JPH08179554A - Production of polymerized toner - Google Patents

Abstract

PURPOSE: To produce a polymerized toner increasing the quantity of triboelectric charges on the toner in a short time in the case of contact with a carrier, etc., and giving toner particles having a uniform distribution of the quantity of triboelectric charges. CONSTITUTION: When a polymerized toner is produced through a process for preparing a suspension contg. polymerizable liq. droplets by adding an oily phase prepd. by dispersing at least a polymerizable monomer, a colorant and a polymn. initiator to an aq. phase, a process for polymerizing the droplets by heating and a process for removing the aq. phase, a hydrophilic liq. contg. an electric charge controlling agent is added after the process for preparing the suspension and before the process for removing the aq. phase.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a polymerized toner produced by suspension polymerization.

[0002]

2. Description of the Related Art Conventionally, toners used in electrophotography and the like are prepared by melt-kneading a binder resin, a colorant, a charge control agent and the like,
It was manufactured by a so-called crushing method of crushing and classifying. The toner produced by this pulverization method had an average particle size of about 10 to 20 μm. In recent years, in electronic copying machines, colorization, high definition, and high image quality have been aimed at, and as a result, toner with a small particle size having an average particle size of 10 μm or less has been earnestly desired. However, it has been difficult to produce a small particle diameter toner with a high yield by the pulverization method. In order to solve such a problem of the pulverization method, a toner is produced from a polymerizable monomer by a suspension polymerization method. When a toner is obtained by a suspension polymerization method, a monomer composition (oil phase) containing at least a polymerizable monomer and a colorant, mainly carbon black and a charge control agent, is mixed with a water-miscible medium (aqueous phase). In (1), a suitable agitator is used to granulate the toner to a particle size (step of obtaining a suspension having polymerizable droplet groups), and a polymerization initiator added in advance or newly added polymerization is added. Radicals generated when the initiator is decomposed by heat polymerize the polymerizable monomer to form a polymer (a step of polymerizing the polymerizable droplet group) to generate a polymerized toner. Since the polymerized toner obtained by this suspension polymerization method has a spherical shape, the polymerized toner has characteristics such as excellent fluidity. However, this suspension polymerization method also has a problem. That is, in the conventional suspension polymerization method, the charge control agent is mixed with the polymerizable monomer in the oil phase and the granulation step and the polymerization step are performed, so that the surface of the polymer particles is covered with the resin component. Therefore, the charge control agent was not exposed on the surface of the particles, so that polymer particles having a problem of triboelectrification were produced. That is, when such polymer particles are practically stirred and mixed with the carrier, the triboelectric charge amount of the polymerized toner does not become large in a short time, or the toner particles having a non-uniform distribution of the triboelectric charge amount of individual toner particles are generated. It is a cause of generation of toner particles having a polarity opposite to the desired polarity. Then, the toner particles are scattered inside the copying machine to cause a background fog in a margin portion of the transfer paper, or to contaminate the inside of the copying machine (hereinafter referred to as toner scattering).

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a polymerized toner in which toner particles having a rapid rise in triboelectric charge amount and a uniform triboelectric charge amount distribution can be obtained upon friction with a carrier or the like. To do.

[0004]

