JP2003316075A - Method for manufacturing polymerization process toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide such a method for manufacturing a polymerization process toner, which method does not exert an adverse influence to product characteristics occurring in much intrusion of the polymerized toner particles failing to attain a desired polymerization conversion rate as a result of the insufficiency in stagnation time and the peeled deposits in a polymerization apparatus into the product, does not intrinsically require the work to remove the deposits in the polymerization apparatus and can achieve high production efficiency. <P>SOLUTION: The method comprises manufacturing the polymerization process toner which is colored polymer particles obtained by dispersing a polymerizable monomer composition containing at least a polymerizable monomer and coloring agents into the aqueous medium by using an agitating machine having a high shearing force, to make a polymerizable monomer composition dispersion and polymerizing this polymerizable monomer composition dispersion, in which the process step of polymerizing the polymerizable monomer composition dispersion is performed by the polymerization apparatus to continuously perform supply 7 and withdrawal 8 of the dispersion. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polymerized toner used in electrophotography, electrostatic recording, magnetic recording and the like.

[0002]

2. Description of the Related Art Conventionally, as an electrophotographic method, U.S. Pat. No. 2,297,691 and JP-B-42-23910 are known.
Although various methods have been proposed as described in Japanese Patent Publication No. 43-24748 and Japanese Patent Publication No. 43-24748, generally, an electric latent image is formed on a photoconductor using a photoconductive substance by various means. Then develop the latent image with toner,
After transferring the toner image to a transfer material such as paper, if necessary,
It is fixed by heat and pressure to obtain a copied image.

The toner used in the electrophotographic method has excellent fluidity and stable triboelectric chargeability, and does not cause fog on the photoreceptor or decrease in image density for a long period of time, and high quality printing is possible. It is required to be possible. If the fluidity of the toner is poor, the supply of the developer will be inadequate, and the image will be blurred or the image density will be reduced. In addition, cleaning failure occurs, the developer remains on the photosensitive member, fog occurs, and filming by toner occurs. When the toner film is formed on the photoreceptor, white spots and black stains occur on the image, and the image quality deteriorates. In order for the toner to exhibit excellent fluidity and form a high quality image, it is desirable that the toner has a spherical shape and a sharp particle size distribution.

Conventionally, toners used for these purposes are generally toners having a desired particle size by a fine pulverizer and a classifier after melt-mixing a colorant consisting of dyes and pigments in a thermoplastic resin and uniformly dispersing them. Has been manufactured as.

While this method of manufacture can produce fairly good toners, it does have certain limitations, ie, the choice of toner materials. For example, the material must have sufficient brittleness to be comminuted in economically sound manufacturing equipment. However, when the material is made brittle in order to meet such requirements, the particle size distribution of the particles formed when the material is pulverized at a high speed is apt to become broad, and the toner shows satisfactory development characteristics. Classify,
It is necessary to remove coarse particles and fine particles. Therefore, generally, the pulverization method has a poor yield and a low toner yield.

Further, according to this method, it is difficult to disperse solid fine particles such as a colorant into the resin completely and uniformly.
Depending on the degree of dispersion, fog may increase, image density may decrease, and color mixture and transparency may be poor. Therefore, sufficient attention should be paid to the dispersion of the colorant. Also,
Exposure of the colorant to the fracture surface of the crushed particles may cause fluctuations in developing characteristics.

Further, the pulverization method cannot produce a spherical toner having a uniform surface, and it is difficult to obtain a toner having satisfactory fluidity and triboelectricity.

In the toner obtained by the pulverization method, there is a limitation in adding a release agent such as wax. That is, in order to obtain a sufficient level of dispersibility of the release agent,
At the kneading temperature with the resin, it is necessary to maintain a certain degree of viscosity, and the content of the release agent is set to about 5% by mass or less. Due to such restrictions, there is a limit to the fixability and releasability of the toner by the pulverization method.

In order to overcome the problems of the toner by the crushing method, Japanese Patent Publications No. 36-10231 and 43-1.
Various polymerization method toners and methods for producing the same have been proposed, including suspension polymerization method toners described in JP-A No. 0799 and 51-14895. For example, in a suspension polymerization method toner, a polymerizable monomer, a colorant, a release agent, a polymerization initiator, and if necessary, a crosslinking agent, a charge control agent, and other additives are uniformly dissolved or dispersed. After forming a monomer composition, the monomer composition is dispersed in an aqueous medium containing a dispersion stabilizer by using a suitable stirrer, and at the same time, a polymerization reaction is performed to obtain a toner having a desired particle size. Get the particles. In this method, the material does not need to be brittle, a soft material can be used as the resin, and the colorant is not exposed on the surface of the particles, which is advantageous in that it has uniform triboelectricity. . Further, since the particle size distribution of the obtained toner is relatively sharp, the classification step can be omitted, and even if classification is necessary, the toner can be obtained in high yield.
Furthermore, according to this method, a release agent such as wax can be surely encapsulated, and good fixability and offset resistance can be obtained. The polymerized toner obtained by this method is spherical and has a uniform surface, so that it has good fluidity and transferability, exhibits good developing characteristics even after performing continuous development a number of times, and has less stress on the toner. The feature is that the occurrence of filming on the photoconductor is small.

[0010]

In the above-mentioned method for producing a toner by the suspension polymerization method, each step is usually carried out in a batch system. Although some of the steps are continuous, there are few examples in which the polymerization step of polymerizing the polymerizable monomer composition suspended and dispersed in an aqueous dispersion medium is continuously performed. For example, according to JP-A-8-305084 and JP-A-11-106407, the polymerizable monomer composition is dispersed in an aqueous dispersion medium by using a stirrer having a high shearing force and granulated. In the former case, continuous or batch granulation is carried out, and in the latter case, continuous granulation is carried out, but the subsequent polymerization steps are all batch systems using a normal vertical stirring tank. Even if the previous process is a continuous process, if the polymerization process is a batch process, the advantages such as high production efficiency, space saving, and stable steady-state operation that should be obtained by the continuous process can be fully achieved. I can't enjoy it.

