JP2748147B2 - Polymerized color toner and method for producing the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a polymerized color toner used for visualizing an electric latent image in electrophotography, electrostatic photography, and the like, and a method for producing the same.

[Prior Art] Conventionally, as a toner, generally, a colorant is melt-mixed in a thermoplastic resin and uniformly dispersed, and then a toner having a desired particle size is produced by a fine pulverizer / classifier.

Although this method can produce a very good toner,
For example, the selection range of the toner material is limited because the resin colorant dispersion is sufficiently brittle and must be able to be pulverized with an economically feasible manufacturing apparatus.

On the other hand, in order to overcome the problems of the toner by these pulverization methods, JP-B-36-10231, JP-B-43-10799 and JP-B-51-1489 have been disclosed.
No. 5 proposes a method for producing a toner by a suspension polymerization method. In the suspension polymerization method, a monomer composition comprising a polymerizable monomer, a colorant, a polymerization initiator and, if necessary, a cross-linking agent, a charge control agent, and other additives is continuously mixed with a dispersion stabilizer. In a water phase, for example, an aqueous phase is dispersed using a suitable stirrer, and at the same time, a polymerization reaction is carried out to obtain toner particles having a desired particle size. Since this suspension polymerization method does not include a mechanical pulverization step, there is no inconvenience caused by pulverization as seen in the pulverization method, and the obtained toner has a spherical shape, excellent fluidity, and triboelectric charging. It has various advantages such as uniformity.

However, there are problems to be solved even in the polymerization method toner having such excellent properties. That is,
Suspension polymerization toner is a method of producing a toner by granulating a polymerizable monomer system in water and performing a polymerization reaction. Materials that inhibit the reaction cannot be used. For this reason, there are considerable restrictions on the material selection of the colorant, which is an essential component as a color toner.

For example, when a dye is used as a colorant, there is no problem with respect to dispersion stability because many are soluble in monomers,
Most of the dyes have polymerization inhibitory properties, so that a cured product cannot be obtained. When a pigment is used as a colorant, there is no problem with respect to polymerization inhibition, but there is a difficulty in dispersion stability in a monomer system, and aggregation of the pigment is likely to occur during granulation. As a result, granulation stability deteriorates,
The resulting toner often has a broad particle size distribution and lacks homogeneity. As described above, the coloring agent has advantages and disadvantages for both the dye and the pigment. However, considering the material cost, the use of the pigment is preferable.

Further, in recent years, there has been a demand for a reduction in the amount of toner consumption in a copying machine. One of the measures is to improve the coloring power of the toner. As a method of improving the coloring power, there is a method of improving the dispersibility of the colorant, eliminating the aggregates, and uniformly dispersing the colorants.

As described above, in the polymerization method toner, improvement of the dispersibility of the colorant, particularly the pigment, in the monomer system is an important issue. Improve the dispersion in such a polymerizable monomer system,
In addition, as a means for preventing the transfer to the aqueous phase, there is a method of lipophilicizing the surface of the pigment.

Methods for lipophilic treatment of pigments have been studied in the past, and derivatization of pigments, coating with resins, treatment with coupling agents, and the like have been proposed.

For example, in the derivatization of pigments, aminoalkylation treatment of copper phthalocyanine pigment according to JP-A-48-15930, introduction of substituents to quinacridone-based pigments according to JP-A-61-168666 and USP3275637, Showa 57-28
No. 162, a method based on intermolecular coupling of a naphthol-based pigment. These are preferred methods because they are treated with a chemical bond to the pigment.However, since the treatment method differs for each pigment, and the properties of the treated pigment vary depending on the pigment, cost and polymerization methods are reduced. However, it is disadvantageous in terms of standardizing prescriptions.
JP-A-58-7648 discloses a toner using a pigment treated with a titanium coupling agent. However, the pigment in the publication is substantially a magnetic substance, carbon black, and has a reactive activity on the surface. There is no treatment effect for organic pigments having no spots.