DISCLOSURE OF THE INVENTION The inventors of the present invention have made extensive studies as a result of solving the above-mentioned problems of the prior art. That is, in the method according to claim 1 of the present invention, an oil phase obtained by dispersing at least a polymerizable monomer, a colorant and a polymerization initiator in an aqueous phase is added to form a polymerizable droplet group. A method for producing a polymerized toner, which comprises a step of obtaining a suspension having the same, a step of polymerizing the polymerizable droplet group by heating, and a step of removing an aqueous phase, wherein the step of obtaining the suspension A method for producing a polymerized toner, characterized in that a hydrophilic liquid having a charge control agent is added during a period from the latter step to the step before the step of removing the aqueous phase. Further, in the method according to claim 2 of the present invention, an oil phase obtained by dispersing at least a polymerizable monomer, a colorant and a polymerization initiator in an aqueous phase is added to form a polymerizable droplet group. A method for producing a polymerized toner, which comprises a step of obtaining a suspension having the same, a step of polymerizing the polymerizable droplet group by heating, and a step of removing an aqueous phase, wherein the step of obtaining the suspension In the method for producing a polymerized toner, a hydrophilic liquid having a charge control agent is added before and after the step of polymerizing the polymerizable droplet groups by heating afterward. Further, in the method according to claim 3 of the present invention, an oil phase obtained by dispersing at least a polymerizable monomer, a colorant and a polymerization initiator in an aqueous phase is added to form a polymerizable droplet group. Obtaining a suspension having
A method for producing a polymerized toner, comprising a step of heating to polymerize the polymerizable droplet group and a step of removing an aqueous phase, wherein charge control is performed during the step of heating to polymerize the polymerizable droplet group. A method for producing a polymerized toner, which comprises adding a hydrophilic liquid containing an agent. Further, in the method according to claim 4 of the present invention, an oil phase obtained by dispersing at least a polymerizable monomer, a colorant and a polymerization initiator in an aqueous phase is added to form a polymerizable droplet group. A method for producing a polymerized toner, comprising: a step of obtaining a suspension having the above; a step of heating to polymerize the polymerizable droplet group; and a step of removing an aqueous phase. In the method for producing a polymerized toner, a hydrophilic liquid having a charge control agent is added after the step of polymerizing the group and before the step of removing the aqueous phase. Further, the method according to claim 5 of the present invention, an aqueous phase, and an oil phase obtained by dispersing at least a polymerizable monomer, a colorant and a polymerization initiator, each is held in an independent tank, And a step of continuously supplying both to the granulator at a controlled ratio through independent paths to obtain a suspension having polymerizable droplet groups of a desired size, and A method for producing a polymerized toner, which comprises a step of taking out a suspension and introducing it into a polymerization tank, a step of polymerizing the polymerizable droplet group by heating in the polymerization tank, and a step of removing an aqueous phase, The method for producing a polymerized toner is characterized in that a hydrophilic liquid having a charge control agent is added between the step of taking out the suspension and introducing it into the polymerization tank and the step before the step of removing the aqueous phase.

The present invention will be described in detail below. The aqueous phase constituting the present invention is a hydrophilic liquid, and contains a hydrophilic medium, a suspension stabilizer and other additives. Examples of the hydrophilic medium include water, ion-exchanged water, distilled water and the like. Further, the suspension stabilizer, a water-soluble polymer having a hydrophilic group and a hydrophobic group in the molecule, for example, polyvinyl alcohol, casein, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, cellulose derivatives such as ethyl cellulose, starch And its derivatives, poly (meth) acrylic acid and salts thereof, and solid fine powders. Examples of the solid fine powder include tricalcium phosphate, calcium carbonate, fine metal powder such as copper and iron, silica, alumina and the like. Of these suspension stabilizers, solid fine powder is insoluble in water and is relatively stable when heated, and therefore, tribasic calcium phosphate and calcium carbonate are particularly preferable. It is preferable because a polymerized toner having a uniform particle size can be obtained regardless of the types, amounts and properties of the monomers, colorants and magnetic powders. These suspension stabilizers may be used alone or in combination of two or more. The amount of the suspension stabilizer added to the aqueous phase is preferably 0.5 to 20 parts by weight with respect to 100 parts by weight of the hydrophilic medium in the aqueous phase. If it is less than 0.5 parts by weight, it is difficult to obtain a polymerized toner having a small particle size of 10 μm or less. On the other hand, if it is more than 20 parts by weight, the viscosity of the aqueous phase increases and it is difficult to obtain a polymerized toner having a small particle size, and it is difficult to obtain a polymerized toner having a uniform particle size. Such a suspension stabilizer has a function of adhering to the surface of a monomer composition composed of a polymerizable monomer in an oil phase, a colorant, etc., and making the monomer composition into uniform particles. At the same time, it has the function of attaching the charge control agent to the surface of the particles made of the monomer composition. A suspension stabilizer composed of tricalcium phosphate and calcium carbonate is used to remove polymerized particles from the surface after polymerized particles are obtained by washing with acid after obtaining polymerized particles in an aqueous phase. It is preferable because it has good properties. Further, in order to stabilize the monomer composition suspended in the aqueous phase and obtain a polymerized toner having uniform particles, a suspending aid is mentioned as another additive, and as the suspending aid, dodecyl sulfone is used. It is preferable to add a surfactant such as sodium acid salt or sodium dodecylbenzenesulfonate to the aqueous phase. The amount of the suspension aid added is preferably 0.005 to 0.05 parts by weight with respect to 100 parts by weight of the aqueous phase.