A general tank reactor equipped with a stirring means is used to carry out the continuous polymerization easily, but when used in a single tank, it is difficult to operate under the condition of a so-called "complete mixing tank", "Short pass" occurs in which the proportion of particles flowing out without a long residence time increases, and those whose polymerization conversion rate has not reached are mixed in the product, which adversely affects the product properties, which is not preferable.

[0012] In addition, the normal tank type reactor is not used in a state of full water, and is operated with a slight gas phase part provided in the upper part, so that it is near the interface between the gas phase part and the liquid phase part on the inner wall of the tank. In addition, deposits derived from the polymerizable monomer composition are easily generated. When the reactor is operated at a high temperature, the deposits are fused and solidified to become strong deposits. If these deposits are left unattended, they will eventually grow up and peel off, causing problems such as product contamination and blockage of the pipes connected to the reaction tank. Work such as cleaning is required. Frequent equipment shutdowns reduce production efficiency and significantly diminish the benefits of continuous polymerization.

Continuous granulation without using a typical tank reactor
An example of continuous polymerization is found in JP-A-7-281480 and JP-A-9-43898, and a tower-type or tube-type reactor is used, but both are in a fluidized state in the reactor. Is insufficient as a method from the viewpoint of preventing deposits.

Therefore, an object of the present invention is a method for producing a toner by a polymerization method in which a polymerizable monomer composition is dispersed in an aqueous medium and then a polymerization step is carried out. Is to provide a method for producing a polymerized toner, which is a device that does not cause the above-mentioned problems.

[0015]

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a polymerizable monomer composition containing at least a polymerizable monomer and a colorant is subjected to high shearing. A colored polymer particle obtained by dispersing a polymerizable monomer composition dispersion in an aqueous dispersion medium using a stirrer having a force and polymerizing the polymerizable monomer composition dispersion. In the method for producing a polymerized toner, the step of polymerizing the polymerizable monomer composition dispersion is carried out in a polymerization device in which the supply and the withdrawal of the dispersion are continuous, The polymerization apparatus is a tank reactor, and the inside thereof is divided into a plurality of small compartments by partition plates, and the partition plates are provided with openings so that liquid can flow between adjacent compartments. , Each small section has a stirring means, and the small section at one end The structure is such that the polymerizable monomer composition dispersion is introduced and withdrawn from the multi-end small compartments, and the proportion of particles with an unachieved degree of polymerization due to the "short path" mixed into the product is small. We have found a method that does not cause the formation of deposits.

In the tank reactor used in this method, the small compartments partitioned by the partition plate inside are connected in series through the openings of the partition plate, and the polymerizable monomer introduced into the reactor is introduced. It may have a structure in which the composition dispersion circulates without backflow, flow splitting, merging, or retention.

A partition plate for partitioning the inside of the tank reactor into a plurality of small compartments is installed perpendicularly to the central axis of the tank reactor, and has a stirring shaft that penetrates each partition plate. May have a structure in which at least one stirring blade is attached to each small section.

Furthermore, in each of the small compartments partitioned by the partition plate inside the tank reactor, the flow rate Q (m ³ / hr) of the inflowing polymerizable monomer composition and the respective small compartments generated by the stirring blades. The circulation flow rate q (m ³ / hr) in the interior satisfies the following equation q / Q ≦ 45, and q and the area A (m ² ) of the opening of the partition plate.
However, it is preferable to carry out under the condition that the following formula A / q ≦ 5 × 10 ⁻⁴ is satisfied.

In the tank reactor of the present invention, it is desirable that the inside of the tank reactor is in a full water state where there is as little vapor phase portion as possible during the polymerization reaction. Since there is no vapor phase portion, deposits at the gas-liquid interface do not occur, and adverse effects on the product properties due to the mixture of the stripped deposits can be avoided.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

In the method for producing the polymerized toner of the present invention, at least a colorant and, if necessary, an additive such as a releasing agent, a charge control agent, a crosslinking agent, a polymerization initiator and the like are added to the polymerizable monomer. A stirring device used, a homogenizer, an ultrasonic disperser, or the like to dissolve or disperse the polymerizable monomer composition into an aqueous dispersion medium containing a dispersion stabilizer, and a stirrer having a high shearing force. Is used to prepare a polymerizable monomer composition suspension having a desired droplet size.
This step is called granulation, and after the suspension of the polymerizable monomer composition is prepared by this step, the particle state is maintained by the action of the dispersion stabilizer, so that the precipitation of particles does not occur. The polymerization step is carried out while maintaining the fluid state until the desired degree of polymerization is obtained.

The polymerization temperature is 40 ° C. or higher, generally 50 to
The temperature is set to 90 ° C. Further, in order to remove unreacted polymerizable monomers, by-products and the like, a part of the aqueous dispersion medium may be distilled off after the reaction by a distillation operation. The distillation operation can be performed under normal pressure or reduced pressure. After the completion of the polymerization reaction or the distillation operation, the produced toner particles are filtered / washed, but the dispersion stabilizer on the obtained particulate surface may be removed by an acid and / or alkali treatment before or after this step. it can. The toner particles finally separated from the liquid phase are dried by a known method.

As the granulation means used in the toner production method by the suspension polymerization method, a method using a stirrer having a high shearing force, a method using ultrasonic waves, and a porous body such as SPG (silica porous glass) is used. The method is generally adopted. Although droplets having a good droplet size distribution can be obtained by using these methods, the method using an agitator having a high shearing force is most suitable in the present invention. As a stirrer having a high shearing force, T.I. K. CLEARMIX (M Technique) that rotates a so-called tooth disk turbine blade at high speed with a plurality of square teeth arranged vertically along the outer circumference of the disk like Homo Disper (made by Tokushu Kika Kogyo Co., Ltd.) Co., Ltd.) or T.I. K. A homomixer (made by Tokushu Kika Kogyo Co., Ltd.) that consists of a stirring blade (rotor) that rotates at high speed and a stator that is arranged so as to surround it, and uses the shearing force generated in the gap between them. There is. In particular, CLEARMIX is suitable for use in the present invention because it has a plurality of slits in the stator and a jet jet from the slits can obtain a higher shearing force.