On the other hand, as a surface treatment method irrespective of the kind of pigment, there is a resin coat. For example, a pigment coat with an aminoalkylate acrylate polymer in JP-A-58-215461, a pigment coat with a urea resin in JP-B-47-14273, and the like can be mentioned. In this case, the monomer functions as a solvent, and the coating agent dissolves and desorbs, so that not only the desired dispersibility cannot be obtained, but also the desorbed polymer adversely affects the granulation properties and toner properties. Undesired results.

As described above, the lipophilic treatment of a pigment suitable for a polymerization method is not yet sufficient, and as a result, a color toner, particularly a polymer toner for full color, which is sufficient in cost and performance, has been obtained. There is no present.

[Problems to be Solved by the Invention] The present invention has been made in view of the above-mentioned situation,
It is a primary object of the present invention to provide a polymerized color toner having excellent spectral reflection characteristics, color mixing properties and transparency, and excellent developability, and a method for producing the same.

It is another object of the present invention to provide a polymerizable color toner which is stable during polymerization of a polymerizable monomer system, has a stable charge characteristic and has excellent developability, and a method for producing the same.

[Means and Actions for Solving the Problems] The above object is achieved by the present invention described below.

That is, the present invention relates to a polymerized color toner obtained by suspension polymerization of a polymer monomer system containing at least a colorant in an aqueous phase, wherein the colorant is an organic pigment having an OH group and a silicon-containing compound. The present invention relates to a polymerized color toner characterized by being processed.

 Hereinafter, the present invention will be described in detail.

The present inventors have conducted intensive studies and found that an oleophilic treatment was performed by treating an organic pigment having an OH group with a silicon-containing compound, thereby significantly improving the dispersibility of the organic pigment. .

The treatment with the silicon-containing compound according to the present invention is characterized in that the treatment is not a mere coating treatment but is carried out through a chemical bond. The treatment through the chemical bond includes a method in which a lipophilic treatment is performed by reacting a surface oxide of the pigment with a silane coupling agent, and a method in which a silicone-based polymer is formed on the surface of an active pigment to perform a lipophilic treatment. Is performed.

Generally, active points such as hydroxyl groups do not exist on the surface of an organic pigment, and therefore, it is necessary to introduce active points in order to treat with a silane coupling agent. Examples of a method for introducing these active sites include treatment of the pigment with an oxidizing agent and oxidation treatment with plasma.

In performing the oxidation treatment with the oxidizing agent, as the oxidizing agent that can be used in the present invention, one that binds oxygen to the surface of the organic pigment by an oxidation reaction and forms a polar compound therewith can be generally used, and is particularly preferably. For example, ozone, hydrogen peroxide, peroxides and derivatives thereof such as ammonium peroxide, or nitric acid and its salts, perchloric acid and its salts, hypochlorous acid and its salts, permanganic acid and its salts,
Oxo acids and salts thereof such as chromic acid and salts thereof.

If necessary, means for increasing the activity of the oxidizing agent, such as using an oxidizing agent in combination with an acid or alkali, or an oxidizing catalyst, can be taken.

It is not clear what kind of structure of the surface imparts the polarity imparted by the oxidation treatment, but by applying an oxidizing agent to the organic pigment, the surface of the organic pigment is oxidized and decomposed, and It is believed that groups are formed on the surface, thereby developing polarity.

The oxidizing agent can be applied to the organic pigment by a dry method in which an oxidizing gas or vapor is brought into contact with the pigment, or by adding an oxidizing agent to an aqueous suspension obtained by suspending an organic pigment in water. There is a wet method in which an organic pigment is suspended in water containing an oxidizing agent, and the wet method can be used particularly conveniently. When the treatment is performed by the wet method, the pigment may be suspended using an anionic, cationic, amphoteric or nonionic surfactant, if necessary.

In order to maximize the effect of the oxidation treatment, it is desirable to uniformly oxidize the surface of the pigment. As the method, when performing the oxidation treatment, it is preferable to stir the aqueous suspension of the pigment, and furthermore, apply a shear to uniformly and finely grind the pigment, and sufficiently widen the surface to be subjected to the oxidation treatment. Is more preferably performed.