On the other hand, the oil phase constituting the present invention comprises at least a polymerizable monomer, a colorant and a polymerization initiator dispersed therein. As the polymerizable monomer used in the present invention, for example, the following polymerizable compounds can be used. That is, for example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-
Methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn Styrene and its derivatives such as hexyl styrene, pn-octyl styrene, pn-nonyl styrene and pn-decyl styrene; ethylenically unsaturated monoolefins such as ethylene, propylene, butylene, isobutylene; Vinyl, vinylidene chloride, vinyl bromide, vinyl fluoride,
Vinyl halides such as; vinyl acetate, vinyl propionate, vinyl benzoate, and other organic acid vinyl esters; methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, n methacrylate -Octyl, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate,
Methacrylic acid and its derivatives such as acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, acrylic Acid stearates, 2-chloroethyl acrylate, phenyl acrylate, and other acrylic acids and their derivatives; Vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, and other vinyl ethers; Vinyl methyl ketone, vinyl hexyl ketone, vinyl isopropenyl ketone , Ketones; N-vinylpyrrole, N-vinylcarbazole, N
-N-vinyl compounds such as vinylindole and N-vinylpyrrolidone; vinylnaphthalenes; acrylonitrile,
Examples thereof include polymerizable monomers such as methacrylonitrile and acrylamide, which may be used alone or as a mixture depending on the purpose. Among the above-mentioned polymerizable monomers, it is preferable to use styrene or a styrene derivative alone or in combination with methacrylic acid and its derivative or acrylic acid and its derivative in order to improve the developing characteristics and durability of the polymerized toner.

The colorant used in the present invention is a card.
Bon black is suitable. That is, the carbon black used in the present invention has a number average particle size,
The oil absorption amount, pH and the like can be used without limitation, and the following are commercially available products. For example, Regal 400, 660, 330, 30 manufactured by Cabot Corporation of the United States
0, SRF-S, STERRING S
O, V, NS, R; Raven H20, MT-P, 410, 42 manufactured by Columbia Carbon Japan Co., Ltd.
0, 430, 450, 500, 760, 780, 100
0, 1035, 1060, 1080; Mitsubishi Kasei Co. # 1
0B, # 5B, # 40, # 2400B, MA-100;
Etc. These carbon blacks may be used alone or in combination of two or more in various compositions. As the colorant other than carbon black, a colorant that is dispersible in the monomer composition and exhibits a clear color and excellent stability over time when used as a toner is used. Examples of such colorants include phthalocyanine pigments, rhodamine lake pigments, azo lake pigments, iron oxides,
Examples thereof include titanium oxide, alumina, barium sulfate and the like.
The amount of the colorant added is 1 to 40 parts by weight, preferably 3 to 20 parts by weight, based on 100 parts by weight of the polymerizable monomer.

The polymerization initiator used in the present invention is preferably soluble in the polymerizable monomer. Examples of such a polymerization initiator include 2,2′-azobisvaleronitrile, 2,2′-azobisisobutyronitrile,
2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, other azo or diazo polymerization initiators; benzoyl peroxide , Methyl ethyl ketone peroxide, isopropyl peroxy carbonate, other peroxide-based polymerization initiators, and the like. However, a benzoyl peroxide-based polymerization initiator or the like may decompose and generate a carboxylic acid such as benzoic acid as a by-product, which may adversely affect the storage stability of the toner, and also has a drawback that an aromatic odor is generated. Therefore, it is preferable to use an azo polymerization initiator. In the present invention,
For the purpose of controlling the molecular weight and the molecular weight distribution, or for the purpose of controlling the reaction time, it is preferable to use two or more of the above polymerization initiators in combination in various compositions. Further, if necessary, a water-soluble initiator such as ammonium persulfate or potassium persulfate may be used in combination. The amount of the polymerization initiator used is usually 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the polymerizable monomer. When the amount of the polymerization initiator is less than 0.1 part by weight, the polymerization time may be long and the molecular weight of the polymerized toner may be too high. On the other hand, if the amount of the polymerization initiator exceeds 20 parts by weight, the molecular weight of the polymerized toner may be too low, which is not preferable. Furthermore, in the oil phase of the present invention, in order to improve blocking resistance and durability in the toner,
There is no problem even if a cross-linking agent for the polymer of the polymerizable monomer is added. As such a cross-linking agent, a cross-linking agent such as divinylbenzene can be added to the monomer composition.

When obtaining a magnetic toner, a magnetic substance is dispersed in an oil phase to obtain a polymerized toner. The magnetic substance is a substance that is strongly magnetized in that direction by a magnetic field, and is preferably black, can be well dispersed in the polymerizable monomer, is chemically stable, and is preferably 1 μm or less. Such magnetic materials include metals such as cobalt, iron and nickel; alloys of metals such as aluminum, cobalt, copper, iron, magnesium, nickel, and mixtures thereof; nitrides such as vanadium nitride; tengusten carbide. Carbides such as; ferrites; mixtures thereof, and the like.