In addition, T. K. A stirrer such as Filmix (made by Tokushu Kika Kogyo Co., Ltd.) that reaches the vicinity of the inner peripheral surface of the container for containing the liquid to be treated is rotated at a high peripheral speed, and the liquid to be treated is separated by the centrifugal force generated thereby. Those that are crimped to the inner surface of the container and utilize a high shearing force due to shear generated by swirling in the shape of a hollow thin film are also suitable for the present invention.

When granulating by high shear stirring,
By adjusting the stirring speed and the granulation time, it is possible to obtain a polymerizable monomer composition dispersion having a desired droplet size.

In order to introduce the aqueous dispersion medium and the polymerizable monomer composition into the granulating device, a method of introducing them in a mixed state by an ordinary stirring and mixing means in advance, or both of them are quantitatively determined in advance. It can be carried out by any of the methods of directly introducing into the granulating apparatus at the ratio of.

A preferred mode of the polymerization apparatus used in the present invention will be described with reference to FIG. In the figure, reference numeral 1 is a tank reactor can, reference numeral 2 is a partition plate for dividing the interior of the reactor into small compartments,
Reference numeral 3 is a heating / cooling jacket, reference numeral 4 is a stirring blade, reference numeral 5
Is a stirring shaft, 6 is a partition plate opening, 7 is a liquid inlet, 8 is a liquid outlet, and 9 is a stirring motor.

The polymerizable monomer composition dispersion liquid that has undergone the granulation step is introduced into the tank reactor through the liquid inlet. At this time, the reactor is preferably filled with water or an aqueous dispersion medium in advance from the viewpoint of the stability of the polymerizable monomer composition-dispersed droplets. The introduced polymerizable monomer composition dispersion liquid is stirred for a predetermined residence time in the first small section divided by the partition plate, and then flows out from the partition plate opening to the next adjacent small section. . Thereafter, the polymerizable monomer composition dispersion liquid is similarly sequentially transferred to the adjacent small compartments and finally discharged from the liquid outlet to the outside of the reactor.

In the polymerization apparatus of the present invention, a general stirring blade can be used as long as it can maintain a uniform dispersed / flowing state of the polymerizable monomer composition dispersed droplets.
In order to prevent the discharge flow due to stirring from affecting the residence time distribution of the polymerizable monomer composition dispersion, it is preferable to use blades with a small discharge in the axial direction, such as turbine blades, paddle blades, and three retreating blades. Used for.

The opening area of the partition plate opening and the ratio of the circulation flow rate by stirring to the inflow amount of the polymerizable monomer composition dispersion have a great influence on the residence time distribution of the polymerizable monomer composition dispersion. Exert. Specifically, the flow rate Q (m ³ / hr) of the polymerizable monomer composition dispersion liquid flowing into each small section partitioned by the partition plate and the circulation flow rate q (generated by the stirring blade in each small section) m ³ / hr) is q / Q ≦
45, and q and the area A (m of the opening of the partition plate
² ) is preferably performed under the condition that A / q ≦ 5 × 10 ⁻⁴ is satisfied. q / Q> 45 or A / q> 5 ×
When it becomes 10 ⁻⁴ , the influence of the circulation flow rate generated by the stirring blade on the residence time distribution becomes large.

The constituent materials of the toner will be described below.

As the polymerizable monomer used in the toner of the present invention, a vinyl-based polymerizable monomer capable of radical polymerization is used. As the vinyl-based polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used.

Styrene as the monofunctional polymerizable monomer,
α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene,
2,4-dimethylstyrene, pn-butylstyrene,
p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-phenyl Styrene derivatives such as styrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-
Butyl acrylate, tert-butyl acrylate,
n-amyl acrylate, n-hexyl acrylate,
Acrylic polymerization such as 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate. Monomers; methyl methacrylate,
Ethyl methacrylate, n-propyl methacrylate,
iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-
Methacrylic polymerizable monomers such as hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethyl phosphate ethyl methacrylate, dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid ester, vinyl acetate , Vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl formate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; vinyl methyl ketone, vinyl hexyl ketone,
Examples thereof include vinyl ketones such as vinyl isopropyl ketone.

As the polyfunctional polymerizable monomer, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6
-Hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 2,2'-bis (4- (acryloxydiethoxy)
Phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate,
1,3-butylene glycol dimethacrylate, 1,6
-Hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis (4- (methacryloxydiethoxy) phenyl) propane, 2,2'-bis (4- (methacryloxypolyethoxy) ) Phenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, divinyl ether and the like.

In the present invention, the above-mentioned monofunctional polymerizable monomers are used alone or in combination of two or more kinds, or the above-mentioned monofunctional polymerizable monomers and polyfunctional polymerizable monomers are combined. To use. Among the above-mentioned monomers, it is preferable to use styrene or a styrene derivative alone or in combination, or to use them in combination with other monomers, from the viewpoint of developing characteristics and durability of the toner.

Examples of the colorant used in the present invention include carbon black, iron black, C.I. I. Direct Red 1, C.I. I. Direct Red 4, C.I. I. Acid Red 1, C.I. I. Basic Red 1, C.I. I.
Mordant Red 30, C.I. I. Direct Blue 1,
C. I. Direct Blue 2, C.I. I. Acid Blue 9, C.I. I. Acid Blue 15, C.I. I. Basic Blue 3, C.I. I. Basic Blue 5, C.I. I. Mordant Blue 7, C.I. I. Direct Green 6, C.I.
I. Basic Green 4, C.I. I. Dyes such as Basic Green 6; Yellow Lead, Cadmium Yellow, Mineral Fast Yellow, Navel Yellow, Naphthol Yellow S, Hansa Yellow G, Permanent Yellow NC
G, tartrazine lake, molybdenum orange, permanent orange GTR, benzidine orange G, cadmium red, permanent red 4R, watching red calcium salt, brilliant carmine 3B, fast violet B, methyl violet lake, navy blue,
Pigments such as cobalt blue, alkali blue lake, Victoria blue lake, quinacridone, rhodamine lake, phthalocyanine blue, fast sky blue, pigment green B, malachite green lake, and final yellow green G are listed.