The shearing force is generated by moving a grinding aid, such as glass, ceramics, metal spheres or sand, in an aqueous suspension by means of a high-speed rotary stirrer. As a device, for example, a device generally used for dispersing a pigment, such as a sand mill, a ball mill, and an attritor, is suitable. In order to effectively generate a shearing force and to sufficiently spread the pigment surface to be oxidized, the pigment content is preferably 1 to 40% by weight in the aqueous suspension, and 5 to 30% by weight. % Is more preferable. The grinding auxiliary is generally used in a volume of 0.3 to 1.5 times the volume of the aqueous suspension.

The treated organic pigment is filtered, washed, dried, pulverized and used in a usual manner.

The concentration of the oxidizing agent, the oxidizing treatment time and the temperature at which the oxidizing agent is applied need to be determined depending on the type of the oxidizing agent. By controlling the oxidation conditions, the organic pigment can be oxidized without substantially affecting the hue, weather resistance, fastness, and the like. The temperature at which the oxidizing agent acts is preferably 60 ° C. or lower. 60 ℃
This is because if the ratio exceeds, the hue change becomes large and it is difficult to control the oxidation conditions. However, depending on the type of the pigment and the oxidizing agent, it may be better to perform the treatment at a temperature higher than 60 ° C.

On the other hand, a method for introducing active sites to the pigment surface by the plasma oxidation treatment is as follows.

The plasma oxidation treatment can be generally performed by an apparatus for performing a plasma treatment. FIG. 1 shows an outline of a typical apparatus. In the figure, 1 is a motor, 2 is a high frequency power supply, 3 is a high frequency supply electrode, 4 is a magnetic stirrer, and 5 is a magnetic stirrer. Less than,
The plasma oxidation treatment using this apparatus will be described.

The pigment is placed in a reaction vessel, the pressure in the reaction vessel is reduced, and the pigment is sufficiently dried. The amount of the pigment to be treated, the degree of reduced pressure, and the drying time vary depending on the state of the pigment, but as a guide, a suitable amount of the treated substance is 20 g, the degree of reduced pressure is 0.2 Torr or less, and the drying time is about one hour.

After drying the pigment, while maintaining a predetermined degree of reduced pressure, oxygen is supplied, the magnetic stirrer 4 is operated, and oxidation is performed by applying high frequency. Although each condition varies depending on the pigment type, the high-frequency output is suitably 20 to 100 W, and if the output is less than 20 W, the pigment is not sufficiently processed. Ashing proceeds.
The degree of decompression is suitably 0.5 to 5 torr, and if it is 0.5 torr or less, the oxygen concentration in the container becomes low and the processing time becomes long, and 5 torr
If it becomes larger, high-frequency output must be increased in order to perform sufficient processing, which is inappropriate. An appropriate processing time is 1 to 60 minutes.

Examples of the silicon-containing compound used when performing the lipophilic treatment of the present invention include the following.

γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ
-(2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane,
Methyltrimethoxysilane, ethyltriethoxysilane, γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane.On the other hand, the method for producing a silicone polymer on the surface of an active pigment is as follows. There is a way.

First, active sites are introduced into the surface of the organic pigment by using the above-described oxidation treatment method. Next, the surface-activated pigment is represented by the general formula (R ₁ HSiO) _a (R ₂ R ₃ SiO) _b (R ₄ R ₅ R ₆ SiO _1/2 ) _c [I] (wherein R ₁ , R ₂ and R ₃ are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with at least one halogen atom,
R ₁ , R ₂ and R ₃ are not simultaneously hydrogen atoms, and R ₄ , R ₅ and R ₆ are each independently a hydrogen atom or substituted by at least one halogen atom. A hydrocarbon group having 1 to 10 carbon atoms, and a is 0
Or an integer of 1 or more, b is 0 or an integer of 1 or more, and c is 0 or 2, provided that when c is 0, the sum of a and b is an integer of 3 or more. Is placed under at least one atmosphere of a silicone compound represented by the formula (1) to form a polymer of the silicone compound on the surface of the pigment.