To carry out the method according to claims 1 to 4 of the present invention using the above-mentioned water phase and oil phase, the following steps are carried out. That is, in a water phase put in a container such as a separable flask, an oil phase is added and stirred with a stirrer such as a homomixer or a homogenizer to disperse the oil phase, and a suspension having polymerizable droplet groups. To get Then, the suspension is heated to polymerize the polymerizable droplet group to obtain polymer particles, and then the polymer particles are cooled, filtered while removing the aqueous phase, and dried to obtain a polymerized toner. It is a thing. In this case, in the present invention, the hydrophilic liquid having the charge control agent is added after the step of obtaining the suspension having the polymerizable droplet group and before the step of removing the aqueous phase. It is characterized by. The removal of the aqueous phase in the present invention means that the aqueous phase is discharged from the container having the aqueous phase and the polymer particles, the polymer particles are taken out from the aqueous phase, and the aqueous phase is relatively separated from the polymer particles. Is meant to be removed. If the hydrophilic liquid having the charge control agent is added before obtaining the suspension having the polymerizable droplet group, the polymerizable droplet group cannot be obtained and the aqueous phase and the oil phase are separated into two layers in the container. On the other hand, even if the hydrophilic liquid containing the charge control agent is added after removing the aqueous phase, the charge control agent does not uniformly adhere to the polymer particles. Causes a problem. The timing of adding the hydrophilic liquid having the charge control agent is from after the step of obtaining the suspension having the polymerizable droplet groups to before the step of heating to polymerize the polymerizable droplet groups, or Examples include a period during heating to polymerize the polymerizable droplet group, and a period before the step of removing the aqueous phase after the polymerizable droplet group is polymerized to complete the heating.
The hydrophilic liquid having a charge control agent is a hydrophilic medium such as water, ion-exchanged water or distilled water, or an organic solvent to which the charge control agent is added. Examples of the charge control agent include a metal complex of an organic compound having a carboxyl group, a sulfonate ester or a nitrogen-containing group, a nigrosine dye, a sulfonic acid or its salt in the main chain or a side chain, a quaternary ammonium salt, and the like. Examples thereof include polymer compounds having a polar functional group. Among these, a metal complex of an organic compound having a carboxyl group, a sulfonic acid ester, or a nitrogen-containing group is preferable because it is well fixed on the surface of the toner particles. These charge control agents may be used alone or in combination of two or more. The charge control agent is preferably added in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the polymerizable monomer, taking into consideration the triboelectric chargeability of the polymerized toner, economy, and the fixability of the polymerized toner, and particularly preferably 0. 5 to 5 parts by weight is preferable.
If the amount is less than 0.1 parts by weight, the triboelectric charge amount is small and it is difficult to obtain good developing characteristics, and the charge amount distribution of the entire polymerized toner tends to be non-uniform. However, it is uneconomical because the charge control agent which is more expensive than necessary is consumed.

Further, the method according to claim 5 of the present invention is carried out as follows. That is, as shown in FIG. 1, the water phase tank 1 containing the water phase and the oil phase tank 2 containing the oil phase are fed to the granulator 5 at a constant ratio via the metering pumps 4 and 4, respectively. It is introduced at the same time, and a shearing force is applied thereto to discharge it as a suspension having a polymerizable droplet group, which is introduced into a polymerization tank 3 equipped with a condenser 6, and which is provided around the polymerization tank 3 for heating. After the required heating is performed by the jacket 7 to cause a polymerization reaction to complete the polymerization to obtain polymer particles, the polymer particles are cooled, filtered while removing the aqueous phase, and dried to obtain a polymerized toner. I will get it. Then, from the step of introducing the suspension having the polymerizable droplets obtained by the granulator 5 into the polymerization tank 3, a hydrophilic liquid having a charge control agent is added while the aqueous phase is removed in the polymerization tank 3. It is a thing. Specifically, while the suspension having the polymerizable droplet group in the polymerization tank 3 is obtained and then heated to polymerize the polymerizable droplet group, or while the suspension is heated, the polymerizable droplet group is polymerized. The hydrophilic liquid having the charge control agent is added during the period of time, or until the polymerizable liquid droplet group is polymerized and heating is completed and the aqueous phase is removed. When the polymerized toner is obtained by such a method as described in claim 5, it is possible to provide the polymerized toner with good triboelectric charging characteristics, and to obtain polymer particles having a small particle size and a uniform particle size distribution. it can. In addition,
An example of the granulator used in the present invention is as shown in FIG. 2, and the granulator has an oil phase supply port 14 and an aqueous phase supply port 13, and both liquids enter the shear region 11. A stirring blade 10 is fixed to the shear region 11 by a rotating shaft 8. Stirring blade 1
0 rotates by the rotating shaft 8 and generates a suspension in the shear region 11 by a shearing force. A discharge control gap 12 is provided at the edge of the shear region 11, and the suspension that has passed through this gap is discharged from the suspension discharge port 9 in the upper portion and guided to the polymerization tank 3. Has become.