In selecting a colorant, it is necessary to pay attention to the polymerization inhibitory property and water phase transfer property of the colorant, and it is preferable to carry out surface modification, for example, hydrophobic treatment with a substance that does not inhibit polymerization. You should keep it. In particular, since many dyes and carbon black have a polymerization inhibitory property, caution is required when using them. A preferred method of surface-treating a dye system is a method of polymerizing a polymerizable monomer in the presence of these dyes in advance, and the obtained colored polymer is added to the polymerizable monomer composition. Furthermore, for carbon black, in addition to the same treatment as the above dye,
The graft treatment may be performed with a substance that reacts with the surface functional groups of carbon black, such as polyorganosiloxane.

As the release agent, a wax in a solid state at room temperature is preferable, and a solid wax having a melting point of 40 to 100 ° C. is particularly preferable in terms of toner blocking resistance, multi-sheet durability, low temperature fixing property and offset resistance. .

Paraffin wax,
Polymethylene wax such as polyolefin wax, microcrystalline wax, Fischer-Tropsch wax, amide wax, higher fatty acid, long chain alcohol, ester wax and graft compounds thereof,
Derivatives such as block compounds are mentioned, and those having a low maximum molecular weight component removed and having a sharp maximum endothermic peak in the DSC (differential scanning calorimeter) endothermic curve are preferable.

The wax preferably used includes linear alkyl alcohols having 15 to 100 carbon atoms, linear fatty acids, linear acid amides, linear esters, and montan derivatives. Those in which impurities such as liquid fatty acid have been previously removed from these waxes are more preferable.

In order to improve the translucency of a fixed image,
A solid ester wax is particularly preferable, and as the solid ester wax, one having a melting point of 40 to 100 ° C. is suitably used.

The release agent is contained in an amount of 1 to 40 parts by weight, preferably 4 to 30 parts by weight, based on 100 parts by weight of the polymerizable monomer.

The toner of the present invention may contain a charge control agent.

As charge control agents, known charge control agents can be used. For example, organometal compounds and chelate compounds are effective as charge control agents for toner, and monoazo dye metal compounds and acetylacetone metal compounds are effective. , Aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives such as bisphenol. Further, urea derivatives, salicylic acid-containing compounds, quaternary ammonium salts, calixarene, silicon compounds, styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene-acrylic-sulfonic acid copolymers, non-metals Examples thereof include carboxylic acid compounds.

To control the toner to be positively charged, modified products of nigrosine and fatty acid metal salts, quaternary compounds such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, etc. Ammonium salts, onium salts such as phosphonium salts which are analogs thereof, lake pigments thereof, triphenylmethane dyes and lake pigments thereof (as a laker, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid) , Tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.), metal salts of higher fatty acids,
Dibutyltin oxide, dioctyltin oxide,
There are diorgano tin oxides such as dicyclohexyl tin oxide, dibutyl tin borate, dioctyl tin borate, and diorgano tin borates such as dicyclohexyl tin borate, and these can be used alone or in combination of two or more kinds. Among these,
Charge control agents such as nigrosine-based and quaternary ammonium salts are particularly preferably used.

These charge control agents are the polymerizable monomers 10
It is preferable to use 0.01 to 20 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 0 parts by mass.

Polymerization initiators that can be used in the present invention include 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'- Azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,
Azo-based polymerization initiators such as 4-dimethylvaleronitrile and azobismethylbutyronitrile; benzoyl peroxide, lauroyl peroxide, di-α-cumyl peroxide, 2,5-dimethyl-2,5-bis (benzoylper) (Oxy) hexane, bis (4-t-butylcyclohexyl) peroxydicarbonate, 1,1-bis (t-butylperoxy) cyclododecane, t-butylperoxymaleic acid, bis (t-butylperoxy)
Isophthalate, methyl ethyl ketone peroxide,
Examples include peroxide polymerization initiators such as tert-butylperoxy-2-ethylhexanoate, diisopropylperoxycarbonate, cumene hydroperoxide, and 2,4-dichlorobenzoyl peroxide. The initiator is selected with reference to the 10-hour half-life temperature and used alone or in combination. The amount of the polymerization initiator added varies depending on the desired degree of polymerization, but generally 0.5 to 20 parts by mass is added to 100 parts by mass of the polymerizable monomer and used.

Examples of the crosslinking agent include divinylbenzene, 4,4′-divinylbiphenyl, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, glycidyl (meth) acrylate, trimethylolpropane tri (meth) acrylate. And other polyfunctional compounds.

As a dispersion stabilizer for favorably dispersing the polymerizable monomer composition in an aqueous medium, for example, inorganic oxides such as tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, Examples thereof include calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina and titania. Examples of the organic compound include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, starch and the like. The dispersion stabilizer is preferably used in an amount of 0.2 to 10.0 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

As these dispersion stabilizers, commercially available products may be used as they are, but in order to obtain dispersed particles having a fine and uniform particle size, the inorganic compound may be formed under stirring. For example, in the case of tricalcium phosphate, a dispersant suitable for the suspension polymerization method can be obtained by adding and mixing an aqueous sodium phosphate solution and an aqueous calcium chloride solution into water whose pH has been adjusted with stirring. Further, in order to make these dispersants finer, 0.001 to 0.1% by mass of a surfactant may be used in combination with water. Specifically, commercially available nonionic, anionic and cationic surfactants can be used, for example, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium dodecylbenzenesulfonate, sodium oleate, sodium laurate. , Potassium stearate, calcium oleate and the like are preferably used.

In the case of a polymerization method using an aqueous dispersion medium such as suspension polymerization, addition of a polar resin to the polymerizable monomer composition can promote the inclusion of a release agent. it can. When the polar resin is present in the polymerizable monomer composition suspended in the aqueous medium, the polar resin easily migrates to the vicinity of the interface between the aqueous medium and the polymerizable monomer composition due to the difference in affinity for water. Therefore, the polar resin is unevenly distributed on the toner surface. As a result, the toner particles have a core-shell structure,
Even when a large amount of release agent is contained, the release agent has good encapsulation property.

As the polar resin, a saturated or unsaturated polyester resin is particularly preferable since the fluidity of the polar resin itself can be expected when the shell is formed unevenly on the toner surface.