More specifically, the silicone compound exemplified by the general formula [I] preferably comprises two groups,
The group corresponds to the compound of general formula [I] where c = 0, and has the general formula (R ₁ HSiO) _a (R ₂ R ₃ SiO) _b [II] [wherein R ₁ , R ₂ , R ₃ , a And b have the same meaning as described above, but preferably a lower alkyl group or aryl having 1 to 4 carbon atoms, wherein R ₁ , R ₂ and R ₃ may be independently substituted with at least one halogen atom. Group (for example, a phenyl group), and the sum of a and b is 3 to 7]. The second group includes compounds of the general formula [I] where c = 2 Equivalent to the general formula (R ₁ HSiO) _a (R ₂ R ₃ SiO) _b (R ₄ R ₅ R ₆ SiO _1/2 ) ₂ [III] [where R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , a and b have the same meaning as described above, and preferably, R _{1 to} R ₆ are independently a lower alkyl having 1 to 4 carbon atoms which may be independently substituted with at least one halogen atom. Group or an aryl group, Is a linear silicone compound sum of b is represented by a 2-5] and.

As a typical example of the former cyclic silicone compound, and so on. These can be used alone or as a mixture.

In the above formulas, n or a + b is preferred in that 3 to 7 are vaporized, and 3 to 4 are particularly preferred in consideration of reactivity.

Examples of these cyclic silicone compounds include, for example, dihydrodienehexamethylcyclotetrasiloxane, trihydrodienepentamethylcyclotetrasiloxane, tetrahydrodienetetramethylcyclotetrasiloxane, dihydrodieneoctamethylcyclopentasiloxane, trihydrodieneheptamethyl Cyclopentacycloxane, tetrahydrodienehexamethylcyclopentasiloxane, pentahydrodienepentamethylcyclopentasiloxane, and the like are used.

Also, typical examples of the latter linear silicone compound include: Is raised.

As this linear silicone compound, for example, 1,1,1,
2,3,4,4,4-octamethyltetrasiloxane, 1,1,1,2,
3,4,5,5,5-nonamethylpentasiloxane, and 1,1,
For example, 1,2,3,4,5,6,6,6-decamethylhexasiloxane is used.

The amount of treatment with the silicone compound described above is governed by the active points on the pigment surface, but is generally 0.005 to 50% of the pigment weight.

Treatment of surface-activated pigments with these silicone compounds is a method in which vaporized organosiloxanes are adsorbed on the pigment surface in a molecular state, and polymerization is carried out from active points on the surface due to the high reactivity of Si-H and cyclic substances. By using a low-molecular silicone compound as described above,
The treatment can be performed at a temperature of preferably 100 ° C. or less.

That is, 120 ° C. or less, preferably put the pigment to be treated in a closed container of 100 ° C. or less, after once degassed under reduced pressure,
A carrier gas (e.g., an inert gas) obtained by vaporizing a silicone compound is introduced at a predetermined partial pressure in another closed container having a temperature of 120 ° C. or lower to cause a treatment reaction. The pressure in the system at this time is not particularly limited, but is desirably set to a pressure of 200 mmHg or less, preferably 100 mmHg or less. The treatment time is generally 30 minutes to 100 hours. After the treatment, the unreacted silicone compound is removed by degassing to obtain a treated pigment.

As the organic pigment used in the present invention, any known organic pigment can be used, but it is preferable that the organic pigment be stable without causing a reaction with other components. The organic pigment having an active site in its structure may be subjected to a silicone compound treatment without performing the above-described oxidation treatment.

The polymerized color toner used in the present invention is obtained by the following method. That is, a monomer system obtained by uniformly dissolving or dispersing a wax, a colorant, a polymerization initiator, and other additives in a polymerizable monomer by using an ultrasonic disperser, a homogenizer, etc., and containing a suspension stabilizer. In an aqueous phase (ie, a continuous phase) to be dispersed using a conventional stirrer, homomixer, homogenizer, or the like. Preferably the monomer droplets are of the desired toner particle size, typically 30 μm
The stirring speed and time are adjusted so as to have the following size, and thereafter, the stirring is performed so that the sedimentation of the particles is prevented so that the state is substantially maintained by the action of the dispersion stabilizer. The polymerization is performed at a polymerization temperature of 40 ° C. or higher, generally 50 to 90 ° C. After completion of the reaction, the generated toner particles are collected by washing, passing, and dried. In the suspension polymerization method, it is generally preferable to use 300 to 3000 parts by weight of water as a dispersion medium with respect to 100 parts by weight of a monomer.