[0012]

EXAMPLES The present invention will be specifically described below based on examples. Example 1 <Preparation of oil phase> 48 g of styrene, 12 g of n-butyl acrylate, carbon black (trade name: # manufactured by Mitsubishi Kasei Co., Ltd.)
40) 6 g, lauric acid peroxide (Kyaku Yuri Co., Ltd. product name: LPO) 0.6 g, and N, N'-azobisisovaleronitrile 3 g were put in a container and then sufficiently homogenized using an ultrasonic cleaner. An oil phase was prepared by dispersion. <Preparation of water phase> 150 g of water, tricalcium phosphate (manufactured by Taihei Chemical Industry Co., Ltd., trade name: TCP-10 · U) 150
g, sodium dodecylbenzene sulfonate 0.06g
After being placed in a container, the mixture was stirred using an ultrasonic cleaner to prepare an aqueous phase. <Preparation of Hydrophilic Liquid Having Charge Control Agent> 150 g of water and a charge control agent composed of a metal complex of an organic compound having a nitrogen-containing group (trade name: T-4-48 manufactured by Hodogaya Chemical Co., Ltd.)
1.2 g was placed in a container and the charge control agent was dispersed by an ultrasonic cleaner to obtain a hydrophilic liquid having the charge control agent. <Preparation of Polymerized Toner> The above oil phase and water phase were added to a separable flask having a volume of 1 L, and the mixture was stirred at room temperature for 1 minute at 10000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to form polymerizable droplets. A suspension with groups was obtained. Next, the suspension is heated at 80 ° C. for 5 hours to carry out polymerization, and immediately before the completion of the polymerization, the hydrophilicity of the charge control agent is adjusted with stirring so that particles do not precipitate. Liquid was dripped. Then, after the polymerization is completed, the aqueous phase is removed by cooling, the polymer particles are acid-treated with dilute sulfuric acid, filtered and dried to obtain a polymerized toner according to the present invention.

Example 2 <Preparation of oil phase> 48 g of styrene, 12 g of n-butyl acrylate, carbon black (trade name: # manufactured by Mitsubishi Kasei Co., Ltd.)
40) 6 g, lauric acid peroxide (Kayaku Nouri Co., Ltd. trade name: LPO) 0.6 g, N, N′-azobisisovaleronitrile 3 g, magnetic powder (Toda Kogyo Co., Ltd. trade name: MAT-305) 6 g , Divinylbenzene 0.18
After putting g in a container, it was dispersed sufficiently uniformly using an ultrasonic cleaner to prepare an oil phase. <Preparation of water phase> 150 g of water, tricalcium phosphate (manufactured by Taihei Chemical Industry Co., Ltd., trade name: TCP-10 · U) 150
g, polyvinyl alcohol 1.5 g, and sodium dodecylbenzenesulfonate 0.06 g were placed in a container, and then stirred using an ultrasonic cleaner to prepare an aqueous phase. <Preparation of Hydrophilic Liquid Having Charge Control Agent> 150 g of water and a charge control agent composed of a metal complex of an organic compound having a nitrogen-containing group (trade name: T-4-48 manufactured by Hodogaya Chemical Co., Ltd.)
1.2 g was placed in a container and the charge control agent was dispersed by an ultrasonic cleaner to obtain a hydrophilic liquid having the charge control agent. <Preparation of Polymerized Toner> A polymerized toner according to the present invention was obtained in the same manner as in Example 1 except that the hydrophilic liquid containing the oil phase, the aqueous phase and the charge control agent was replaced.

Example 3 <Preparation of oil phase> 42 g of styrene, 18 g of n-butyl acrylate, carbon black (trade name: # manufactured by Mitsubishi Kasei Co., Ltd.)
40) 6 g, lauric acid peroxide (Kyaku Yuri Co., Ltd. product name: LPO) 0.6 g, and N, N'-azobisisovaleronitrile 3 g were put in a container and then sufficiently homogenized using an ultrasonic cleaner. An oil phase was prepared by dispersion. <Preparation of water phase> 150 g of water, tricalcium phosphate (manufactured by Taihei Chemical Industry Co., Ltd., trade name: TCP-10 · U) 150
g, sodium dodecylbenzene sulfonate 0.06g
After being placed in a container, the mixture was stirred using an ultrasonic cleaner to prepare an aqueous phase. <Preparation of Hydrophilic Liquid Having Charge Control Agent> 150 g of water and a charge control agent comprising a metal complex of an organic compound having a nitrogen-containing group (trade name: Bontron S manufactured by Orient Chemical Industry Co., Ltd.
-44) 1.2 g was placed in a container and the charge control agent was dispersed for 30 seconds by an ultrasonic cleaner to obtain a hydrophilic liquid having the charge control agent. <Preparation of Polymerized Toner> The above oil phase and water phase were added to a separable flask having a volume of 1 L, and the mixture was stirred at room temperature for 1 minute at 10000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to form polymerizable droplets. A suspension with groups was obtained. Then, the suspension is heated at 80 ° C. for 5 hours to carry out polymerization, and after the completion of the polymerization, a hydrophilic property having a charge control agent prepared with stirring so that particles do not precipitate. The liquid was dripped. Then, after the polymerization is completed, the aqueous phase is removed by cooling, the polymer particles are acid-treated with dilute sulfuric acid, filtered and dried to obtain a polymerized toner according to the present invention.