As the polyester resin, those obtained by condensation polymerization of the following acid component monomers and alcohol component monomers can be used. Acid component monomers include terephthalic acid, isophthalic acid, phthalic acid, fumaric acid, maleic acid, malonic acid, succinic acid, glutaric acid, adipic acid,
Pimelic acid, suberic acid, azelaic acid, sebacic acid,
Examples include camphoric acid, cyclohexanedicarboxylic acid, trimellitic acid and the like. As the alcohol component monomer, ethylene glycol, diethylene glycol,
Alkylene glycols and polyalkylene glycols such as triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-bis (hydroxymethyl) cyclohexane and the like, Examples thereof include bisphenol A, hydrogenated bisphenol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, glycerin, trimethylolpropane and pentaerythritol.

In using the toner produced by the present invention, an external additive can be used for the purpose of imparting various characteristics. The external additive preferably has a particle diameter of 1/10 or less of the average particle diameter of the toner particles from the viewpoint of durability when added to the toner. The particle size of the additive means the average particle size obtained by observation with an electron microscope. Examples of the external additive include metal oxides (aluminum oxide, titanium oxide, strontium titanate, cerium oxide, magnesium oxide, chromium oxide, tin oxide, zinc oxide, etc.), nitrides (silicon nitride, etc.), carbides (silicon carbide, etc.). Etc.), inorganic metal salts (calcium sulfate, barium sulfate, calcium carbonate, etc.), fatty acid metal salts (zinc stearate, calcium stearate, etc.), carbon black, silica and the like.

These external additives are used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the toner particles. The external additives may be used alone or in combination of two or more, but those subjected to a hydrophobic treatment are more preferable.

Further, the toner produced by the present invention is
It can also be used as a magnetic toner by containing a magnetic material. In this case, the magnetic material can also serve as a coloring agent. In the present invention, as the magnetic material contained in the magnetic toner, iron oxide such as magnetite, hematite and ferrite, metals such as iron, cobalt and nickel, or these metals and aluminum, cobalt, copper, lead, magnesium and tin. , Zinc, antimony, beryllium, bismuth,
Cadmium, calcium, manganese, selenium, titanium,
Examples thereof include alloys of metals such as tungsten and vanadium and mixtures thereof.

These ferromagnetic materials have an average particle size of 2 μm or less, preferably about 0.1 to 0.5 μm. The amount of the polymerizable monomer 10 is contained in the toner.
About 20 to 200 parts by mass relative to 0 parts by mass, particularly preferably 40 to 150 parts by mass based on 100 parts by mass of the polymerizable monomer.

Further, the magnetic characteristics under application of 800 kA / m are coercive force (Hc) of 1.6 to 24 kA / m and saturation magnetization (σ
s) 50 to ²⁰⁰ Am ² / kg, remanent magnetization (σr) 2
It is preferably ²⁰ Am ² / kg.

In order to improve the dispersibility of these magnetic substances in the toner particles, it is also preferable to make the surface hydrophobic. Coupling agents such as a silane coupling agent and a titanium coupling agent are used for the hydrophobic treatment, and among them, the silane coupling agent is preferably used. As the silane coupling agent, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, methyltrimethoxysilane, methyltriethoxysilane, isobutyltrimethoxysilane, dimethyldimethoxysilane, dimethyl. Examples thereof include diethoxysilane, trimethylmethoxysilane, hydroxypropyltrimethoxysilane, phenyltrimethoxysilane, n-hexadecyltrimethoxysilane and n-octadecyltrimethoxysilane.

The toner of the present invention can be used as a one-component or two-component developer in any developing method. For example, in the case of a magnetic toner in which a magnetic material is contained in the toner as a one-component developer, there is a method of transporting and charging the magnetic toner by using a magnet incorporated in the developing sleeve. When a non-magnetic toner containing no magnetic substance is used, there is a method in which a blade and a fur brush are forcibly triboelectrically charged by a developing sleeve and the toner is adhered onto the sleeve to carry the toner.

On the other hand, when it is used as a two-component type developer, a carrier is used together with the toner obtained by the present invention to be used as a developer. The carrier used in the present invention is not particularly limited, but mainly iron,
It is composed of single and composite ferrite states consisting of copper, zinc, nickel, cobalt, manganese and chromium elements. The carrier shape is also important in that saturation magnetization and electric resistance can be controlled over a wide range, and it is preferable to select, for example, a spherical shape, a flat shape, or an indeterminate shape, and also to control the fine structure of the carrier surface state such as surface irregularity.
Generally, a method of forming carrier core particles in advance by firing and granulating the oxide of the above metal and then coating with a resin is used, but from the viewpoint of reducing the load on the toner of the carrier. A method of kneading a metal oxide and a resin, then pulverizing and classifying the resin to obtain a low-density dispersed carrier, and further, a kneaded product of a metal oxide and a monomer is directly suspension-polymerized in an aqueous medium to obtain a true spherical dispersed carrier. It is also possible to use a method of obtaining a polymerized carrier for obtaining

A system in which the surface of the carrier is coated with a resin or the like is particularly preferable. As the method, any conventionally known method such as a method of dissolving or suspending a coating material such as a resin in a solvent and applying the coating material and adhering it to a carrier, or a method of simply mixing with a powder can be applied.

The substance adhered to the surface of the carrier varies depending on the toner material. For example, polytetrafluoroethylene, monochlorotrifluoroethylene polymer, polyvinylidene fluoride, silicone resin, polyester resin, metal compound of di-tert-butylsalicylic acid, Styrene resin, acrylic resin, polyamide, polyvinyl butyral, nigrosine, amino acrylate resin, basic dye and its lake, silica fine powder, alumina fine powder and the like are suitable, but it is not always necessary to use them. Not restricted.

The total amount of the above compounds treated is generally 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the carrier.

The average particle size of these carriers is 10 to 100.
It is desirable that the thickness is μm, more preferably 20 to 50 μm.

As a particularly preferred embodiment of the carrier,
Cu-Zn-Fe ternary ferrite, the surface of which is a combination of resins such as fluorine resin and styrene resin, for example, polyvinylidene fluoride and styrene-methyl methacrylate resin, polytetrafluoroethylene and styrene-methyl methacrylate. 0.01 to 5% by mass, preferably a mixture of a resin, a fluorine-based copolymer and a styrene-based copolymer in a ratio of 90:10 to 20:80, preferably 70:30 to 30:70. Examples of the coated ferrite carrier include 0.1 to 1% by mass of coating, 250 mesh pass, 400 mesh on carrier particles having the above-mentioned average particle size of 70% by mass or more. As the fluorine-based copolymer, vinylidene fluoride-tetrafluoroethylene copolymer (10:90 to 9)
0:10), and the styrene-based copolymer is styrene-2-ethylhexyl acrylate (20: 80-
80:20), styrene-2-ethylhexyl acrylate-methyl methacrylate (20-60: 5-30: 10).
˜50) are illustrated.

