JP2003140386A - Method for manufacturing toner by polymerization - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing toner by which a toner having sharp distribution of grain size, constant distribution of molecular weight without changing with time and excellent image characteristics can be obtained, the work to remove depositing substances in the polymerization apparatus is not required but the apparatus can be continuously operated and a high production efficiency can be obtained. SOLUTION: In the method for manufacturing toner including a polymerization process, the polymerization apparatus used for the polymerization process is a tubular reactor equipped with a reaction tube. The inner diameter d of the reaction tube constituting the tubular reactor, the flow line speed u of the dispersion liquid of the polymerizable monomer composition and its physical properties are controlled to satisfy A/B>=1 with respect to A and B defined by formulae (1) and (2), respectively. The tubular reactor has such a structure that the polymerizable monomer composition is continuously introduced into the one end of the reaction tube and that the liquid after completion of the polymerization process is continuously discharged from the other end of the reaction tube. In formulae (1) and (2), dp represents the drop diameter of the liquid drops of the polymerizable monomer composition, ρp represents the density of the liquid drops of the polymerizable monomer composition, ρL represents the density of the aqueous dispersion medium, ηrepresents the viscosity of the polymerizable monomer composition dispersion liquid, and ϕ represents the volume fraction of the polymerizable monomer composition to the whole dispersion liquid of the polymerizable monomer composition.

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 for electrostatic image development 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.
Various methods have been proposed as described in JP-A-43-24748 and JP-A-43-24748. Generally, a photoconductive substance is used to form an electrostatic latent image on a photoconductor by various means. Then, the latent image is developed with toner and, if necessary, the toner image is transferred to a transfer material such as paper, and then heat / heat is applied.
It is fixed by pressure or the like to obtain a copied image.

The toner used in the electrophotographic method has excellent fluidity and stable triboelectrification property, does not cause fog on the photosensitive member and a decrease in image density for a long time, and enables high quality printing. Is required. If the fluidity of the toner is poor, the toner may be poorly supplied, and the image may be blurred or the image density may be reduced. In addition, cleaning failure occurs, and the toner remains on the photoconductor, causing fog or filming due to the toner. When a toner film is formed on the photoconductor, white spots or 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 prepared by melting and mixing a coloring agent such as a dye / pigment in a thermoplastic resin,
After being uniformly dispersed, it has been manufactured as a toner having a desired particle diameter by a fine pulverizer and a classifier.

This manufacturing method has a certain limitation, that is, the selection range of the toner material. 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 actually finely pulverized at a high speed tends to be broad, and particularly the ratio of the formed fine particles is large. The problem arises. In order for the toner to exhibit satisfactory developing characteristics, its particle size distribution must be narrow to some extent. Therefore, it is necessary to classify the particles obtained by pulverization to remove coarse particles and fine particles. Therefore, in general, the pulverization method tends to have a poor yield and a low toner yield.

Furthermore, such a brittle material is liable to undergo further fine pulverization or pulverization when used for development in a copying machine or the like, which adversely affects the developability. Further, it is difficult to completely uniformly disperse solid fine particles such as a colorant in the resin by this method. Depending on the degree of the dispersion, fog increases, image density decreases, and color mixing / transparency is poor. Care must be taken in dispersing the colorant, as this may cause the problem. In addition, the exposure of the colorant on 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 triboelectrification.

There is a limitation in adding a releasing agent such as wax when the toner is manufactured by the pulverization method. That is, in order to obtain a sufficient level of dispersibility of the release agent, it is necessary to maintain a certain viscosity at the kneading temperature with the resin, and the content of the release agent needs to be about 5 mass% or less. There is something like that. Due to such restrictions, there are limits to the fixing property and releasability of the toner by the pulverization method.

In order to overcome the problems of the toner due to the pulverization method, Japanese Patent Publication Nos. 36-10231 and 43-10.
Various polymerization method toners and methods for producing the same have been proposed, including suspension polymerization method toners disclosed in Japanese Patent Publication Nos. 799 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 to perform polymerization. After forming the polymerizable monomer composition, the polymerizable monomer composition is dispersed in a continuous phase containing a dispersion stabilizer, for example, water using a suitable stirrer, and a polymerization reaction is performed at the same time to obtain desired particles. Obtaining toner particles having a diameter. Since this method does not include a crushing step at all, the toner 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, resulting in uniform friction. It has an advantage of having a charging property.
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.

