Thereafter, the mixture was reacted at 60 ° C. for 1 hour while stirring with a paddle stirring blade, and then reacted at 80 ° C. for 12 hours. After completion of the polymerization reaction, the reaction product was cooled, hydrochloric acid was added to dissolve Ca ₃ (PO ₄ ) ₂ , filtered, washed with water and dried to obtain a polymerized toner.

  When the particle diameter of the obtained toner was measured with a Coulter counter, it had a weight average diameter of 8.2 μm. When the toner surface was observed by SEM as in Example 3, no pigment particles were observed as in Example 3. Further, when the cross section of the particles was observed by TEM in the same manner as in Example 3, the same capsule structure as in Example 2 was confirmed, and about 55 nm pigment particles were finely dispersed in the styrene-acrylic resin layer. confirmed.

  When a developer was produced in the same manner as in Example 1, the charge amount was -19.0 μC / g. Using this developer, an image was produced in the same manner as in Example 1 using a Canon full color copier CLC-500 remodeling machine. The obtained image had an appropriate amount of applied toner, high density, good reproducibility of fine lines, and a high quality image was obtained. When this evaluation was performed at low temperature and low humidity (15 ° C./15%) and high temperature and high humidity (30 ° C./75%), no fogging occurred, there was little change in density, and the toner showed good charging characteristics. I found out. Further, when an image was similarly formed on the OHP sheet and projected on the OHP, a highly transparent magenta projection image was obtained.

[Example 11]
-Styrene monomer 200 parts-n-butyl acrylate 50 parts-Quinacridone (Pigment Violet 19) 12.5 parts-Pigment dispersant of formula (2) -2 2.5 parts-Styrene-methacrylic acid copolymer (95: 5, Mw 50,000) 6.3 parts. Di-tert-butylsalicylic acid metal compound 3.8 parts were well premixed in a container, and then dispersed in a bead mill for about 5 hours while maintaining at 20 ° C or lower.

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

The monomer composition was charged into a dispersion medium prepared in the same manner as in Example 3. The monomer composition was granulated by stirring at 60 ° C. for 20 minutes at 10,000 rpm using a TK homomixer in a nitrogen atmosphere. Thereafter, the mixture was reacted at 60 ° C. for 1 hour while stirring with a paddle stirring blade, and then reacted at 80 ° C. for 12 hours. After completion of the polymerization reaction, the reaction product was cooled, hydrochloric acid was added to dissolve Ca ₃ (PO ₄ ) ₂ , filtered, washed with water and dried to obtain a polymerized toner.

  When the particle diameter of the obtained toner was measured with a Coulter counter, it had a weight average diameter of 8.5 μm. When the toner surface was observed by SEM as in Example 3, no pigment particles were observed as in Example 3. Further, when the cross section of the particles was observed by TEM in the same manner as in Example 3, the same capsule structure as in Example 3 was confirmed, and the pigment particles of about 55 to 70 nm were uniformly finely dispersed in the styrene-acrylic resin layer. It was confirmed that

  When a developer was prepared using the obtained toner in the same manner as in Example 1, the charge amount was -20.5 μC / g. Using this developer, an image was produced in the same manner as in Example 1 using a Canon full color copier CLC-500 remodeling machine. The obtained image had an appropriate amount of applied toner, high density, good reproducibility of fine lines, and a high quality image was obtained. When this evaluation was performed at low temperature and low humidity (15 ° C./15%) and high temperature and high humidity (30 ° C./75%), no fogging occurred, there was little change in density, and the toner showed good charging characteristics. I found out.

Claims (9)

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).

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

) The vinyl polymer component in which the substituent Y ₂ and Y _{3 of the} pigment dispersant contains, as a monomer unit, a monomer selected from the group consisting of styrene, styrene derivatives, (meth) acrylic acid and (meth) acrylic acid ester The toner according to claim 1, wherein the toner is a polyester component.   The toner according to claim 1, wherein the content of the pigment dispersant is 2 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the pigment. 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 and classifying the obtained kneaded product, wherein the pigment dispersant is represented by the following formula ( 2) A method for producing toner, which is represented by

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

) 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, pulverizing and classifying the obtained kneaded product, and the pigment dispersant comprising: A toner production method represented by the following formula (2):

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

) A method for producing a toner, comprising: preparing a polymerizable monomer composition containing at least a polymerizable monomer and a pigment; and polymerizing the polymerizable monomer in the composition to prepare a toner, the pigment comprising Is a surface-treated with a pigment dispersant represented by the following formula (2) before being added to the polymerizable monomer composition.

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

)   The method for producing a toner according to claim 6, wherein the toner is produced by suspension polymerization. A method for producing a toner, comprising 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 to prepare a toner. The pigment dispersant is represented by the following formula (2).

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

)   The toner production method according to claim 8, wherein the toner is produced by suspension polymerization.