JP2001188382A - Method for manufacturing polymerized toner, polymerization device for manufacturing polymerized toner and distillation device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing polymerized toners which does not form scale-like deposits on the surfaces of parts projecting to the gaseous phase section of a polymerization vessel among the members constituting a polymerization device in a polymerization stage. SOLUTION: The method for manufacturing the polymerized toners having the colored polymer particles obtained by polymerizing a polymerizable monomer composition having at least a polymerizable monomer, coloring agents, release agent and crosslinking agent in an aqueous dispersion medium consists in cooling the surfaces of the parts projecting to the gaseous phase section of the polymerization vessel 1 among the members constituting the polymerization device by a cooling medium during polymerization.

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 by a polymerization method used in electrophotography, electrostatic recording, magnetic recording, toner jet recording, and the like. Further, the present invention relates to a manufacturing apparatus for manufacturing such a polymerized toner.

[0002]

2. Description of the Related Art Conventionally, electrophotography has been disclosed in U.S. Pat. No. 2,297,691, Japanese Patent Publication No. 42-23910.
Many methods are known as described in Japanese Patent Application Laid-Open Nos. 43-48748 and 43-24748. Generally, a photoconductive substance is used to form an electric latent image on a photoreceptor by various means. The latent image is formed, then developed using toner, and a toner image is transferred to a transfer material such as paper as necessary, and then fixed by heat, pressure, etc. to obtain a copy image. Various methods have been conventionally proposed as a method of developing with toner or a method of fixing a toner image.

[0003] The toner is required to have excellent fluidity and stable triboelectrification, not to cause fogging on the photoreceptor or to reduce the image density for a long period of time, and to be capable of high quality printing. Can be If the fluidity of the toner is poor, the supply of the developer becomes defective, so that the image is blurred or the image density is reduced. In addition, cleaning failure occurs, the developer remains on the photoconductor, fogging occurs, and filming with toner occurs. When a toner film is formed on the photoreceptor, white spots and black stains occur on the image, and the image quality is reduced.

In order for the toner to exhibit excellent fluidity and form a high quality image, it is desirable that the toner be spherical and have a small particle size distribution.

Conventionally, toners used for these purposes are generally prepared by melt-mixing a colorant comprising a dye and a pigment in a thermoplastic resin and uniformly dispersing the same, and then using a pulverizer or a classifier to obtain a toner having a desired particle size. It has been manufactured as

[0006] Although this method can produce fairly good toners, it does have certain limitations, namely the choice of toner materials. For example, the resin colorant dispersion must be sufficiently brittle and capable of being pulverized in economically feasible manufacturing equipment. However, if the resin colorant dispersion is made brittle to satisfy these requirements, the particle size range of the particles formed when actually pulverized at high speed tends to be widened,
In particular, there is a problem that a relatively large proportion of fine particles are contained therein. In order for a toner to exhibit satisfactory development characteristics, its particle size distribution must be somewhat narrow. Therefore, it is necessary to classify the particles obtained by grinding to remove coarse particles and fine particles. Therefore, in the pulverization method, the yield is low and the toner yield is low.

Further, such a highly brittle material is susceptible to further fine pulverization or powdering when used for development in a copying machine or the like, which adversely affects the developability.

Further, in this method, it is difficult to completely and uniformly disperse solid fine particles such as a colorant in a resin.
Depending on the degree of dispersion, fog may increase, image density may decrease, and color mixing / transparency may be impaired. Therefore, sufficient attention must be paid to the dispersion of the colorant. Also,
Exposure of the colorant to the fracture surface of the pulverized particles may cause fluctuations in development characteristics. Further, it is difficult to produce a spherical toner having a uniform surface by the pulverization method, and it is difficult to obtain a toner having satisfactory fluidity and triboelectricity.

In addition, in the case of toners obtained by these pulverization methods, there is a limitation in the case where a releasable substance such as wax is added. That is, in order to obtain a sufficient level of dispersibility of the releasable substance, it is necessary to maintain a certain degree of viscosity at the kneading temperature with the resin, and the content of the releasable substance is reduced to about 5% by mass or less. And so on. Due to such restrictions, there is a limit to the fixability of the toner by the pulverization method.

In order to overcome the problems of the toner caused by these pulverizing methods, Japanese Patent Publication Nos. 36-10231 and 43-1
Various polymerization toners and production methods thereof have been proposed, including suspension polymerization toners disclosed in Japanese Patent Application Laid-Open Nos. 0799 and 51-14895 and the like. For example, in a suspension polymerization method toner, a polymerizable monomer, a colorant, a polymerization initiator, and if necessary, a crosslinking agent, a charge control agent, and other additives are uniformly dissolved or dispersed to form a monomer composition. After that, the monomer composition is dispersed in a continuous phase containing a dispersion stabilizer, for example, an aqueous phase using a suitable stirrer, and simultaneously subjected to a polymerization reaction, thereby obtaining a toner having a desired particle size. Get the particles. Since this method does not include a pulverizing step at all, the toner does not need to be brittle, a soft material can be used as a resin, and the colorant is not exposed on the surface of the particles. There is an advantage of having a triboelectric charging property. Further, since the particle size distribution of the obtained toner is relatively sharp, even if the classification step is omitted or the classification is performed, the toner can be obtained in a high yield. Further, according to this method, in addition to the restrictions imposed on the above-mentioned pulverized toner, the wax can be securely included, and good fixing properties and anti-offset properties can be obtained. The polymerized toner obtained by this method is spherical, has a uniform surface, and exhibits good development characteristics.

[0011] As described above, the polymerized toner by the suspension polymerization method generally has a uniform shape close to a sphere, and thus has good fluidity and transferability. Of the film, and the occurrence of filming on the photoreceptor is small.

However, a close observation of the polymerized toner revealed that a small amount of a colorless toner having no irregular shape or containing no colorant (hereinafter, referred to as “unregular toner”) was present. Amorphous toners are considered to have a different production process from ordinary polymerized toners.If this proportion increases, toner characteristics such as triboelectricity and development characteristics when images are evaluated are adversely affected, and image density fluctuations and white Streaks, fogging, etc. are seen. Therefore, in the production method of the polymerized toner, preventing the generation of the irregular toner is an important matter not only in the characteristics of the toner but also in the production cost.