Further, according to this method, there is no restriction imposed on the above-mentioned pulverized toner, and in addition, a release agent such as wax can be surely included, resulting in good fixing property and offset resistance. can get. Since the polymerized toner obtained by this method is spherical and has a uniform surface,
It is characterized by good transferability, good development characteristics even after continuous development a number of times, less stress on the toner, and less filming on the photoconductor.

On the other hand, in the 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, a type of stirrer having a high shearing force in dispersing and granulating a polymerizable monomer composition in an aqueous dispersion medium. In the former, continuous or batch granulation is carried out, and in the latter, continuous granulation is carried out, but the subsequent polymerization steps are all batch systems using tank-type containers. Even if the previous process is a continuous process, if the polymerization process is a batch process, you will enjoy the advantages that should be obtained by a continuous process such as high production efficiency, space saving, and stable steady-state operation. I can't.

In order to carry out the continuous polymerization easily, an ordinary tank type reactor equipped with a stirring means is used, and a liquid is continuously supplied to the reactor so as to extract an overflow.
In this method, a so-called "short pass" or the like occurs in which a portion flowing out does not pass through a sufficient residence time, and the degree of polymerization varies among particles, resulting in nonuniform product properties, which is not preferable.

On the other hand, JP-A-7-281480 and JP-A-9-43898 describe continuous polymerization using a tubular reactor. This type of reactor is generally suitable as a continuous reactor because of its simple structure and no distribution of residence time.However, in any case, the polymerizable monomer content is limited in terms of the flow linear velocity and the tube diameter of the reactor. No consideration has been given to the physical properties of the body composition suspension, and the guarantee of the flow state in the reactor pipeline is insufficient. For example, when the specific gravity of the polymerizable monomer composition is somewhat higher than that of the aqueous dispersion medium, sedimentation or deposition of the polymerizable monomer composition is likely to occur in the middle of the pipeline, which is fused and solidified to form the inner wall of the pipeline. It becomes a deposit on. If these deposits are peeled off, they may be mixed in the product and adversely affect the product properties. In addition, since the adhered material that has grown may cause the blockage of the pipeline, frequent operation stoppages and disassembly and cleaning of the reactor are unavoidable, resulting in a decrease in production efficiency.

[0016]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a polymerization toner in which a polymerizable monomer composition is dispersed in an aqueous dispersion medium and then continuously polymerized. Another object of the present invention is to provide a method for producing a toner by a polymerization method, wherein the polymerization apparatus used in the polymerization step is an apparatus that does not cause the above-mentioned problems.

[0017]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found the following method.

That is, in the present invention, a polymerizable monomer composition containing at least a polymerizable monomer is dispersed in an aqueous dispersion medium to obtain a polymerizable monomer composition dispersion, which is then polymerized. In the method for producing a toner having a polymerization step, the polymerization apparatus used in the polymerization step is a tubular reactor having a reaction tube, and the inner diameter of the reaction tube constituting the tubular reactor, the polymerizable monomer composition A and B represented by the following formulas (1) and (2) in which the distribution linear velocity of the substance dispersion liquid and its physical properties are A / B ≧
1, preferably A / B ≧ 3, and the polymerization apparatus continuously introduces the polymerizable monomer composition into one end of the tubular reactor to obtain the tubular reactor. A method for producing a polymerized toner, which has a structure in which the liquid that has undergone the polymerization process is continuously discharged from the other end of the.