Example 4 <Preparation of oil phase> 42 g of styrene, 18 g of n-butyl acrylate, carbon black (trade name: # manufactured by Mitsubishi Kasei Co., Ltd.)
40) 6 g, lauric acid peroxide (Kyaku Yuri Co., Ltd. product name: LPO) 0.6 g, and N, N'-azobisisovaleronitrile 3 g were put in a container and then sufficiently homogenized using an ultrasonic cleaner. An oil phase was prepared by dispersion. <Preparation of water phase> 150 g of water, tricalcium phosphate (manufactured by Taihei Chemical Industry Co., Ltd., trade name: TCP-10 · U) 150
g, sodium dodecylbenzene sulfonate 0.06g
After being placed in a container, the mixture was stirred using an ultrasonic cleaner to prepare an aqueous phase. <Preparation of Hydrophilic Liquid Having Charge Control Agent> 150 g of water and 1.2 g of a charge control agent consisting of a nigrosine dye (trade name: Nigrosine EX manufactured by Orient Chemical Industry Co., Ltd.) were placed in a container and the charge was controlled by an ultrasonic cleaner. The agent was dispersed to obtain a hydrophilic liquid having a charge control agent. <Preparation of Polymerized Toner> A polymerized toner according to the present invention was obtained in the same manner as in Example 1 except that the hydrophilic liquid containing the oil phase, the aqueous phase and the charge control agent was replaced.

Example 5 <Preparation of Oil Phase> 1600 g of styrene, 400 g of n-butyl acrylate, 200 g of carbon black (trade name: # 40 manufactured by Mitsubishi Kasei Co., Ltd.), and 100 g of 2,2'-azobisisovaleronitrile were placed in a container. After that, the oil phase was sufficiently dispersed using an ultrasonic cleaner to prepare an oil phase. <Preparation of Aqueous Phase> 300 g of tricalcium phosphate (trade name: TCP-10 · U manufactured by Taihei Chemical Industry Co., Ltd.) and 2 g of sodium dodecylbenzenesulfonate are dissolved in a small amount of water, and then added to 10000 g of water in a container. Then, the mixture was stirred to prepare an aqueous phase. <Preparation of hydrophilic liquid having charge control agent> 1000 g of water
And a charge control agent composed of a metal complex of an organic compound having a nitrogen-containing group (Hodogaya Chemical Co., Ltd. product name: T-4-48)
40 g was placed in a container and stirred to obtain a hydrophilic liquid having a charge control agent. <Preparation of Polymerized Toner> The above oil phase and water phase were placed in the oil phase tank 2 and the water phase tank 1 of the apparatus as shown in FIG. 1, respectively.
Then, the aqueous phase was supplied to the granulator 5 at a flow rate of 300 ml / min and the oil phase was supplied at 100 ml / min to the granulator 5 for 10000 rpm.
The aqueous phase and the oil phase were stirred at the number of revolutions of 1 to obtain a suspension having polymerizable droplet groups, and the suspension was introduced into the polymerization tank 3. Then, the polymerization tank 3 was heated by the heating jacket 7 at 60 ° C. for 10 hours to polymerize the polymerizable droplet group. Then, before the completion of the polymerization, the hydrophilic liquid containing the charge control agent is added little by little over about 30 minutes, and then at 80 ° C.
It was heated for 2 hours to complete the polymerization. Then, after the polymerization is completed, the aqueous phase is removed by cooling, the polymer particles are acid-treated with dilute sulfuric acid, filtered and dried to obtain a polymerized toner according to the present invention.

Comparative Example 1 A charge control agent comprising a metal complex of an organic compound having a nitrogen-containing group in the oil phase (trade name: T-4-4 manufactured by Hodogaya Chemical Co., Ltd.)
A polymerized toner for comparison was obtained in the same manner as in Example 1 except that 1.5 g of 8) was added and the hydrophilic liquid having a charge control agent was not added during the preparation of the polymerized toner.