[0013]

The present inventors have focused on the polymerization step and the distillation step as causes of the formation of the irregular toner in the above-mentioned polymerization method toner, and have studied in detail the phenomena occurring during both steps. Was done. Then, at the time of the polymerization step and the distillation step, of the members constituting the polymerization apparatus and the distillation apparatus, that is, the stirrer shaft, baffle plate, various sensors and their protective tubes, etc., protruded into the gas phase of the polymerization vessel and the distillation vessel. It was discovered that scale-like deposits were formed in the portions, and it was found that there was a correlation between the amount of the scale-like deposits and the proportion of the irregular toner in the obtained polymerized toner. This scale-like deposit is mixed in by peeling and is observed as an irregular toner.

The process for producing the scale-like deposits is considered to be as follows. . The unreacted polymerizable monomer vapor condenses on the surface of the member that protrudes into the gas phase in the vessel, and is heated and polymerized in the gas phase, resulting in a composition different from the normal polymerization reaction in the liquid phase.
The in-process polymer forms and attaches / deposits. . Due to the droplets and foaming of the suspension polymerization reaction liquid, the suspended polymer particles adhere to the surface of the member protruding into the gas phase in the container, and are dried / coagulated by heat. If the surface temperature of the accessory is higher than the glass transition temperature of the polymer formed by the polymerization of the polymerizable monomer, fusion occurs and the adhesion becomes strong. . The above and the above occur in combination.

In the course of the study, if the scale-like deposit grows to a sufficient size and peels off / falls off, it becomes clogged or adhered by a pipe or valve connected to the polymerization vessel or distillation vessel. Turned out to be the cause.
This is not preferable because frequent removal of scale-like deposits is required, which lowers the operation rate of the manufacturing apparatus and, as a result, increases the cost of the product toner.

Accordingly, an object of the present invention is to provide, in a polymerization step and a distillation step, a scale-shaped surface of a part of a member constituting a polymerization apparatus and a distillation apparatus, which protrudes into a gas phase portion of a polymerization vessel and a distillation vessel. An object of the present invention is to provide a method for producing a polymerized toner which does not generate a kimono, and a polymerization apparatus and a distillation apparatus for realizing the method.

[0017]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in order to suppress the formation of scale-like deposits in the polymerization and distillation steps. As a result, of the members constituting the polymerization apparatus and the distillation apparatus, It has been found that the following effects can be obtained by cooling the portions of the polymerization vessel and the distillation vessel that protrude into the gas phase. . The polymerization rate of the unreacted monomer condensed on the surface of the above member is reduced, and the formation of a polymer in a composition and a production process different from a normal polymerization reaction is suppressed. . Suppression of drying / coagulation by heat of suspended polymer fine particles adhered on the surface of the member by splashing or foaming of the suspension polymerization reaction solution. . The amount of vapor condensed on the surface of the member increases, and the condensed liquid always flows down the surface and keeps a wet state, whereby an adhesion preventing / cleaning effect can be obtained.

Based on the above findings, the present inventors have completed the present invention.

That is, the present invention provides a colored polymer obtained by polymerizing a polymerizable monomer composition having at least a polymerizable monomer, a colorant, a release agent and a crosslinking agent in an aqueous dispersion medium. In the method for producing a polymerized toner having coalesced particles, during polymerization, of the members constituting the polymerization apparatus,
The present invention relates to a method for producing a polymerized toner, characterized in that a surface of a portion protruding into a gas phase portion in a polymerization vessel is cooled by a cooling medium.

Further, the present invention provides a method for polymerizing a polymerizable monomer composition having at least a polymerizable monomer, a colorant, a release agent and a cross-linking agent in an aqueous dispersion medium, followed by a distillation operation. In a method for producing a polymerized toner having colored polymer particles obtained through a step of removing unreacted polymerizable monomer out of the system, a polymerization apparatus and / or a distillation apparatus are configured during polymerization and / or distillation. The present invention relates to a method for producing a polymerized toner, characterized in that the surface of a part of the member to be projected, which protrudes into the gas phase in a polymerization vessel and / or a distillation vessel, is cooled by a cooling medium.

Further, the present invention provides a colored polymer obtained by polymerizing a polymerizable monomer composition having at least a polymerizable monomer, a colorant, a release agent and a crosslinking agent in an aqueous dispersion medium. A polymerization apparatus used in a method for producing a polymerized toner having coalesced particles, among members constituting the polymerization apparatus, a member having a portion protruding into a gas phase portion in a polymerization container is provided inside the portion. The present invention relates to a polymerization apparatus, which is a member capable of cooling the surface of the portion by flowing a cooling medium.

Further, the present invention provides a method for polymerizing a polymerizable monomer composition having at least a polymerizable monomer, a colorant, a releasing agent and a crosslinking agent in an aqueous dispersion medium, and then performing a distillation operation. A distillation apparatus used in a method for producing a polymerized toner having colored polymer particles, which is obtained through a step of removing unreacted polymerizable monomers, wherein, among members constituting the distillation apparatus, inside a distillation container The present invention relates to a distillation apparatus, characterized in that a member having a portion protruding into the gas phase portion is a member capable of cooling the surface of the portion by flowing a cooling medium into the portion.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The method for producing the polymerized toner of the present invention includes:
A releasing agent, a colorant, a charge control agent, a polymerization initiator, a crosslinking agent and other additives are added to the polymerizable monomer, and the mixture is uniformly dissolved or dispersed with an ordinary stirrer such as a homogenizer or an ultrasonic disperser. The monomer composition was dispersed in an aqueous phase containing a dispersion stabilizer using a stirrer having a high shearing force such as Clearmix or a homomixer. The agitation speed / time is adjusted so as to have a size of and granulation is performed. In the suspension polymerization method, 100 to 3% of water is usually added to 100% by mass of the monomer system.
Preferably, 000% by mass is used as the dispersion medium. Thereafter, the state of the particles is maintained by the action of the dispersion stabilizer, so that the stirring may be performed to such an extent that the particles are prevented from settling. The polymerization is performed at a polymerization temperature of 40 ° C. or higher, generally 50 to 90 ° C. In addition, the temperature may be raised in the latter half of the polymerization reaction in order to obtain a desired molecular weight distribution. In addition, in order to remove unreacted polymerizable monomers and by-products, the temperature may be increased in the latter half of the reaction or after the reaction is completed. The partial aqueous medium may be distilled off by a distillation operation. After the reaction, the generated toner particles are collected by washing and filtration, and dried.