[0019]

[Equation 2] (However, u is the flow velocity of the polymerizable monomer composition dispersion (m
/ S), d is the inner diameter (m) of the reaction tube constituting the tubular reactor, d _p is the droplet diameter (m) of the polymerizable monomer composition droplets,
ρ _p is the density (kg / m ³ ) of the polymerizable monomer composition droplets, ρ
_L is the density of the aqueous dispersion medium (kg / m ³ ), η is the viscosity (Pa.s) of the polymerizable monomer composition dispersion, and φ is the polymerizable monomer amount with respect to the entire polymerizable monomer composition dispersion. It represents the volume fraction of the body composition. )

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention comprises emulsion polymerization, dispersion polymerization,
It can be applied to a method for producing a toner by a polymerization method using various polymerization methods such as suspension polymerization and seed polymerization. The production of a polymerized toner by the suspension polymerization method will be described below as an example.

In the present invention, the "polymerizable monomer composition" means at least a polymerizable monomer, and more specifically, a colorant and, if necessary, a release agent, a charge control agent, a crosslinker. It is prepared by uniformly dissolving or dispersing the agent and other additives in the polymerizable monomer with a commonly used stirring device, homogenizer, ultrasonic disperser or the like.

The polymerizable monomer composition is added to an aqueous dispersion medium which may contain a dispersion stabilizer, and T. K. Homo Mixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), Clearmix (M
A polymerizable monomer composition dispersion is prepared by a dispersing means such as a stirring disperser such as Technic Co., Ltd. or an ultrasonic disperser.
Or using a porous body such as Shirasu porous glass,
It is also possible to obtain a polymerizable monomer composition dispersion by pressing the polymerizable monomer composition into an aqueous dispersion medium. This is not performed once at the time of preparing the polymerizable monomer composition dispersion, and a conventional stirrer or T.W. K. After performing a preliminary dispersion operation in a batch system using a stirrer such as Homo Disper (manufactured by Tokushu Kika Kogyo Co., Ltd.) that imparts a high shearing force, the dispersion operation is performed again by the various dispersion means described above and desired. It is also possible to prepare a polymerizable monomer composition dispersion having a droplet diameter of.
In addition, an ordinary stirrer or T.I. K. Preliminary dispersion of polymerizable monomer composition obtained by batchwise preliminarily dispersing operation using a stirrer such as Homodisper (made by Tokushu Kika Kogyo Co., Ltd.) that imparts high shearing force. It is also preferable that the polymerization initiator is introduced into the dispersing means at a predetermined ratio with respect to the polymerizable monomer composition pre-dispersion liquid through an independent route at the same time as it is reintroduced into the dispersing means.

If the polymerization initiator is not liquid at the temperature at which it is used, it is desirable to use it as a solution or suspension for easy handling. If the polymerization initiator used at this time is oil-soluble, it is dissolved in a polymerizable monomer or a polymerization-inert organic solvent to form a polymerization initiator solution, or suspended in water or an aqueous dispersion medium to suspend the polymerization initiator. It is preferably used as a liquid. If the polymerization initiator to be used is water-soluble, it is dissolved in water or an aqueous dispersion medium to form a polymerization initiator solution, or a part of the polymerizable monomer or a polymerization-inert organic solvent to dissolve the polymerization initiator. It is preferably used as a suspension. The polymerizable monomer composition dispersion obtained by these means is continuously supplied to a polymerization apparatus to carry out polymerization.

The polymerization apparatus used in the present invention is a tubular reactor having a reaction tube, and the tubular reactor has a reaction tube which may have a bent portion or a curved portion in the middle thereof. When the polymerizable monomer composition dispersion is continuously supplied to the tubular reactor, it is desirable to operate so as not to generate a gas phase part in the reaction tube.
If there is a gas phase part in the reaction tube, deposits tend to be generated in that part, which reduces the heat transfer efficiency, clogging of the reaction tube, deterioration of quality due to the inclusion of detached deposits in the product, etc. It may occur and is not preferable.