Examples of the polymerizable monomer applicable to the above-described polymerized toner include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, and p-methylstyrene.
Styrene such as ethylstyrene and derivatives thereof; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, methacrylic acid Methacrylates such as stearyl, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate Acrylates such as, for example, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate;
There are vinyl monomers such as acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide.

These monomers can be used alone or as a mixture.
Among the above-mentioned monomers, it is preferable to use styrene or a styrene derivative alone or as a mixture with other monomers as a polymerizable monomer from the viewpoint of the developing characteristics and durability of the toner.

It is more preferable to add a polymer or a copolymer having a polar group as an additive during the polymerization of the monomer to polymerize the monomer. In the present invention, a polymerizable monomer system to which a polymer, a copolymer or a cyclized rubber having a polar group is added at the time of polymerization is suspended in an aqueous phase in which the polar polymer and a dispersant having an opposite charge are dispersed. It is preferable to conduct turbidity and polymerize. That is, the cationic or anionic polymer, copolymer or cyclized rubber contained in the polymerizable monomer system is undergoing polymerization with a reverse-charged anionic or cationic dispersant dispersed in the aqueous phase. The particles are electrostatically attracted to the surface of the toner particles, and the dispersant covers the surface of the particles to prevent the particles from coalescing and stabilize, and the polar polymer added during polymerization collects on the surface layer of the toner particles. The resulting particles form a kind of shell, and the obtained particles become pseudo capsules. A relatively high molecular weight polar polymer, copolymer or cyclized rubber is used to give the toner particles excellent properties of blocking property and development abrasion resistance. By performing polymerization so as to contribute, it is possible to obtain a toner that satisfies conflicting requirements of fixing property and blocking property. The polar polymer (including the polar copolymer) and the reverse charge dispersant which can be used in the present invention are exemplified below.

(I) Examples of the cationic polymer include a polymer of a nitrogen-containing monomer such as dimethylaminoethyl methacrylate and diethylaminoethyl acrylate and a copolymer of styrene, an unsaturated carboxylic acid ester and the like with the nitrogen-containing monomer. .

(Ii) Examples of the anionic polymer include nitrile monomers such as acrylonitrile, halogen-containing monomers such as vinyl chloride, unsaturated carboxylic acids such as acrylic acid, unsaturated dibasic acids, and unsaturated dibasic acids. There are polymers of anhydrides and nitro monomers.

(Iii) Aerosil # 200,
There are colloidal silicas such as # 300 and # 380 (manufactured by Nippon Aerosil Co., Ltd.).

(Iv) Examples of the cationic dispersant include fine particles of hydrophilic positively chargeable silica such as aluminum oxide and aminoalkyl-modified colloidal silica. A cyclized rubber may be used instead of the polar polymer.

Such a dispersant is based on 100 parts by weight of the polymerizable monomer.
0.2 to 20 parts by weight is preferred. More preferably, it is 0.3 to 15 parts by weight.

On the other hand, as the charge control substance to be added as needed, generally known substances are used. For example, nigrosine,
Azine dyes containing an alkyl group having 2 to 16 carbon atoms, metal complex salts of monoazo dyes, metal complex salts of salicylic acid and dialkylsalicylic acid, and the like are used.

As the polymerization initiator, any suitable polymerization initiator, for example, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'- Azobis (cyclohexane-1-carbonitrile), 2,
2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, other azobisisobutyronitrile (AIBN)
Azo-based or diazo-based polymerization initiators such as benzoyl peroxide, methyl ethyl ketone peroxide, isopropyl peroxycarbonate, cumene hydroperoxide, peroxide polymerization such as 2,4-dichlorylbenzoyl peroxide and lauroyl peroxide Agents. Generally, about 0.5 to 10% of these polymerization initiators by weight of the polymerizable monomer is sufficient.