As the polymerizable monomer used in the toner of the present invention, a vinyl polymerizable monomer capable of radical polymerization is used. As the vinyl polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used. Monofunctional polymerizable monomers include styrene; α-methylstyrene, β-methylstyrene, o-
Methyl styrene, m-methyl styrene, p-methyl styrene, 2,4-dimethyl styrene, pn-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, p- Styrene derivatives such as n-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene and p-phenylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-
Propyl acrylate, n-butyl acrylate, is
o-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate Acrylic polymerizable monomers such as ethyl acrylate, dibutyl phosphate ethyl acrylate and 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate , Tert
-Butyl methacrylate, n-amyl methacrylate,
Methacrylic polymerizable monomers such as n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethyl phosphate ethyl methacrylate, dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid esters; acetic acid Vinyl esters such as vinyl, vinyl propionate, vinyl butyrate, vinyl benzoate and vinyl formate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone. No.

Examples of the polyfunctional polymerizable monomer include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, and 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- (methacryloxy diethoxy) phenyl) propane, 2,
2'-bis (4- (methacryloxypolyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethanetetramethacrylate, divinylbenzene, divinylnaphthalene, divinylether, and the like.

In the present invention, the above-mentioned monofunctional polymerizable monomers may be used alone, in combination of two or more, or
The monofunctional polymerizable monomer and the polyfunctional polymerizable monomer described above are used in combination. 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 the developing characteristics and durability of the toner.

The coloring agent used in the present invention includes, for example, carbon black, iron black and 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.
Modant 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. Modant Blue 7, C.I. I. Direct Green 6, C.I.
I. Basic Green 4, C.I. I. Dyes such as Basic Green 6; graphite, 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.

In the present invention in which the polymerization is carried out in an aqueous dispersion medium, it is necessary to pay attention to the polymerization inhibitory property and the aqueous phase migration property of the colorant. It is better to perform a hydrophobic treatment.
In particular, attention must be paid to the use of dyes and carbon black since many of them have polymerization inhibitory properties. As a preferable method for surface-treating the dye system, there is a method in which a polymerizable monomer is polymerized in the presence of these dyes in advance, and the obtained colored polymer is added to the monomer system. Further, regarding carbon black, in addition to the same treatment as the above-described dye, a graft treatment with a substance that reacts with the surface functional group of carbon black, for example, a polyorganosiloxane may be performed. In the present invention, a magnetic material may be added, but it is also preferable to use the material after performing a surface treatment.

As the release agent, a wax in a solid state at room temperature is preferable. In particular, a solid wax having a melting point of 40 to 100 ° C. is good in terms of the anti-blocking property, the durability of many sheets, the low-temperature fixing property, and the anti-offset property of the toner. .

As the wax, paraffin wax,
Polyolefin wax, microcrystalline wax, polymethylene wax such as 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 sharp maximum endothermic peak in a DSC endothermic curve from which low molecular weight components have been removed are preferred.

Preferred waxes include linear alkyl alcohols having 15 to 100 carbon atoms,
Examples include linear fatty acids, linear acid amides, linear esters, and montan derivatives. It is also preferable that impurities such as liquid fatty acids have been removed from these waxes in advance.

Further, preferably used wax is
Low molecular weight alkylene polymer obtained by radical polymerization of alkylene under high pressure or low pressure under Ziegler catalyst or other catalyst; alkylene polymer obtained by thermal decomposition of high molecular weight alkylene polymer; A product obtained by separating and purifying a low-molecular-weight alkylene polymer produced as a by-product; from a synthetic polymer gas consisting of carbon monoxide and hydrogen, obtained from the distillation residue of a hydrocarbon polymer obtained by the Age method or from a synthetic carbon obtained by hydrogenating the distillation residue A polymethylene wax obtained by extracting and separating a specific component from hydrogen can be used. An antioxidant may be added to these waxes.

In order to improve the translucency of the fixed image,
Solid ester waxes are preferred, and those having a melting point of 40 to 100 ° C. are particularly preferred.

The ester wax used in the present invention is formed of a compound represented by the following formulas (I) to (VI) and has a melting point of 40 to 100 ° C.

[0036]

Embedded image (Where a and b are integers from 0 to 4, and a + b is 4
It is. R ₁ and R ₂ are organic groups having 1 to 40 carbon atoms, and the difference between R ₁ and R ₂ is 3 or more. m and n are integers from 0 to 25, and m and n do not become 0 at the same time. )

[0037]

Embedded image (Where a and b are integers of 0 to 3, and a + b is 1 to 3)
3. R ₁ and R ₂ are organic groups having 1 to 40 carbon atoms, and the difference between R ₁ and R ₂ is 3 or more. R ₃ is a hydrogen atom and an organic group having 1 or more carbon atoms. Where a + b =
In the case of 2, one of R ₃ is an organic group having 1 or more carbon atoms. k is an integer of 1 to 3. m and n are 0 to
This is an integer of 25, and m and n do not become 0 at the same time. )

[0038]

Embedded image (Wherein, R ₁ and R ₃ are organic groups having 6 to 32 carbon atoms, and R ₁ and R ₃ may or may not be the same.
₂ represents an organic group having 1 to 20 carbon atoms. )

[0039]

Embedded image (Wherein R ₁ and R ₂ are organic groups having 6 to 32 carbon atoms, and R ₁ and R ₃ may or may not be the same.
_{2 -CH 2 CH 2 OC 6 H 4} OCH 2 CH 2 -,

[0040]

Embedded image (In the formula, a is an integer of 0 to 4, b is an integer of 1 to 4, a + b is 4. R ₁ is an organic group having 1 to 40 carbon atoms. M and n are 0. An integer of 〜25, m and n
Do not become 0 at the same time. )

[0041]

Embedded image (Wherein R ₁ and R ₂ are the same or different and each have 15 to 45 carbon atoms)
Represents a hydrocarbon group. )

The melting point of the ester wax is from 40 to
100 ° C. is preferred. When the melting point is less than 40 ° C., the blocking resistance and shape retention of the toner are insufficient, and when it exceeds 100 ° C., the releasing effect becomes insufficient. The following are exemplified as ester waxes as a release agent comprising an ester compound.