An example of the tubular reactor used in the present invention is shown in FIG. The tubular reactor includes a body 1, a reaction tube 2, a baffle plate 3,
Liquid inlet 4, liquid outlet 5, heat transfer medium inlet 6, heat transfer medium outlet 7
Have. The polymerizable monomer composition dispersion liquid introduced into the liquid inlet 4 is polymerized while passing through the reaction tube 2 whose temperature is controlled by the heat transfer medium flowing in the body 1 to form a polymer fine particle dispersion liquid. And is discharged from the liquid outlet 5. The reaction tube 2 is folded by a plurality of 180 ° bends and housed in the body 1 to form one tubular reactor. The length of the channel of the reaction tube 2 and the number of times of folding can be arbitrarily determined depending on the required residence time, installation conditions of the tubular reactor, and the like. The tubular reactor has a pipe length for a predetermined residence time, but it may be used as one machine, but if it is desired to change the polymerization temperature during the polymerization process, multiple tubular reactors should be connected in series. It can also be used by changing the polymerization temperature in each case.

The relationship between the inner diameter of the reaction tube 2, the flow rate of the polymerizable monomer composition dispersion and the physical properties thereof is represented by the following formula (1):
It is operated under the condition that A and B represented by (2) satisfy A / B ≧ 1, preferably A / B ≧ 3.

[0027]

[Equation 3] (However, u is the flow velocity of the polymerizable monomer composition dispersion (m
/ S), d is the inner diameter (m) of the reaction tube constituting the tubular reactor, d _p is the droplet diameter (m) of the polymerizable monomer composition droplets,
ρ _p is the density (kg / m ³ ) of the polymerizable monomer composition droplets, ρ
_L is the density of the aqueous dispersion medium (kg / m ³ ), η is the viscosity (Pa.s) of the polymerizable monomer composition dispersion, and φ is the polymerizable monomer amount with respect to the entire polymerizable monomer composition dispersion. It represents the volume fraction of the body composition. )

When A / B is less than 1, the floating state of the polymerizable monomer composition droplets tends to be non-uniform, and a sliding flow is formed in the lower portion of the reaction tube, and a retention portion tends to occur. In the retention part, the polymerizable monomer composition is likely to be fused to the reaction tube wall and there is a possibility that a strong deposit is formed. Accumulation / growth of the deposits is not preferable because the heat transfer performance is deteriorated, the reaction tube is clogged, and the detached deposits are mixed into the product.
In addition, since the plug flow property is impaired, the polymerization conversion rate and the molecular weight distribution tend to be non-uniform.

Flow velocity, drop diameter of polymerizable monomer composition droplets, density of polymerizable monomer composition droplets, density of aqueous dispersion medium, viscosity of polymerizable monomer composition dispersion, and The volume fraction of the polymerizable monomer composition with respect to the entire polymerizable monomer composition dispersion can be measured by a usual method.

A single or a plurality of static mixing elements may be installed in the reaction tube 2 for the purpose of assisting in maintaining the uniformity of the polymerizable monomer composition dispersion. The type of static mixing element used here can be selected arbitrarily as long as it has a function of dividing or dividing / reversing a fluid.

The polymerization reaction is carried out at 40 ° C. or higher, generally 50
It is carried out at a temperature of ~ 90 ° C. When multiple tubular reactors are connected and used, the polymerization temperature may be the same for all tubular reactors, but different polymerization temperatures should be set for each reactor in order to obtain the desired molecular weight distribution. You can also

After the completion of the polymerization step, a part of the aqueous dispersion medium may be distilled off by a distillation operation in order to remove volatile impurities such as unreacted polymerizable monomers and by-products. The distillation operation can be performed under normal pressure or reduced pressure. After the completion of the polymerization step or the distillation operation, the produced toner particles are filtered and washed, but the dispersion stabilizer on the surface of the obtained particles 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 polymerizable monomer used in the method for producing a toner by the polymerization method 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. As the monofunctional polymerizable monomer, styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene,
p-methylstyrene, 2,4-dimethylstyrene, p-
n-butyl styrene, p-tert-butyl styrene,
Styrene derivatives such as pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, and p-phenylstyrene; 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, 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, etc. Acrylic polymerizable monomer; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate,
n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethyl phosphate ethyl methacrylate, dibutyl phosphate ethyl Methacrylic polymerizable monomers such as methacrylate; vinyl esters such as methylene aliphatic monocarboxylic acid ester, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl formate; vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl Vinyl ethers such as ethers; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, vinyl isopropyl ketone and the like.