The above-mentioned coated ferrite carrier has a sharp particle size distribution, provides the toner of the present invention with favorable triboelectric charging properties, and has the effect of improving electrophotographic characteristics.

When a two-component developer is prepared by mixing with the toner of the present invention, the mixing ratio is 2 to 15% by mass, preferably 4 to 13% by mass as the toner concentration in the developer.
A good result is usually obtained. If the toner concentration is less than 2% by mass, the image density is too low to be practical, and if it exceeds 15% by mass, fog and scattering in the machine are increased and the useful life of the developer is shortened.

Further, the magnetic characteristics of the carrier are as follows. Intensity of magnetization at 80 kA / m after magnetically saturated is required to be 30~300Am ² / kg. To achieve higher image quality, it is preferably 35 to 250 Am ² / kg. 300
If it is larger than Am ² / kg, it becomes difficult to obtain a high-quality toner image. If it is less than 30 Am ² / kg, the magnetic binding force is reduced and carrier adhesion is likely to occur.

[0070]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited to these.

In the examples, the following measuring methods were used.

(1) Measurement of particle size distribution and volume average particle size In 100 to 150 ml of a 1% by mass aqueous sodium chloride solution, an alkylbenzene sulfonate as a surfactant was added in an amount of 0.
1 to 5 ml was added, and 0.5 to 50 mg of the measurement sample was further added. This solution was subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and then, with a Coulter Multisizer (manufactured by Coulter Co.), a dispersion of 2 to 4 using a 100 μm aperture.
The volume particle size distribution of 0 μm particles was measured, and the volume average particle size was obtained from this.

(2) Image quality evaluation of image quality of color two-component color developer With respect to the obtained toner particles, a hydrophobic silica fine powder having a specific surface area of 200 m ² / g measured by the BET method was used.
External addition was carried out so that the content would be 7% by mass. A ferrite carrier coated with an acrylic resin was mixed so that the externally added toner was 8% by mass to obtain a color two-component developer. Under the environment where this developer does not fluctuate, a full-color copying machine CLC700 manufactured by Canon Inc. was used to perform an image output durability test by continuous paper feeding, and visually evaluated fluctuations in image density and unevenness. 1. Image quality evaluation of monochrome one-component type developer 1. To the obtained toner particles, a hydrophobic silica fine powder having a specific surface area of 250 m ² / g measured by BET method was prepared.
External addition was carried out so as to be 2% by mass to obtain a monochrome one-component developer. Under the environment where this developer did not fluctuate, an image output durability test by continuous paper feeding was performed using a laser printer LBP-1760 manufactured by Canon, and the fluctuation and unevenness of the image density were visually evaluated.

(3) Measurement of fog The measurement of fog was conducted by the REFLECTROMETER MO
It measured using DEL TC-6DS (made by Tokyo Denshoku Co., Ltd.), and calculated from the following formula. The smaller the number, the less fog. Fog (reflectance) (%) = reflectance of standard paper (%)-reflectance of non-image part of sample (%)

(4) Measurement of triboelectric charge amount of toner The triboelectric charge amount of toner was measured by the following procedure based on the blow-off method after leaving the toner and the carrier for one day under an environment where the toner triboelectric charge amount did not change.

FIG. 2 is an explanatory view of an apparatus for measuring the triboelectric charge amount of toner. 50 to 100 m of a mixture of a toner and a carrier whose mass ratio is 8:92, whose triboelectric charge amount is to be measured.
The mixture was placed in a polyethylene bottle having a volume of 1 and shaken by hand 200 times to mix. About 0.2 g of this mixture is placed in a metal measuring container 12 having a 500-mesh screen 13 at the bottom, and a metal lid 14 is placed. At this time, the total mass of the measuring container 12 is weighed and set as W ₁ (g). Next, the suction device 11 (the portion in contact with the measurement container 12 is an insulator) sucks through the suction port 17 to read the instruction of the vacuum gauge 15, and the pressure is adjusted to 2450 Pa by the air volume control valve 16. In this state, the toner is removed by suction for about 2 minutes. Electrometer 19 at this time
The maximum value of the potential indicated by V (volt), capacitor 1
When the capacity of 8 is C (μF) and the mass of the entire measuring container after suction is W ₂ (g), the triboelectric charge amount (mC / mC /
kg) is calculated by the following formula. Triboelectric charge amount (mC / kg) = C × V ÷ (W ₁ −W ₂ ).

(5) Measurement of polymerization conversion rate A part of the suspension of the polymerizable monomer composition during suspension polymerization is withdrawn, and 0.2 g of each is diluted with 15 g of acetone. This is irradiated with ultrasonic waves for 30 minutes, and then filtered through a membrane filter having a pore size of 0.45 μm to remove the one insoluble in acetone. The filtrate is gas chromatographically analyzed to quantify the unreacted polymerizable monomer dissolved in acetone and converted into the polymerization conversion rate.

Example 1 An aqueous dispersion medium and a polymerizable monomer composition were prepared as follows.

(Preparation of Aqueous Dispersion Medium) Water 98.4% by mass Na ₃ PO ₄ 1.0% by mass After mixing the above components in the container, nitrogen gas was introduced to adjust the oxygen concentration in the gas phase portion of the container to 0. It was set to 5% or less. C here
was added NaCl ₂ 0.6 wt% T. K. Ca ₃ (PO ₄ ) was obtained by stirring for 30 minutes using a homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.) at a rotation speed of 1500 rpm.
_An aqueous dispersion medium containing the fine particles of ₂ was obtained.