[0043]

Embedded image

[0044]

Embedded image

When the release agent is an ester wax having an ester compound having the above structural formula, it exhibits good transparency, and exhibits good fixability when incorporated in toner particles. is there.

In the present invention, the release agent is blended in an amount of 5 to 40% by mass (more preferably 10 to 30% by mass) with respect to 100% by mass of the polymerizable monomer. The releasing agent is preferably contained in the toner particles in an amount of 5 to 40% by mass (more preferably 10 to 30% by mass) per 100% by mass of the binder resin formed from the monomer.

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

As the charge control agent, known ones can be used. For example, organometallic compounds and chelate compounds are effective for controlling the toner to be negatively charged, and monoazo metal compounds, acetylacetone metal compounds and aromatic compounds are effective. There are aromatic hydroxycarboxylic acids and aromatic dicarboxylic acid-based metal compounds. Others include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and metal salts thereof,
Examples include anhydrides, esters, and phenol derivatives such as bisphenol.

Also, urea derivatives, metal-containing salicylic acid compounds, quaternary ammonium salts, calixarenes, silicon compounds, styrene-acrylic acid copolymers, styrene-
Examples include methacrylic acid copolymers, styrene-acrylsulfonic acid copolymers, and nonmetal carboxylic acid compounds.

The toner is controlled to have a positive charge by modifying the toner with nigrosine and a fatty acid metal salt, and quaternary compounds such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate and tetrabutylammonium tetrafluoroborate. Onium salts such as ammonium salts and phosphonium salts, which are analogs thereof, and their lake pigments, triphenylmethane dyes, and these lake pigments (as a lake-forming agent, 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,
Cyorganotin oxides such as dicyclohexyltin oxide; diorganotin borates such as dibutyltin borate, dioctyltin borate and dicyclohexyltin borate; and these can be used alone or in combination of two or more. Of these, charge control agents such as nigrosine and quaternary ammonium salts are particularly preferably used.

These charge control agents are preferably used in an amount of 0.01 to 20% by mass (more preferably 0.5 to 10% by mass) based on 100% by mass of the resin component.

In the case of a color toner, a charge control agent which is colorless and has a high charge speed of the toner and can stably maintain a constant charge amount is particularly preferable. Further, in the case of a toner obtained by a polymerization method, a charge control agent having no polymerization inhibitory property and having no soluble substance in an aqueous system is particularly preferable.

As a polymerization initiator required for polymerizing the polymerizable monomer, for example, 2,2′-azobis- (2,
4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4-
Azo polymerization initiators such as methoxy-2,4-dimethylvaleronitrile and azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, t-
A peroxide polymerization initiator such as butylperoxy-2-ethylhexanoate, diisopropylperoxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide and the like is used. The amount of the polymerization initiator varies depending on the desired degree of polymerization, but is generally used in an amount of 0.5 to 20% by mass based on the monomer. Although the type of the initiator slightly varies depending on the polymerization method, it is used alone or in combination with reference to the 10-hour half-life temperature.

Examples of the crosslinking agent include polyfunctional compounds such as divinylbenzene, 4,4′-divinylbiphenyl, ethylene glycol di (meth) acrylate, glycidyl (meth) acrylate, and trimethylolpropane tri (meth) acrylate. Can be mentioned.

Examples of dispersion stabilizers for dispersing the polymerizable monomer composition in an aqueous medium favorably include, for example, inorganic oxides such as tricalcium phosphate, magnesium phosphate, aluminum phosphate and phosphoric acid. Examples include zinc, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina, magnetic material, and ferrite.
As the organic compound, for example, polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salt of carboxymethylcellulose, starch and the like are used by being dispersed in an aqueous phase. These dispersion stabilizers are polymerizable monomers 100
It is preferable to use 0.2 to 10.0% by mass based on the mass%.

As these dispersion stabilizers, commercially available ones may be used as they are, but in order to obtain finely dispersed particles having a uniform particle size, the inorganic compound is formed under high-speed stirring in a dispersion medium. You can also. For example, in the case of tricalcium phosphate, a dispersant suitable for a suspension polymerization method can be obtained by mixing an aqueous solution of sodium phosphate and an aqueous solution of calcium chloride under high-speed stirring. Further, 0.001 to 0.1% by mass of a surfactant may be used in combination for making these dispersants finer. Specifically, commercially available nonions,
Anionic and cationic surfactants can be used, for example, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, 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 as in the case of suspension polymerization, it is possible to promote the inclusion of a release agent by adding a polar resin to the polymerizable monomer composition. it can. When a polar resin is present in the polymerizable monomer composition in the aqueous medium, the polar resin migrates to the vicinity of the interface between the aqueous medium and the polymerizable monomer composition due to a difference in hydrophilicity. Resin is unevenly distributed. As a result, the toner particles have a capsule structure, and even when a large amount of the release agent is contained, the encapsulation of the release agent is improved.

When the polar resin is unevenly distributed on the toner surface, the flowability of the polar resin itself can be expected.
Particularly, a polyester resin is preferable.

The polar resins that can be used in the toner of the present invention include terephthalic acid, isophthalic acid, phthalic acid, fumaric acid, maleic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, Acid component monomers such as azelaic acid, sebacic acid, succinic acid, cyclohexanedicarboxylic acid and trimellitic acid; and ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3
Alkylene glycols and polyalkylene glycols such as propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-bis (hydroxymethyl) cyclohexane, bisphenol A, hydrogenated bisphenol, and ethylene oxide adduct of bisphenol A And phenol oxide adduct of bisphenol A, glycerin, trimethylolpropane, and polyhydric alcohol monomers such as pentaerythritol.