Comparative Example 2 1.2 g of a charge control agent (trade name: Bontron S-44 manufactured by Orient Chemical Industry Co., Ltd.) consisting of a metal complex of an organic compound having a nitrogen-containing group in the oil phase was added, and a hydrophilic property having a charge control agent was added. Polymerization was carried out in the same manner as in Example 1 except that the liquid was not added during the preparation of the polymerized toner, but polymer particles could not be formed.

Comparative Example 3 Example 1 was repeated except that the aqueous phase was changed to the following and the hydrophilic liquid containing the charge control agent was not added during the preparation of the polymerized toner.
Polymerization was carried out in the same manner as above, but polymer particles could not be formed. <Preparation of water phase> 150 g of water, tricalcium phosphate (manufactured by Taihei Chemical Industry Co., Ltd., trade name: TCP-10 · U) 150
g, sodium dodecylbenzene sulfonate 0.06
g, 1.2 g of a charge control agent (trade name: Bontron S-44, manufactured by Orient Chemical Industry Co., Ltd.) consisting of a metal complex of an organic compound having a nitrogen-containing group was placed in a container, and then stirred using an ultrasonic cleaner. Further, the mixture was pulverized with a ball mill at 100 rpm for 1 hour to prepare an aqueous phase.

Comparative Example 4 Example 4 was repeated except that the aqueous phase was changed to the following one and the hydrophilic liquid having the charge control agent was not added during the preparation of the polymerized toner.
Polymerization was carried out in the same manner as above, but polymer particles could not be formed. <Preparation of water phase> 150 g of water, tricalcium phosphate (manufactured by Taihei Chemical Industry Co., Ltd., trade name: TCP-10 · U) 150
g, sodium dodecylbenzene sulfonate 0.06
g, 1.2 g of a charge control agent (trade name: Nigrosine EX, manufactured by Orient Chemical Industry Co., Ltd.) consisting of a nigrosine dye, was placed in a container, then stirred using an ultrasonic cleaner, and further 100 rpm for 1 hour with a ball mill. Crush under the conditions,
The aqueous phase was prepared.

<Evaluation of rising of triboelectric charge amount> Next,
5 parts of each of the polymerized toners obtained in Examples 1 to 5 and Comparative Example 1 and a non-coated ferrite carrier (trade name: DFC-200 type S3, manufactured by Dowa Iron Powder Co., Ltd.) 9
5 parts were mixed with stirring using a V blender at 60 rpm. In this case, the stirring time is 0.5 minutes, 1 minute, 2 minutes, 5
Minutes, 10 minutes and 30 minutes, the triboelectric charge amount of the polymerized toner was measured with a blow-off charge amount measuring device (manufactured by Toshiba Chemical Co., Ltd.), and the change in the triboelectric charge amount of the polymerized toner over time was evaluated. 3 and FIG. As is clear from FIG. 3 and FIG. 4, it was confirmed that the polymerized toners of Examples 1 to 5 had a large triboelectric charge amount in a short period of time, and the triboelectric charge amount started rising quickly. On the other hand, Comparative Example 1
It was confirmed that the polymerized toner (1) did not increase the triboelectric charge amount in a short time and the rise of the triboelectric charge amount was inferior.

<Evaluation of Charge Amount Distribution> In addition, Example 1, Example 3, Example 4, Example 5 and Comparative Example 1 obtained above were obtained.
5 parts of each polymerized toner and non-coated ferrite carrier (trade name: DFC-200 type manufactured by Dowa Iron Powder Co., Ltd.)
e S3) 95 parts with a V blender at 60 rpm
And stirred for 30 minutes to prepare a developer. Next, the charge amount distribution of the polymerized toner in each developer obtained above was measured by a charge amount distribution meter (trade name: q-MATER, manufactured by PES), and the result is shown in FIG. As is apparent from FIG. 5, the charge amount distributions of the polymerized toners of the respective examples are such that all the toner particles have a charging property on the negative side or the positive side, the distribution is sharp, and the distribution of the triboelectric charge amount is uniform. It was confirmed that many toner particles were present. On the other hand, it was confirmed that in the charge amount distribution of the polymerized toner of Comparative Example 1, there were many cases in which the q / d charge amount was around 0, and the distribution was broad. It was confirmed that the polymerized toner of Example 5 had a sharper charge amount distribution than the polymerized toner of Example 1.