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 method for producing the polymerized toner of 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. 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 NCG, Tartrazine Lake, Molybdenum Orange, Permanent Orange GT
R, benzidine orange G, cadmium red, permanent red 4R, watching red calcium salt,
Brilliant Carmine 3B, Fast Violet B,
Pigments such as methyl violet lake, dark blue, 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 the method for producing a polymerized toner of the present invention, when selecting a colorant, it is necessary to pay attention to the polymerization inhibitory property and the water phase transfer property of the colorant, and preferably surface modification such as polymerization. It is better to make the colorant hydrophobic by a non-inhibiting substance. 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 the above-mentioned polymerizable monomer in the presence of these dyes in advance, and the obtained colored polymer is used as a polymerizable monomer composition. Added to. Further, carbon black may be subjected to a treatment similar to the above dye, or a graft treatment with a substance that reacts with the surface functional groups of carbon black, for example, polyorganosiloxane.

As the release agent used in the method for producing a toner by the polymerization method of the present invention, 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 a toner blocking resistance and durability for many sheets. Good in low temperature fixing property and offset resistance.

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 their graft compounds, derivatives such as block compounds, and the like can be used to remove low molecular weight components. It is preferable that the maximum endothermic peak of the DSC endothermic curve is sharp.

Examples of waxes preferably used include linear alkyl alcohols having 15 to 100 carbon atoms, linear fatty acids, linear acid amides, linear esters, and montan derivatives. It is more preferable that impurities such as liquid fatty acid have been previously removed from these waxes.

In order to improve the translucency of a fixed image,
Particularly, solid ester wax is preferably used. The release agent is contained in an amount of 1 to 40 parts by mass, preferably 4 to 30 parts by mass, based on 100 parts by mass of the polymerizable monomer.

The polymerization toner of the present invention may contain a charge control agent. Known charge control agents can be used. For example, organometallic compounds and chelate compounds are effective for controlling the toner to be negatively charged, and monoazo dye metal compounds, acetylacetone metal compounds, aromatic hydroxycarboxylic compounds. Examples thereof include acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives such as bisphenol. Further, urea derivatives, metal-containing salicylic acid compounds, 4
Examples thereof include a quaternary ammonium salt, a calixarene, a silicon compound, a styrene-acrylic acid type copolymer, a styrene-methacrylic acid type copolymer, a styrene-acrylic-sulfonic acid type copolymer, and a non-metal carboxylic acid type compound.

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.

As the water-insoluble powder solid state polymerization initiator that can be used in the present invention, 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 (benzoylperoxy) hexane, bis (4-t-butylcyclohexyl) peroxydicarbonate, 1,1-bis (t-butylperoxy) cyclododecane, t-butylperoxymaleic acid, bis (T
Examples thereof include peroxide-based polymerization initiators such as -butylperoxy) isophthalate. The polymerization initiator is selected with reference to the 10-hour half-life temperature and used alone or in combination. The addition amount of the polymerization initiator varies depending on the intended 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 cross-linking agent used in the method for producing a polymerization toner according to the present invention include divinylbenzene, 4,4′-divinylbiphenyl, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate and glycidyl ( Mention may be made of polyfunctional compounds such as (meth) acrylate and trimethylolpropane tri (meth) acrylate.

As a dispersion stabilizer for favorably dispersing the polymerizable monomer composition in an aqueous dispersion medium, for example, inorganic compounds such as tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate and carbonic acid can be used. Examples thereof include calcium, 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 ones may be used as they are, but in order to obtain dispersed particles having a fine and uniform particle size, the above-mentioned inorganic compound can be produced in a dispersion medium under high speed stirring. . For example, in the case of tricalcium phosphate, a dispersion stabilizer suitable for the suspension polymerization method can be obtained by introducing and mixing an aqueous sodium phosphate solution and an aqueous calcium chloride solution into water under high-speed stirring. Further, due to the miniaturization of these dispersion stabilizers, 0.001 to
You may use 0.1 mass% of surfactant together. 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 a suspension polymerization method, a polar resin is added to the polymerizable monomer composition to promote the inclusion of a release agent. It is preferable because it can When the polar resin is present in the polymerizable monomer composition suspended in the aqueous dispersion medium, the polar resin migrates to the vicinity of the interface between the aqueous dispersion medium and the polymerizable monomer composition due to the difference in affinity for water. Since it is easy, the polar resin is unevenly distributed on the toner surface. As a result, the toner particles have a core-shell structure, and even when a large amount of the release agent is contained, the release agent has good encapsulation property.