In using the toner produced by the present invention, an external additive can be used for the purpose of imparting various properties. As the external additive, from the viewpoint of durability when added to the toner, 1/1 of the weight average diameter of the toner particles is used.
The particle size is preferably 0 or less. The particle size of the additive means an average particle size obtained by observing the surface of the toner particles with an electron microscope. As the external additive, for example, the following are used.

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.), metals Salts (calcium sulfate, barium sulfate, calcium carbonate, etc.), fatty acid metal salts (zinc stearate, calcium stearate, etc.), carbon black, silica, etc.

These external additives consist of 100% by mass of toner particles.
Is used in an amount of 0.01 to 10% by mass, and preferably 0.05 to 5% by mass. These external additives may be used alone or in combination. Those subjected to a hydrophobic treatment are more preferable.

Further, the toner of the present invention may be used as a magnetic toner by containing a magnetic material. In this case, the magnetic material can also serve as a colorant. In the present invention, the magnetic material contained in the magnetic toner includes iron oxides such as magnetite, hematite, and ferrite; metals such as iron, cobalt, and nickel; or aluminum, cobalt, copper, lead, magnesium, and the like of these metals. Tin, zinc, antimony, beryllium, bismuth, cadmium,
Examples include alloys of metals such as calcium, manganese, selenium, titanium, tungsten, and vanadium, and mixtures thereof.

These ferromagnetic materials preferably have an average particle size of 2 μm or less, preferably about 0.1 to 0.5 μm. The amount to be contained in the toner is preferably about 20 to 200% by mass with respect to 100% by mass of the resin component, and particularly preferably 40 to 150% by mass with respect to 100% by mass of the resin component.

The magnetic characteristics at an applied voltage of 800 kA / m are such that the coercive force (Hc) is 1.6 to 24 kA / m and the saturation magnetization (σ
s) 50 to ²⁰⁰ Am ² / kg, remanent magnetization (σr) 2
Those having ²⁰ Am ² / kg are preferred.

In the manufacturing method and apparatus according to the present invention,
Among the members constituting the polymerization / distillation apparatus, those having a portion protruding from the gas phase in the polymerization / distillation vessel include nozzles such as a stirrer shaft, baffle plates, material input ports, various sensors, and their protective tubes. And the like. As a material of each of these members, a commonly used material such as stainless steel, glass, or FRP can be used. In addition, these surfaces may be subjected to treatment such as electrolytic polishing, Teflon coating, and glass lining.

A method of cooling a member having a portion projecting from a gas phase in a polymerization / distillation vessel has a hollow portion such as a double-pipe structure therein, and the inside of the portion is formed of water, ethylene glycol or the like. Is carried out by flowing a general cooling medium. When the member having a portion protruding from the gas phase in the polymerization / distillation vessel has a portion that comes into contact with the suspension, it is necessary to devise not to cool the contact portion. It is preferable from the viewpoint of minimizing heat loss in the distillation step.

The temperature and the flow rate of the cooling medium for cooling the above-mentioned members greatly vary depending on the scale of the apparatus.
At the time of the distillation step, the amount is appropriately adjusted so as not to impair the distillation efficiency and to obtain a necessary and sufficient amount of vapor condensation on the surface of the member. The temperature of the introduced cooling medium is usually -10 to
Set within the range of 50 ° C, more preferably 0 to 40 ° C
Is set within the range. Further, the flow rate of the cooling medium is adjusted so that the difference between the inlet temperature and the outlet temperature of the above-mentioned member to the cooling section is within 10 ° C, more preferably within 5 ° C.

The stirring blade used in the polymerization apparatus according to the present invention is not particularly limited as long as the suspension is stirred without stagnation, and general stirring blades such as paddle blades, turbine blades, anchor blades and the like can be used. Commercially available full zone wings (manufactured by Shinko Pantech Co., Ltd.) and Max Blend wings (manufactured by Sumitomo Heavy Industries, Ltd.) can be used. Among these, a full zone blade and a max blend blade are preferable from the viewpoint of stirring efficiency, and a full zone blade is particularly preferably used.

Further, in the distillation apparatus according to the present invention,
A stirring device is used from the viewpoint of distillation efficiency. In this case, the same stirring blade as that used in the polymerization device can be selected.

One preferred embodiment of the polymerization apparatus used in the present invention will be described with reference to FIG. The polymerization apparatus according to this embodiment includes a polymerization vessel 1, a coolable stirrer shaft 2, a stirring blade 3, a coolable baffle 4, a heating jacket 5, and a stirring motor 6.
And a raw material inlet 7 that can be cooled.

Reference numeral 19 denotes the liquid level of the suspension, but the cooling refrigerant does not flow through the liquid contact portions of the stirrer shaft 2 and the baffle plate 4 which are indicated by oblique lines.

Various pipes are connected to this polymerization apparatus. In one example, reference numeral 8 denotes a liquid outlet, and reference numeral 9 denotes a liquid outlet.
And 10 indicate the inlet and outlet of hot water or steam for the heating jacket, respectively, 13 and 15 indicate the inlet of the cooling refrigerant for the baffle plate, and 14 and 16 respectively.
Indicates the outlet of the cooling refrigerant for the baffle plate, and reference numerals 17 and 18
Indicates an inlet and an outlet of the cooling refrigerant at the raw material input port, respectively.

Next, a preferred embodiment of the distillation apparatus used in the present invention will be described with reference to FIG. The distillation apparatus according to the present embodiment includes a distillation vessel 21, a coolable stirrer shaft 22, a stirring blade 23, a coolable baffle 24, and a heating jacket 2.
5. Stirring motor 26 and raw material inlet 2 that can be cooled
Seven.

Reference numeral 40 denotes the liquid level of the suspension. The liquid contact portion of the stirrer shaft 22 and the baffle plate 24, which is indicated by oblique lines, is provided so that the cooling refrigerant does not flow through the cooling liquid contact portion. Has become.