<Evaluation of Image in Copier> Further, 5 parts of each polymerized toner obtained in Example 1, Example 2, Example 3 and Example 5 and a non-coated ferrite carrier (product of Dowa Iron Powder Industry Co., Ltd.) Name: DFC-200 type S
3) 95 parts with V blender 30 at 60 rpm
After stirring and mixing for a minute to prepare a developer, continuous copying of up to 10,000 sheets was performed using a commercially available copying machine using the developer. As a result, it was confirmed that practically problem-free development characteristics having sufficient image density without problems such as background fog and toner scattering were obtained.

[0024]

EFFECTS OF THE INVENTION According to the present invention, polymerized toner having a rapid rise in triboelectric charge amount can be obtained, and toner particles having a sharp triboelectric charge amount distribution and insufficient triboelectric charge amount or toner particles having opposite polarity are produced. A difficult polymerized toner is obtained. Therefore, a polymerized toner having excellent developing characteristics can be obtained as a toner for electrophotography without problems such as background fog and toner scattering.

[Brief description of drawings]

FIG. 1 is an explanatory view showing an example of a polymerization apparatus used in the present invention.

FIG. 2 is an explanatory diagram showing an example of a granulator used in the present invention.

FIG. 3 is a diagram showing changes in the triboelectric charge amount of polymerized toner in Example 1, Example 2, Example 3, Example 5, and Comparative Example 1.

FIG. 4 is a diagram showing a transition of a triboelectric charge amount of polymerized toner in Example 4.

5 is a diagram showing charge amount distributions of polymerized toners in Example 1, Example 3, Example 4, Example 5, and Comparative Example 1. FIG.

[Explanation of symbols]

 1 Water Phase Tank 2 Oil Phase Tank 3 Polymerization Tank 4 Metering Pump 5 Granulator 6 Condenser 7 Heating Jacket 8 Rotating Shaft 9 Suspension Discharge Port 10 Stirrer Blade 11 Shearing Area 12 Emission Control Gap 13 Water Phase Supply Port 14 Oil phase supply port

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takayuki Hamanaka 3-1, Soba-machi, Shizuoka-shi, Shizuoka Prefecture Tomagawa Paper Mill Technical Research Institute

Claims (5)

[Claims] 1. A step of adding an oil phase obtained by dispersing at least a polymerizable monomer, a colorant and a polymerization initiator to an aqueous phase to obtain a suspension having polymerizable droplet groups, A method for producing a polymerized toner comprising a step of heating to polymerize the polymerizable droplet group and a step of removing an aqueous phase, the method comprising the steps of removing the aqueous phase after the step of obtaining the suspension. A method for producing a polymerized toner, characterized in that a hydrophilic liquid having a charge control agent is added before the above. 2. A step of adding an oil phase obtained by dispersing at least a polymerizable monomer, a colorant and a polymerization initiator into an aqueous phase to obtain a suspension having polymerizable droplet groups, A method for producing a polymerized toner, which comprises a step of heating to polymerize the polymerizable droplet group and a step of removing an aqueous phase, wherein the polymerizable droplet is heated after the step of obtaining the suspension. A method for producing a polymerized toner, wherein a hydrophilic liquid having a charge control agent is added before the step of polymerizing the group. 3. A step of adding an oil phase obtained by dispersing at least a polymerizable monomer, a colorant and a polymerization initiator into an aqueous phase to obtain a suspension having polymerizable droplet groups, A method for producing a polymerized toner, comprising a step of heating to polymerize the polymerizable droplet group and a step of removing an aqueous phase, wherein charge control is performed during the step of heating to polymerize the polymerizable droplet group. A method for producing a polymerized toner, which comprises adding a hydrophilic liquid containing an agent. 4. A step of adding an oil phase obtained by dispersing at least a polymerizable monomer, a colorant and a polymerization initiator into an aqueous phase to obtain a suspension having polymerizable droplet groups, A method for producing a polymerized toner comprising a step of heating to polymerize the polymerizable droplet groups and a step of removing an aqueous phase, wherein water is added after the step of heating to polymerize the polymerizable droplet groups. A method for producing a polymerized toner, which comprises adding a hydrophilic liquid having a charge control agent before the step of removing the phase. 5. An aqueous phase and an oil phase obtained by dispersing at least a polymerizable monomer, a colorant, and a polymerization initiator are kept in independent tanks, and both are passed through independent paths. A step of continuously supplying to the granulator at a controlled ratio to obtain a suspension having polymerizable droplet groups of a desired size, and removing the suspension from the granulator in a polymerization tank A method for producing a polymerized toner, which comprises the steps of: leading to the step (1), heating in a polymerization tank to polymerize the polymerizable droplet groups, and removing the aqueous phase, wherein the suspension is taken out and the polymerization tank is removed. A method for producing a polymerized toner, which comprises adding a hydrophilic liquid having a charge control agent between the step of leading to the step of before the step of removing the aqueous phase.