(Preparation of Polymerizable Monomer Composition) Styrene monomer 63.9% by mass n-Butyl acrylate monomer 13.1% by mass Quinacridone pigment 6.2% by mass Unsaturated polyester resin 3.9 Mass% Divinylbenzene 0.2 mass% Di-tert-butylsalicylic acid aluminum compound 0.8 mass% Ester wax 9.6 mass% 2,2'-Azobis- (2,4-dimethylvaleronitrile) 2.3 mass% Of the above components, a part of the styrene monomer, a quinacridone pigment, and an aluminum di-tert-butylsalicylate compound are mixed and dispersed for 5 hours using a handy mill (manufactured by Mitsui Mining Co., Ltd.). The rest of the monomer and the composition other than 2,2'-azobis- (2,4-dimethylvaleronitrile) are added and heated to 60 ° C to be sufficiently compatible. It was mixed up. Then 2,2'-azobis- (2,
4-Dimethylvaleronitrile) was added 1 minute before the start of the next granulation step to obtain a polymerizable monomer composition.

(Granulation step) As the granulation apparatus, CLEARMIX (manufactured by M Technique Co., Ltd.) equipped with a continuous attachment was used. The aqueous dispersion medium is preheated to 60 ° C., and the mass flow ratio of this and the polymerizable monomer composition is 3: 1,
The mixture was quantitatively introduced into Clearmix so that the residence time was 2 minutes, and granulation was performed at a rotation speed of 15,000 rotations / minute to obtain a polymerizable monomer composition suspension.

(Polymerization Step) The polymerizable monomer composition suspension obtained in the granulation step was continuously introduced into the polymerization vessel shown in FIG. 1 and polymerization was carried out at 80 ° C. with stirring. At this time, the internal volume of the polymerization container is such that the introduced polymerizable monomer composition suspension is retained for 8 hours and then discharged, the number of rotations of the stirring blade, the opening area of the partition plate. Is q / Q = 50 and A / q = 3 × 10 ⁻⁴ [Q (m ³ / hr) is the flow rate of the inflowing polymerizable monomer composition dispersion liquid, and q (m ³ / hr) is depending on the stirring blade. The generated circulation flow rate in each small section, A (m ² ) indicates the area of the opening of the partition plate. ] Was set to meet.

Dilute hydrochloric acid was added to the polymer composition suspension discharged from the polymerization container to dissolve the dispersant covering the surface of the polymer particles, and solid-liquid separation was performed, followed by washing with water, filtration, and drying to obtain a polymerized toner. The particles were obtained. After continuously polymerizing for 24 hours, when the inside of the polymerization vessel was observed after the liquid was completely discharged from the polymerization vessel, no deposits were found in the polymerization vessel, and even if the continuous operation was restarted as it was There was no problem.

(Evaluation of Toner) When the particle size distribution of the toner particles was measured, the volume average particle size was 8.1 μm, the particle size distribution was sharp, and the triboelectric charge amount was −40 mC / kg, which was a good value. . The polymerization conversion of the obtained toner is 98.
%Met.

Next, hydrophobic silica was externally added to the toner particles, and a ferrite carrier coated with an acrylic resin was mixed to obtain a two-component type developer. When an image output test was performed on 20,000 sheets, fog was 1.3%, and the image density was stable and stable from beginning to end, and a clear image having excellent fixability was stably obtained.

Comparative Example 1 A polymerized toner was produced in exactly the same manner as in Example 1 except that continuous polymerization was carried out using a normal vertical stirring tank as a polymerization device. After the polymerization, there was a considerable amount of polymer deposits near the gas-liquid interface in the polymerization vessel, and some deposits were peeled off at the bottom of the tank.Continuous operation without removing deposits It was an unfavorable situation to restart. The volume average particle diameter of the obtained toner particles was 8.5 μm, and the particle size distribution was larger on the coarse powder side than in Example 1. The triboelectric charge amount was -35 mC / kg. The polymerization conversion rate was 88%, which shows that a large proportion of particles flowed out of the polymerization apparatus without the desired polymerization time.

Next, when an image output test of 20000 sheets was carried out in the same manner as in Example 1, fog was 2.1%, and white streaks and density unevenness occurred from a relatively early stage.

Example 2 q / Q was set to 4 by changing the stirring speed and the area of the partition plate opening.
A polymerized toner was produced in exactly the same manner as in Example 1 except that 0 and A / q were set to 6 × 10 ⁻⁴ . The volume average particle diameter of the obtained toner particles is 8.2 μm, and the triboelectric charge amount is −38 mC.
It was / kg. The polymerization conversion rate was 96%.

Next, an image output test of 20,000 sheets was carried out in the same manner as in Example 1. As a result, the fog was 1.2, and the image density was stable and stable throughout the image with stable and excellent fixing property. It was obtained.

Example 3 A polymerized toner was produced in exactly the same manner as in Example 1 except that the stirring speed was changed to q / Q of 40. The obtained toner particles have a volume average particle size of 7.8 μm and a triboelectric charge amount of −45.
It was mC / kg. The polymerization conversion rate was 100%.

Next, an image output test of 20,000 sheets was carried out in the same manner as in Example 1. As a result, the fog was 1.1, and the image density was stable and stable throughout the image. It was obtained.

Example 4 A water dispersion medium and a polymerizable monomer composition were prepared as follows.

(Preparation of Aqueous Dispersion Medium) An aqueous dispersion medium was prepared in exactly the same manner as in Example 1 except that the composition was changed as follows. Water 98.1% by mass Na ₃ PO ₄ 1.2% by mass CaCl ₂ 0.7% by mass

(Preparation of Polymerizable Monomer Composition) Styrene monomer 39.0% by mass n-butyl acrylate monomer 11.0% by mass Silane coupling-treated magnetic iron oxide particles 45.0% by mass Unsaturated Polyester resin 2.0% by mass Saturated polyester resin 0.5% by mass Monoazo dye iron compound 0.5% by mass Ester wax 2.0% by mass Part of styrene monomer among the above components, silane coupling treatment magnetic Iron oxide particles and monoazo dye iron compound were mixed and dispersed for 5 hours using a handy mill (manufactured by Mitsui Mining Co., Ltd.), and then the rest of the styrene monomer and other compositions were added and heated to 60 ° C. Then, they were mixed until they were sufficiently compatible to obtain a polymerizable monomer composition.