Various pipes are connected to the distillation apparatus. For example, reference numeral 29 denotes a liquid outlet, and reference numerals 30 and 31 denote an inlet and an outlet of hot water or steam for a heating jacket, respectively. , 32 and 33 indicate the inlet and outlet of the cooling refrigerant of the stirrer shaft, 34 and 36 indicate the inlet of the cooling refrigerant of the baffle plate, and 35 and 37 indicate the outlet of the cooling refrigerant of the baffle plate. Numerals 38 and 39 denote an inlet and an outlet of the cooling refrigerant at the raw material input port, respectively. Reference numeral 28 indicates an outlet for distilling a fraction, and if necessary, a condenser is connected to condense the distillate to take it out. Further, when depressurization in the container is necessary, the outlet 28 for the fraction can be connected to a decompression device such as a vacuum pump.

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

On the other hand, when used as a generally used two-component developer, a carrier is used as a developer together with the toner of the present invention. The carrier used in the present invention is not particularly limited, but is mainly composed of a single ferrite and a composite ferrite composed of iron, copper, zinc, nickel, cobalt, manganese, and chromium. The carrier shape is also important because saturation magnetization and electric resistance can be controlled in a wide range. For example, it is preferable to select a spherical shape, a flat shape, an irregular shape, and the like, and to further control the fine structure of the carrier surface state, for example, the surface unevenness. . Generally, the above inorganic oxide is calcined
A method of coating the resin after forming carrier core particles in advance by granulation is used.However, from the viewpoint of reducing the load on the toner of the carrier, the inorganic oxide and the resin are kneaded and then pulverized. -A method of obtaining a low-density dispersed carrier by classification or a method of directly obtaining a polymerized carrier to obtain a spherically dispersed carrier by suspension-polymerizing a kneaded product of an inorganic oxide and a monomer in an aqueous medium is also used. It is possible to

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, coating and adhering to a carrier, and a method of simply mixing with a powder can be applied.

The substance to be fixed to the carrier surface varies depending on the toner material. Examples thereof include polytetrafluoroethylene, monochlorotrifluoroethylene polymer, polyvinylidene fluoride, silicone resin, polyester resin, metal compound of ditersharry butylsalicylic acid, and styrene-based compounds. It is appropriate to use resin, acrylic resin, polyamide, polyvinyl butyral, nigrosine, aminoacrylate resin, basic dye and its lake, silica fine powder, alumina fine powder, etc. alone or in combination, but it is not necessarily limited to this. Not done.

The treatment amount of the above compound is generally 0.1 to 30% by mass, preferably 0.5 to 20% by mass, based on 100% by mass of the carrier.

The average particle size of these carriers is 10 to 100.
μm, preferably 20 to 50 μm.

Particularly preferred modes of the carrier include:
Cu-Zn-Fe ternary ferrite whose surface is a combination of a resin such as a fluorine resin and a styrene resin, for example, polyvinylidene fluoride and styrene-methyl methacrylate resin; polytetrafluoroethylene and styrene-methyl methacrylate Resin, fluorine-based copolymer and styrene-based copolymer;
It is preferably a mixture having a ratio of 70:30 to 30:70, and 0.01 to 5% by mass, preferably 0.1 to 1% by mass.
The carrier is a coated ferrite carrier having the above-mentioned average particle size in which the carrier particles are coated by mass% and the carrier particles of 250 mesh pass and 100 mesh on are 70 mass% or more. As the fluorine-based copolymer, vinylidene fluoride-tetrafluoroethylene copolymer (10: 90-
90:10). Examples of the styrene copolymer include styrene-2-ethylhexyl acrylate (20:80).
８０80: 20), styrene-2-ethylhexyl acrylate-methyl methacrylate (20-60: 5-30: 1)
0 to 50).

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

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. Then usually good results are obtained. If the toner concentration is less than 2% by mass, the image density is low and cannot be used practically. If the toner concentration is more than 15% by mass, fog and scattering in the machine are increased, and the useful life of the developer is shortened. Further, the magnetic properties of the carrier are preferably as follows. Magnetization intensity at 80 kA / m after magnetic saturation is 30 to 300 A
It needs to be m ² / kg. In order to achieve higher image quality, it is preferable to use 100 to 250 Am ² /
kg. When it is larger than 300 Am ² / kg, it is difficult to obtain a high quality toner image. Three
If it is less than 0 Am ² / kg, carrier adhesion tends to occur because the magnetic binding force is reduced.

[0086]

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

The respective measuring methods used in the present invention will be described below.

(1) Measurement of Particle Size Distribution and Volume Average Particle Size Alkylbenzenesulfonate as a surfactant was added in an amount of 0.1 to 100 ml in 100 to 150 ml of a 1% aqueous sodium chloride solution.
5 ml was added, and 0.5 to 50 mg of a measurement sample was further added. This solution was subjected to a dispersion treatment for about 1 to 3 minutes with an ultrasonic dispersing machine, and then, with a Coulter Multisizer (manufactured by Coulter Inc.), using a 100 μm aperture to obtain 2 to 40 minutes.
The particle size distribution of the μm particles was measured, and the volume average distribution and the number average distribution were obtained, from which the volume average particle size was obtained.

(2) Image Quality Hydrophobic silica having a specific surface area of 200 m ² / g by the BET method was externally added to the obtained toner particles so as to be 0.7% by mass. A ferrite carrier coated with an acrylic resin was mixed so that the amount of the externally added toner was 8% by mass to obtain a two-component developer. In an environment in which the developer does not fluctuate, an image endurance test by continuous paper passing was performed using a modified full-color copying machine CLC500 manufactured by Canon, and fluctuation and unevenness in image density were visually evaluated.

(3) Measurement of fog The measurement of fog was performed in a REFLECTOMETER MOD.
It was measured using EL TC-6DS (manufactured by Tokyo Denshoku Co., Ltd.) and calculated by the following equation. The smaller the value, the less fog.

Fog (reflectance) (%) = reflectance of standard paper (%) − reflectance of non-image portion of sample (%)

(4) Measurement of triboelectric charge of toner The triboelectric charge of the toner was determined by blowing off the toner and carrier for 24 hours under an environment with no fluctuation, based on the blow-off method.
The triboelectric charge was measured in the following manner.