The fluidity modifier may be mixed (externally added) with the toner particles and used. Colloidal silica as a fluidity modifier,
Examples include fatty acid metal salts and fine powder of Teflon. In addition, fillers such as calcium carbonate and finely powdered silica are used in an amount of 0.
It may be blended in the toner in the range of 5 to 20% by weight.

The polymerized toner obtained in the present invention can be applied to a known dry electrostatic image developing method without any particular limitation. For example, two-component developing methods such as a cascade method, a magnetic brush method, a microtoning method, and a two-component AC bias developing method; a powder cloud method and a fur brush method; Non-Magnetic-Component Developing Method Conveyed to Developing Unit and Provided for Development: The present invention is applicable to an electric field curtain developing method in which toner is carried to a developing unit by an electric field curtain method and provided for development.

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples.

First, an example of an oxidation treatment of a pigment and then an example of a lipophilic treatment are described, and then an example is described.

All parts in the following formulations are parts by weight.

<Oxidation treatment example 1> Copper phthalocyanine blue (CI Pigment Blue 15: 3)
Plasma oxidation treatment: 20 g of copper phthalocyanine blue was added to the reaction vessel of the plasma oxidation treatment apparatus shown in FIG.
The pressure was reduced to rr, and the copper phthalocyanine blue was dried for about 2 hours.

After drying, supply oxygen at 100 ml / min into the container and reduce the degree of vacuum.
Adjusted to 1.2torr. After adjusting the number of rotations of the reaction vessel and the magnetic stirrer so that copper phthalocyanine blue was sufficiently stirred, high-frequency (13.56 MHz, 30 W) oxidation was performed for 40 minutes to obtain a treated pigment.

<Oxidation treatment example 2> Plasma oxidation treatment of quinacridone magenta (CI Pigment Red 122): A treated pigment was obtained by performing the same operation as in the case of copper phthalocyanine blue except that the high-frequency output was 100 W and the treatment time was 15 minutes.

<Oxidation treatment example 3> Oxidation treatment of quinacridone magenta (CI Pigment Red 122) with an oxidizing agent (sodium hypochlorite): 25 g of quinacridone magenta was added to 200 g of an aqueous solution of sodium hypochlorite (effective chlorine concentration 5%), Room temperature (approximately 20
C) for 48 hours. After washing and drying,
The treated pigment was obtained by pulverization. Table 1 shows the physical property values of each treated pigment.

Next, examples of the lipophilic treatment using the oxidized pigment obtained in the preceding section are shown below.

<Example 1 of lipophilic treatment> 20 g of oxidized β-copper phthalocyanine blue (oxidation example 1 of the preceding paragraph) and 20 g of tetramethyltetrahydrocyclotetrasiloxane were placed in separate containers and left at 50 ° C for 6 hours in the same desiccator. did. Thereafter, the pigment container was left in a vacuum dryer at 50 ° C. for 2 hours under reduced pressure and dried to obtain 20.4 g of a treated pigment.

<Example 2 of lipophilic treatment> Oxidized quinacridone magenta (Example 2 of oxidative treatment)
20 g and 10 g of hexamethylcyclotrisiloxane were placed in separate containers and left in a vacuum dryer at 30 ° C. and 300 mmHg for 4 hours. Thereafter, the atmosphere in the dryer was replaced with an air atmosphere, and further left at 30 ° C. under vacuum for 2 hours and dried to obtain 20.6 g of a treated pigment.

<Example 3 of lipophilic treatment> Oxidized quinacridone magenta (Example 3 of oxidative treatment)
20g and formula Were placed in separate containers and left at 80 ° C. for 3 hours in the same desiccator.
Thereafter, the pigment container was left in a vacuum dryer under reduced pressure at 50 ° C. for 2 hours to obtain 20.8 g of a dried treated pigment.

<Example 4 of lipophilic treatment> 5 g of γ2-aminoethyl) aminopropyltrimethoxysilane was added to 200 g of water, and 20 g of quinacridone magenta (oxidation treatment example 3) was added under vigorous stirring. After vigorous stirring for minutes, the mixture was excessively dried to obtain 20.4 g of a treated pigment.

Examples of the polymerized toner using these lipophilic pigments are described below.