As the polar resin, a saturated or unsaturated polyester resin is particularly preferable because 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 acid component monomer and the alcohol component monomer listed below can be used.

The acid component monomers include terephthalic acid, isophthalic acid, phthalic acid, fumaric acid, maleic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid,
Examples thereof include suberic acid, azelaic acid, sebacic acid, camphoric acid, cyclohexanedicarboxylic acid and trimellitic acid. As the alcohol component monomer, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3
-Alkylene glycols such as propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-bis (hydroxymethyl) cyclohexane, and polyalkylene glycols, bisphenol A, hydrogenated bisphenol, ethylene oxide addition of bisphenol A Compounds, propylene oxide adducts of bisphenol A, glycerin, trimethylolpropane, pentaerythritol and the like.

In using the toner produced by the present invention, an external additive may 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.

In the present invention, the toner obtained by the polymerization method is referred to as "toner particles", and the toner obtained by mixing the toner particles with an external additive is referred to as "toner". However, the toner particles may be used as they are without using an external additive, and in that case, the toner particles themselves are referred to as “toner”.

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.), and carbides. (Silicon carbide and the like), inorganic metal salts (calcium sulfate, barium sulfate, calcium carbonate and the like), fatty acid metal salts (zinc stearate, calcium stearate and the like), carbon black, silica and the like are used.

These external additives are used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight 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.

The toner produced according to the present invention may contain a magnetic material and be used as a magnetic toner. 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, ferrite, etc .;
Metals such as iron, cobalt, nickel; or these metals and aluminum, cobalt, copper, lead, magnesium,
Examples thereof include alloys of metals such as tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten and vanadium; and mixtures thereof.

The volume average particle diameter of these magnetic materials is 2 μm.
Hereafter, it is preferably about 0.1 to 0.5 μm. The amount of the polymerizable monomer 1 included in the toner is
About 20 to 200 parts by mass relative to 00 parts by mass, particularly preferably 40 to 150 parts by mass based on 100 parts by mass of the polymerizable monomer.

Further, the magnetic properties under application of 800 kA / m are: coercive force (Hc) 1.6 to 24 kA / m, saturation magnetization (σ
s) 10 to ²⁰⁰ Am ² / kg, remanent magnetization (σr) 2
It is preferably 100 Am ² / kg. Further, in the present invention, the strength of magnetization of the magnetic material is determined by the vibration type magnetometer VSM.
Using P-1-10 (manufactured by Toei Industry Co., Ltd.), measurement is performed at room temperature of 25 ° C. with an external magnetic field of 800 kA / m.

In order to improve the dispersibility of these magnetic materials 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 in any developing system as a one-component or two-component developer.
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 using a magnet incorporated in a developing sleeve to convey and charge the magnetic toner. When a non-magnetic toner containing no magnetic material 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 attached onto the developing sleeve to carry the toner.

On the other hand, when used as a commonly used two-component developer, a carrier is used together with the toner obtained by the present invention and used as a developer. The carrier used in the present invention is not particularly limited, but mainly iron, copper, zinc, nickel, cobalt,
It is composed of single and composite ferrites composed of 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 is used in which the above-mentioned metal is fired and granulated to form carrier core particles in advance, and then the resin is coated. In order to reduce the load on the toner of the carrier, after kneading the inorganic oxide and the resin, pulverizing and classifying to obtain a low-density dispersed carrier, or directly kneading the inorganic oxide and the monomer in an aqueous medium It is also possible to use a method of obtaining a polymerized carrier by suspension polymerization in which a true spherical dispersion carrier is obtained.