FIG. 3 is an explanatory view of an apparatus for measuring the triboelectric charge amount of toner. First, a mixture of a toner and a carrier having a mass ratio of 8:92 to be measured for a triboelectric charge amount is placed in a polyethylene bottle having a volume of 50 to 100 ml in a metal measuring container 52 having a 500-mesh screen 53 at the bottom. Shake by hand 200 times and mix the mixture (developer) about 0.2
g and a metal lid 54 is formed. At this time, the mass of the entire measurement container 52 is weighed and is defined as W ₁ (g). Next, in the suction device 51 (at least the portion in contact with the measurement container 52 is at least an insulator), the pressure from the vacuum gauge 55 is adjusted to 2450 Pa by adjusting the air volume control valve 56 by suction from the suction port 57. In this state, suction is sufficiently performed, preferably for 2 minutes, to remove the toner by suction. The maximum value of the potential indicated by the electrometer 59 at this time is defined as V (volt). Here, 58 is a capacitor whose capacity is C (μF). Further, the weight of the whole measurement container after suction is weighed to be W ₂ (g). The triboelectric charge (mC / kg) of this toner is calculated as in the following equation.

Amount of triboelectric charge (mC / kg) = C × V ÷ (W ₁ −W ₂ )

(5) Abundance of amorphous toner The toner was observed using a scanning electron microscope, and the abundance of amorphous toner was calculated. The abundance (%) of amorphous toner is calculated as in the following equation.

Irregular toner abundance (%) = number of irregular toners / number of all toners × 100

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

(Preparation of Aqueous Dispersion Medium) In a vessel having an internal volume of 160 liters, the following components were mixed and heated to 60 ° C., and then a high-speed rotary shear stirrer CLEARMIX (manufactured by M Technic Co., Ltd.) And the mixture was stirred at 6,000 rpm.・ Water 98.4% by mass ・ Na ₃ PO ₄ 1.0% by mass

Next, the inside of the vessel was replaced with nitrogen, and CaCl ₂ was added thereto at a concentration of 0.6% by mass to cause a reaction.
_An aqueous dispersion medium containing ₃ (PO ₄ ) ₂ fine particles was obtained.

(Preparation of polymerizable monomer composition) 63.9% by mass of styrene monomer 13.1% by mass of n-butyl acrylate monomer 6.2% by mass of quinacridone pigment 6.2% by mass of terephthalic acid 3.9% by mass of propylene oxide-modified bisphenol A ・ 0.2% by mass of divinylbenzene and 0.8% by mass of aluminum di-tert-butylsalicylate compound ・ 9.6% by mass of ester wax (release agent No. 5) 9.6% by mass A handy mill (manufactured by Mitsui Mining Co., Ltd.) was prepared by mixing a part of a styrene monomer, a quinacridone pigment, and an aluminum di-tert-butylsalicylate compound among the components.
After dispersing for 5 hours, the remainder of the styrene monomer and other components were added, and the mixture was heated to 60 ° C. and mixed until it was sufficiently compatible. Then, the polymerization initiator 2,
2'-azobis (2,4-dimethylvaleronitrile)
2.3% by mass was added to obtain a polymerizable monomer composition.

The above polymerizable monomer composition was put into an aqueous dispersion medium prepared in advance, and the mixture was stirred for 10 minutes at a CLEAR MIX rotation speed of 6000 rpm to perform granulation.

(Polymerization Step) The suspension granulated in the above step was introduced into the polymerization apparatus shown in FIG. 1, and polymerization was carried out at a rotation speed of a stirring blade of 80 rotations / minute and a liquid temperature of 60 ° C. After 5 hours, the polymerization temperature was raised to 80 ° C., and the heating and stirring were continued for another 3 hours to complete the polymerization. During the polymerization process, cooling water at an inlet temperature of 14.5 ° C. was introduced into the stirrer shaft and the baffle plate,
When the liquid temperature at the time of polymerization is 60 ° C., 3 liter / min, 80
In the case of ° C., cooling was performed by flowing through only the gas phase at a flow rate of 6.5 liter / min.

(Evaluation of Toner and Adhesion Condition) After the temperature of the suspension in the polymerization apparatus was lowered, the suspension was discharged from the polymerization apparatus, and diluted hydrochloric acid was added thereto to dissolve the dispersant fixed on the surface of the toner particles. After solid-liquid separation, the polymer was washed with water, filtered and dried to obtain polymerized toner particles. The abundance of the irregular toner was 0.2%. 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 as high as −40 mC / kg. Further, when the inside of the polymerization vessel after the suspension was discharged was examined, it was found that a total of 15.
6 g of scale-like deposits were produced, but even when the toner was repeatedly produced without removing the deposits, the level was no problem at all.

Next, hydrophobic silica was externally added to the obtained toner particles, and a ferrite carrier coated with an acrylic resin was mixed to obtain a two-component developer. When an image output test was performed on 20,000 sheets, fog was 0.3%, and there was no fluctuation or unevenness in image density throughout, and a clear and excellent fixability image was obtained stably.

Comparative Example 1 A toner was obtained in exactly the same manner as in Example 1, except that cooling water was not passed through the shaft of the stirrer and the baffle plate during the polymerization step. The abundance of the irregular toner was 3.4%. When the particle size distribution of the toner particles was measured, the volume average particle size was 8.
At 6 μm, the particle size distribution was almost the same as in Example 1. The triboelectric charge was -35 mC / kg. The amount of scale-like deposits was a total of 75.3 g in terms of dry mass, was partly peeled off, and was in a situation where it was impossible to repeatedly manufacture without removing the deposits.

Next, when an image output test was performed on 20,000 sheets in the same manner as in Example 1, the fog was 1.0%, and the image density was initially stable with no fluctuation or unevenness in the image density, and a stable image was obtained. However, white streaks and unevenness occurred in the second half.

Example 2 After the steps up to the polymerization step were carried out in exactly the same manner as in Example 1, the suspension was discharged from the polymerization apparatus and introduced into the distillation apparatus shown in FIG. 2, where the number of rotations of the stirring blade was 100. / Min, liquid temperature 80
Distillation was performed at 4 ° C. and a pressure in the distillation vessel of 49.3 kPa (absolute pressure) for 5 hours. During the distillation process, cooling water at an inlet temperature of 14.5 ° C. was introduced into the stirrer shaft and the baffle plate and circulated at a flow rate of 6.5 liter / min. After the distillation step was completed, the toner was evaluated.
3%. When the particle size distribution of the toner particles was measured, the volume average particle size was 8.3 μm.
It was almost the same. The triboelectric charge was -42 mC / kg. The amount of scale-like deposits in the distillation step was a total of 19.5 g in terms of dry mass, which was a level that would be satisfactory even if toner was repeatedly produced without removing the deposits.