<Example 1> 0.25 g of γ-aminopropyltrimethoxysilane was added to 1200 ml of ion-exchanged water, and 5 g of Aerosil 200 (manufactured by Nippon Aerosil) was further added.
The mixture was dispersed at 10,000 rpm for 15 minutes using a mold (manufactured by Tokushu Kika Kogyo). Further, 1 / 10N-HCl was added to adjust the pH in the system to 6.

The components of the above formulation were heated to 70 ° C. in a container, and dissolved and dispersed using an ultrasonic disperser (10 KHz, 200 W) to obtain a monomer mixture. Further, while maintaining the temperature at 70 ° C, the initiator V-601 was used.
10 parts (manufactured by Wako Pure Chemical Industries) were added and dissolved to prepare a monomer composition.

The above monomer composition was put into a 2 liter flask containing the dispersion medium obtained above, and the mixture was stirred under a nitrogen atmosphere at 70 ° C. for 60 minutes at 7500 rpm using a TK type homomixer. The product was granulated. Then, at 70 ° C, 20 while stirring with paddle stirring blades
Polymerized in time. After the completion of the polymerization reaction, the reaction product was cooled, NaOH was added, the dispersant was dissolved, and the mixture was washed, washed with water and dried to obtain a polymerized toner.

The particle diameter of the obtained toner was measured with a Coulter counter (aperture diameter: 100 μm), and the volume average diameter was 11.
It had a sharp particle size distribution of 2 μm. The toner had a triboelectric charge of −20 μc / g by the blow-off method with respect to iron powder (200/300 mesh). 0.8 parts of hydrophobic silica (Taranox 500, Talco) was mixed with 100 parts of the obtained toner. 92 parts of an acrylic-coated ferrite carrier was mixed with 8 parts of the toner to prepare a developer.

Using the developer obtained in this way, Canon
When 20,000 images were continuously output on the CLC-1, the copy was clear and free of fogging, exhibited a cyan color with excellent spectral reflection characteristics, and was stable at an image density of 1.4 or more.

 The image on the OHP film was excellent in transparency.

Example 2 A polymerized toner was obtained in the same manner as in Example 1, except that the formulation used in Example 1 was changed as follows.

The particle diameter of the obtained toner was measured with a Coulter counter (aperture diameter: 100 μm), and the volume average diameter was 11.
It had a sharp particle size distribution at 0 μm. The triboelectric charge of the toner with respect to iron powder (200/300 mesh) by a blow-off method was -21.2 μc / g. A developer was prepared in the same manner as in Example 1, and continuous printing of 20,000 sheets was performed using Canon CLC-1.

The obtained image was clear, had no fog, exhibited a good magenta color with a good spectral reflection characteristic, and was stable at an image density of 1.4 or more.

 Further, the image on the OHP film was excellent in transparency.

<Example 3> 5 g of Aerosil 200 (manufactured by Nippon Aerosil) was added to 1200 ml of ion-exchanged water, heated to 70 ° C, and dispersed using a TK homomixer M type (manufactured by Tokushu Kika Kogyo) at 10,000 rpm for 15 minutes. Was.

The components of the above formulation were heated to 70 ° C. in a container, and dissolved and dispersed using an ultrasonic disperser (10 KHz, 200 W) to obtain a monomer mixture. Further, while maintaining the temperature at 70 ° C, the initiator V-601 was used.
10 parts (Wako Pure Chemical Industries, Ltd.) were added and dissolved to prepare a monomer composition.

The above monomer composition was put into a 2 liter flask containing the dispersion medium obtained above, and stirred at 7,500 rpm for 60 minutes at 70 ° C. using a TK type homomixer under a nitrogen atmosphere to obtain a monomer composition. The product was granulated. Then, while stirring with a paddle stirring blade, 70 ° C, 2
It polymerized in 0 hours. After completion of the polymerization reaction, the reaction product was cooled, NaOH was added, the dispersant was dissolved, and the mixture was washed with water, washed and dried to obtain a polymerized toner.