A system in which the surface of the carrier particles 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 to the carrier particles, a method of simply mixing with a powder, or the like can be applied.

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

The treatment amount of the above-mentioned adhered substance is generally 0.1 to 30 parts by mass, preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of carrier particles.

The volume average particle diameter of the carrier is 10 to 100 μm.
m, more preferably 20 to 50 μm. As a particularly preferred embodiment of the carrier, Cu-Zn
-Fe is a ternary ferrite of which the surface 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 resin, fluorine 90 to 20:80, preferably 70:30 to 90% by weight based resin and styrene resin
A mixture having a ratio of 30:70 is coated in an amount of 0.01 to 5% by mass, preferably 0.1 to 1% by mass.
An example is a coated ferrite carrier having the above-mentioned average particle size in which carrier particles of 50 mesh pass and 400 mesh on are 70% by mass or more. Other examples of the fluorine-based resin include vinylidene fluoride-tetrafluoroethylene copolymer (10:90 to 90:10), and examples of the styrene-based resin include styrene-2-ethylhexyl acrylate (20: 80-80: 20) and styrene-2-ethylhexyl acrylate-methyl methacrylate (20-60: 5-30: 10-50).

The above-mentioned coated ferrite carrier has a sharp particle size distribution, and it is possible to obtain a preferable triboelectrification property for the toner of the present invention and to improve 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 tends to be low and the toner tends to be impractical.

Further, the following magnetic properties of the carrier are preferable. The magnetic strength at 80 kA / m after magnetic saturation is preferably 30 to 300 Am ² / kg, and more preferably 35 to 250 in order to achieve higher image quality.
It is preferably Am ² / kg. If it exceeds 300 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.

[0071]

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 mass% sodium chloride aqueous 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.) using a 100 μm aperture for 2-4
The particle size distribution of 0 μm particles was measured, the volume average distribution was obtained, and the volume average particle size was obtained from this.

(2) Calculation of coefficient of variation The sharpness of the particle size distribution was evaluated by the coefficient of number variation calculated by the following equation (3). The smaller the coefficient of variation, the sharper the particle size distribution.

[0075]

[Equation 4] Coefficient of variation = number standard deviation / number average particle size x 100 (3)

(3) Image quality evaluation of two-component developer image quality Toner particles obtained were treated with a hydrophobic silica fine powder having a specific surface area of 200 m ² / g measured by the BET method of 0.
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 would be 8% by mass to obtain a two-component developer. Under the environment where this developer was not changed, an image development durability test by continuous paper feeding was carried out using a modified machine of Canon full-color copying machine CLC700, and the fluctuation and unevenness of image density were visually evaluated.

Evaluation of Image Quality of One-Component Developer For the obtained toner particles, 1. 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 one-component developer. Under the environment where this developer did not change, an image development durability test by continuous paper feeding was carried out by using a modified machine of Canon laser printer LBP-1760, and the fluctuation of image density and unevenness were visually evaluated.

(4) Measurement of Fog The measurement of fog was conducted by using REFLECTROMETER MODELTC-6DS (manufactured by Tokyo Denshoku Co., Ltd.) and calculated from the following formula (4). The smaller the number, the less fog.

[0079]

[Equation 5] Fog (reflectance) (%) =       Standard paper reflectance (%)-Sample non-image area reflectance (%) (4)

(5) Measurement of triboelectric charge amount of toner The triboelectric charge amount of toner was measured by the following procedure according to 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 diagram of an apparatus for measuring the triboelectric charge amount of toner. A mixture of a toner and a carrier whose mass ratio was 8:92, whose triboelectric charge was to be measured, was put into a polyethylene bottle having a volume of 50 to 100 ml and shaken by hand 200 times to mix. About 0.2 g of this mixture is put into a metal measuring container 12 having a 500-mesh screen 13 at the bottom, and a metal lid 14 is placed on it. At this time, the total mass of the measuring container 12 is weighed and set as W ₁ (g).