(Granulation step) The aqueous dispersion medium was previously heated to 60 ° C., and benzoyl peroxide was added thereto so as to be 1.5% by mass with respect to the polymerizable monomer composition.
K. A homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.) was stirred and sufficiently suspended. This and the polymerizable monomer composition were quantitatively introduced into CLEARMIX (manufactured by M Technique Co., Ltd.) equipped with a continuous attachment such that the mass flow rate ratio was 2: 1, and the residence time was 2 minutes. , Rotation speed 15000
Granulation was performed at rotation / minute to obtain a polymerizable monomer composition suspension.

(Polymerization Step) The polymerizable monomer composition suspension obtained in the granulation step was continuously introduced into the polymerization vessel shown in FIG. 1 and polymerization was carried out at 80 ° C. with stirring. At this time, the internal volume of the polymerization container is such that the introduced polymerizable monomer composition suspension is retained for 8 hours and then discharged, the rotation speed of the stirring blade, the opening area of the partition plate. Is q / Q = 35 and A / q = 1.5 × 10 ⁻⁴ [Q (m ³ / hr) is the flow rate of the inflowing polymerizable monomer composition dispersion liquid, and q (m ³ / hr) is stirring Circulation flow in each sub-compartment caused by blades, A
(M ² ) indicates the area of the opening of the partition plate. ] Was set to meet.

Dilute hydrochloric acid was added to the polymer composition suspension discharged from the polymerization container to dissolve the dispersant covering the surface of the polymer particles, and solid-liquid separation was performed, followed by washing with water, filtration and drying to obtain a polymerized toner. The particles were obtained. After continuously polymerizing for 24 hours, when the inside of the polymerization vessel was observed after the liquid was completely discharged from the polymerization vessel, no deposits were found in the polymerization vessel, and even if the continuous operation was restarted as it was There was no problem.

(Evaluation of Toner) When the particle size distribution of the toner particles was measured, the volume average particle size was 7.3 μm, the particle size distribution was sharp, and the triboelectric charge amount was −38 mC / kg, which was a good value. . The resulting toner has a polymerization conversion rate of 10
It was 0%.

Next, hydrophobic silica was externally added to the obtained toner particles to obtain a one-component developer. When an image output test was performed on 20,000 sheets, the fog was 0.6%, and the image density was not fluctuated from beginning to end, and a clear image having excellent fixability was stably obtained.

[0100]

According to the present invention, in the method for producing a polymerization toner by a continuous suspension polymerization method, the inside of the tank reactor is divided into a plurality of small partitions by partition plates, and the partition plates are Is provided with an opening so that the liquid can flow between the adjacent compartments, each small compartment has a stirring means, and the polymerizable monomer composition dispersion liquid is introduced into one small compartment to introduce a multi-ended small compartment. By using a polymerization device that has a structure that allows it to be withdrawn from the compartment, and operating it under conditions where there is essentially no gas phase in the reactor, the polymerization toner that has not reached the desired polymerization conversion rate due to insufficient residence time. There is no adverse effect on the product properties due to a large amount of particles or delaminated deposits in the polymerization equipment being mixed in the product, and the work of removing the deposits in the polymerization equipment is essentially unnecessary and continuous. Polymerization method that can be operated so that high production efficiency can be achieved Method for producing a toner is provided.

[Brief description of drawings]

FIG. 1 is a diagram illustrating an example of a continuous polymerization apparatus according to the present invention.

FIG. 2 is a diagram illustrating an apparatus used to measure a triboelectric charge amount of toner.

[Explanation of symbols]

1. Tank type reactor can 2. Partition board 3. Heating cooling jacket 4. Stirring blade 5. Stirring shaft 6. Partition plate opening 7. Liquid inlet 8. Liquid outlet 9. Stirring motor 11. Suction machine 12. Measuring container 13. screen 14. lid 15. Vacuum gauge 16. Air flow control valve 17. Suction port 18. condenser 19. Electrometer

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Takeshi Tsujino             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation (72) Inventor Yoshinori Tsuji             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation F-term (reference) 2H005 AB06                 4J011 AA06 AB09 AC06 BA01 BB01                       DA03 DB13 DB19

Claims (5)

[Claims] 1. A polymerizable monomer composition comprising a polymerizable monomer composition containing at least a polymerizable monomer and a colorant dispersed in an aqueous dispersion medium using a stirrer having a high shearing force. In the method for producing a polymerization toner, which is a colored polymer particle obtained by preparing a dispersion liquid and polymerizing the dispersion liquid of the polymerizable monomer composition, a step of polymerizing the dispersion liquid of the polymerizable monomer composition. Is carried out in a polymerization device in which the supply and the withdrawal of the dispersion liquid are carried out continuously. 2. The polymerization apparatus is a tank reactor, the inside of which is divided into a plurality of small compartments by partition plates, and the partition plates are provided with openings so that liquid can flow between adjacent compartments. Each of the small compartments is provided with a stirring means, and the polymerizable monomer composition dispersion liquid is introduced into the small compartment at one end and withdrawn from the small compartment at the multi-end. 1. The method for producing a polymerization toner according to 1. 3. Small compartments partitioned by a partition plate inside the tank reactor are connected in series through the opening of the partition plate, and the polymerizable monomer composition dispersion introduced therein is provided. The method for producing a polymerized toner according to claim 2, wherein the method has a structure that allows the toner to flow without backflow, splitting, joining, and retention of the flow. 4. A partition plate for partitioning the inside of the tank reactor into a plurality of small compartments is installed perpendicularly to the central axis of the tank reactor, and has a stirring shaft that penetrates each partition plate. The method for producing a polymerized toner according to claim 2, wherein at least one agitating blade is attached to each of the small compartments. 5. The flow rate Q (m ³ / hr) of the inflowing polymerizable monomer composition dispersion and each small amount generated by a stirring blade in each small section partitioned by a partition plate inside the tank reactor. The circulation flow rate q (m ³ / hr) in the compartment satisfies the following equation q / Q ≦ 45, and q and the area A (m ² ) of the opening of the partition plate.
The method for producing a polymerized toner according to any one of claims 2 to 4, characterized in that the above formula A / q ≦ 5 × 10 ⁻⁴ is satisfied.