The particle diameter of the obtained toner was measured with a Coulter counter (aperture diameter: 100 μm), and the volume average diameter was 11.
It had a sharp particle size distribution of 6 μm. The triboelectric charge of this toner by iron on iron powder (200/300 mesh) by a blow-off method was +13 μc / g. Amita silicone oil treated Shitaka 0.5 parts per 100 parts of the obtained toner
Were mixed with 95 parts of a styrene-acrylic resin-coated ferrite carrier with 5 parts of the toner to prepare a developer.

Using the developer obtained in this way, Canon
After outputting 20,000 images continuously with the NP-3525,
The copy was clear, had no fog, exhibited a good magenta color with excellent spectral reflection characteristics, and was stable at an image density of 1.4 or more.

Example 4 A polymerized toner was obtained in the same manner as in Example 1 except that the colorant was changed to 10 parts of the magenta pigment shown in Example 4 of the lipophilic treatment.

The particle diameter of the obtained toner was measured with a Coulter counter (aperture diameter: 100 μm), and the volume average diameter was 11.
It had a sharp particle size distribution of 2 μm. Further, the triboelectric charge of this toner by iron on iron powder (200/300 mesh) by a blow-off method was −18 μc / g. 0.8 parts of hydrophobic silica (Taranox 500, Talco) was mixed with 100 parts of the obtained toner. 92 parts of an acrylic-coated ferrite carrier was mixed with 8 parts of the toner to prepare a developer.

Using the developer obtained in this way, Canon
When 20,000 continuous images were output on the CLC-1,
The copy was clear, had no fog, exhibited a good magenta color with excellent spectral reflection characteristics, and was stable at an image density of 1.4 or more.

Further, the image on the OHP film was excellent in transparency.

Comparative Example 1 A polymerized toner was obtained in the same manner as in Example 1, except that 8 parts of untreated copper phthalocyanine pigment was added as a colorant. The particle size of the obtained toner was the same as that of Example 1, but the triboelectric charge amount by a blow-off method for iron powder (200/300 mesh) was −24 μc / g. The presence of fine particles having a particle diameter of 2 μm or less was confirmed.

When a developer was prepared and an image was formed in the same manner as in Example 1, the image density was low at 1.4 or less, and the transparency of the image on the OHP film was poor.

<Comparative Example 2> In Example 1 of lipophilic treatment, lipophilic treatment was performed using untreated copper phthalocyanine blue as a coloring agent. Using 8 parts of this coloring agent, a polymerized toner was obtained in the same manner as in Example 1. The resulting toner has a broad particle size distribution,
Pigments were unevenly distributed among the particles, and were not suitable for use as a toner as it was.

<Comparative Example 3> In Example 3 of lipophilic treatment, lipophilic treatment was performed using untreated quinacridone magenta as a coloring agent. Using 10 parts of this colorant, a polymerized toner was obtained in the same manner as in Example 3. The obtained toner had a broad particle size distribution, and uneven distribution of the pigment among the particles was observed, and as such, the toner was not suitable for use as a toner.

[Effects of the Invention] As described above, according to the polymerized toner of the present invention and the method for producing the same, the use of the colorant treated with the silicon-containing compound provides a clear color tone, high coloring power, and transparency. And an excellent toner can be obtained.

[Brief description of the drawings]

 FIG. 1 is a schematic view of an apparatus for performing a plasma process.

 ──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Tatsuya Nakamura 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (56) References JP-A-63-158566 (JP, A) JP-A-62 -280755 (JP, A)

Claims (4)

(57) [Claims] 1. A polymerized color toner obtained by suspension polymerization of a polymer monomer system containing at least a colorant in an aqueous phase, wherein the colorant is obtained by treating an organic pigment having an OH group with a silicon-containing compound. A polymerized color toner, comprising: 2. An organic pigment having an OH group, wherein OH is added to the organic pigment.
2. The polymerized color toner according to claim 1, which has been subjected to a treatment for introducing a group. 3. A method for producing a polymerized color toner, wherein a polymerized monomer system containing at least a colorant is subjected to suspension polymerization in an aqueous phase to produce a polymerized color toner. And producing the polymerized color toner as the colorant. 4. The polymerized color toner according to claim 3, wherein the organic pigment having an OH group is subjected to a treatment for introducing an OH group into the organic pigment before the treatment with the silicon-containing compound. Production method.