Next, an image output test was performed on 20,000 sheets in the same manner as in Example 1. As a result, the fog was 0.5%, and there was no fluctuation or unevenness in the image density throughout, and a clear and excellent fixation image was obtained. Obtained stably.

Comparative Example 2 A toner was obtained in exactly the same manner as in Example 2 except that cooling water was not passed through the agitator shaft and the baffle plate during the distillation process. The abundance of the irregular toner was 6.1%. When the particle size distribution of the toner particles was measured, the volume average particle size was 8.4 μm, and the particle size distribution was almost the same as in Example 1. The triboelectric charge was -30 mC / kg. The amount of scale-like deposits in the distillation step was 93.
9 g, the scale-like deposits were partially peeled off and dropped off, and the production could not be repeated unless the deposits were removed.

Next, when an image output test was performed on 20,000 sheets in the same manner as in Example 1, fog was 1.5%, and a stable image was obtained at the initial stage. White streaks and unevenness occurred. Filming was slightly observed on the photoreceptor.

[0111]

According to the present invention, in a process for producing a toner by a suspension polymerization method, a part of a member constituting a polymerization / distillation apparatus, which protrudes into a gas phase portion of a polymerization / distillation vessel, is provided.
The generation of scale-like deposits can be suppressed. When the adhered substance is peeled off and mixed into a spherical toner having a regular particle size, the toner becomes an irregular-shaped toner and deteriorates the performance of the toner. However, according to the present invention, the production of the adhered substance is significantly reduced. , The removal work is essentially unnecessary,
In addition, when an image is formed, it is possible to obtain a toner capable of stably obtaining a clear image having excellent fixability without fluctuation or unevenness in image density.

Further, according to the present invention, in the step of producing a toner by the suspension polymerization method, of the members constituting the polymerization / distillation apparatus, a scale-like portion is attached to a portion of the polymerization / distillation vessel that protrudes into the gas phase. A polymerization / distillation apparatus capable of suppressing formation of a kimono is provided.

[Brief description of the drawings]

FIG. 1 is a schematic view showing one embodiment of a polymerization apparatus according to the present invention.

FIG. 2 is a schematic diagram showing one embodiment of a distillation apparatus according to the present invention.

FIG. 3 is an explanatory diagram of an apparatus for measuring a triboelectric charge amount of a toner.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Polymerization container 2,22 Stirrer shaft 3,23 Stirrer blade 4,24 Baffle plate 5,25 Heating jacket 6,26 Stirrer motor 7,27 Raw material input port 11,32 Inlet of cooling medium for stirrer shaft 12,33 Stirrer shaft Outlets for cooling refrigerants 13, 15, 34, 36 Inlets for cooling refrigerant in baffle plates 14, 16, 35, 37 Outlets for cooling refrigerants in baffle plates 17, 38 Inlet for cooling refrigerant in raw material input port 18, 39 Cooling refrigerant outlet at raw material input port 19,40 Liquid level 21 Distillation vessel

Claims (10)

[Claims] Claims 1. A colored polymer particle obtained by polymerizing a polymerizable monomer composition having at least a polymerizable monomer, a colorant, a release agent and a crosslinking agent in an aqueous dispersion medium. A method for producing a polymerization toner, comprising: cooling a surface of a part of a member constituting a polymerization apparatus, which protrudes into a gas phase part in a polymerization container, with a cooling medium during polymerization. . 2. The polymerized toner according to claim 1, wherein the method of cooling the surface of the portion projecting into the gas phase portion in the polymerization container is performed by circulating a cooling medium inside the portion. Manufacturing method. 3. The method for producing a polymerized toner according to claim 1, wherein water or ethylene glycol is circulated as the cooling medium. 4. A polymerizable monomer composition having at least a polymerizable monomer, a colorant, a release agent and a cross-linking agent is polymerized in an aqueous dispersion medium, and subsequently unreacted polymerization is carried out by a distillation operation. A method for producing a polymerized toner having colored polymer particles obtained through a step of removing a reactive monomer out of the system, wherein during polymerization and / or during distillation, among members constituting a polymerization apparatus and / or a distillation apparatus, A method for producing a polymerized toner, comprising: cooling a surface of a portion of a polymerization vessel and / or a distillation vessel that protrudes into a gas phase in a distillation vessel with a cooling medium. 5. The method for cooling the surface of a portion protruding into a gas phase in a polymerization vessel and / or a distillation vessel is performed by flowing a cooling medium through the inside of the portion. 3. The method for producing a polymerized toner according to item 1. 6. The method for producing a polymerized toner according to claim 4, wherein water or ethylene glycol is circulated as the cooling medium. 7. Colored polymer particles obtained by polymerizing a polymerizable monomer composition having at least a polymerizable monomer, a colorant, a release agent and a crosslinking agent in an aqueous dispersion medium. A polymerization apparatus used in a method for producing a polymerization toner, wherein a member having a part protruding into a gas phase part in a polymerization container among members constituting the polymerization apparatus circulates a cooling medium inside the part. A polymerization apparatus characterized in that the member is a member capable of cooling the surface of the portion by causing the member to cool. 8. The polymerization apparatus according to claim 7, wherein water or ethylene glycol is passed as the cooling medium. 9. After polymerizing a polymerizable monomer composition having at least a polymerizable monomer, a colorant, a release agent and a cross-linking agent in an aqueous dispersion medium, unreacted polymerization is performed by a distillation operation. A distillation apparatus used in a method for producing a polymerized toner having colored polymer particles, which is obtained through a step of removing into a reactive monomer, wherein a gas phase part in a distillation vessel among members constituting the distillation apparatus A distillation apparatus characterized in that a member having a portion protruding from the surface is a member capable of cooling the surface of the portion by flowing a cooling medium through the portion. 10. The distillation apparatus according to claim 9, wherein water or ethylene glycol is passed as the cooling medium.