Next, the vacuum gauge 15 is used to suck through the suction port 17 with the suction device 11 (the portion in contact with the measurement container 12 is an insulator).
Read the instruction, and the pressure is adjusted to 2450P by the air flow control valve 16.
Adjust to be a. In this state, the toner is removed by suction for about 2 minutes. At this time, the maximum value of the potential indicated by the electrometer 19 is V (volt), and the capacity of the capacitor 18 is C (μ
F), where W ₂ (g) is the mass of the entire measurement container after suction, the triboelectric charge amount (mC / kg) of this toner is calculated by the following equation (5).

[0082]

[Equation 6] Triboelectric charge amount (mC / kg) = C × V ÷ (W ₁ −W ₂ ) (5)

(6) 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.

[0084]

Example 1 A polymerization toner composed of polymer fine particles was manufactured by the following procedure. (Preparation of polymerizable monomer composition) -Styrene monomer 60.2 parts by mass-n-butyl acrylate monomer 14.4 parts by mass-Carbon black 8.5 parts by mass-Unsaturated polyester resin 4.2 Parts by mass divinylbenzene 0.2 parts by mass di-tert-butylsalicylic acid aluminum compound 0.6 parts by mass monoazo dye iron compound 0.2 parts by mass ester wax 11.7 parts by mass

Of the above components, a part of the styrene monomer, carbon black, an aluminum compound of di-tert-butylsalicylate and an iron compound of a monoazo dye are mixed and a handy mill (manufactured by Mitsui Mining Co., Ltd.) is used. After being dispersed for a period of time, this, the rest of the styrene monomer, and other compositions are put into a temperature-controllable stirring tank, and the temperature is 60 ° C.
The mixture was heated to and mixed until fully compatible to obtain a polymerizable monomer composition.

(Preparation of Aqueous Dispersion Medium) Water 96.7 parts by mass Na ₃ PO ₄ 1.6 parts by mass 10% aqueous hydrochloric acid solution 0.8 parts by mass The above components were put into a stirring tank and Na ₃ PO ₄ was added. Was stirred until completely dissolved. Next, 0.9 part by mass of CaCl ₂ was added to the T. K. A homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.) was stirred at a rotation speed of 1500 rpm for 30 minutes to give C.
An aqueous suspension of fine particles of a ₃ (PO ₄ ) ₂ was obtained. Then, this was heated to 60 ° C. with gentle stirring to obtain an aqueous dispersion medium.

(Preparation of Polymerization Initiator Solution) 2.5 parts by weight of 2,2'-azobis- (2,4-dimethylvaleronitrile) and its 4 times the amount of 100 parts by weight of the polymerizable monomer composition. A certain amount of styrene was put into a stirring tank and mixed by stirring to prepare a polymerization initiator solution.

(Preparation of Preliminary Dispersion Liquid) The polymerizable monomer composition and the aqueous dispersion medium were put into a preliminary dispersion tank so that the mass ratio was 3: 7, and T. K. Using a homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.), stirring was carried out at a rotation speed of 3000 rpm for 5 minutes to prepare a preliminary dispersion liquid.

(Preparation of Polymerizable Monomer Composition Dispersion) The pre-dispersion liquid obtained in the above-mentioned step was flowed at a flow rate of 122 ml / min with CLEARMIX (M.
It was continuously introduced into Technic Co., Ltd. and stirred at 15,000 rpm. Simultaneously with this, the above-mentioned polymerization initiator solution is continuously supplied to CLEARMIX at a flow rate of 15.3 ml / min so that the polymerizable monomer composition contains the polymerization initiator. A product dispersion was obtained.

(Polymerization step) The polymerizable monomer composition dispersion obtained continuously from the above-mentioned steps was placed in a tubular reactor of the type shown in FIG. 198
m first tubular reactor and inner diameter of reaction tube 0.016
m, the second tube reactor having a pipe length of 158.4 m was continuously introduced into the apparatus connected in series in this order, and the polymerization temperature in the first tube reactor was 60 ° C. Polymerization was carried out at a polymerization temperature of 80 ° C. in the second tubular reactor to obtain a polymer fine particle dispersion liquid. At this time, d _p is 7 × 10 ⁻⁶ m, ρ _p
Is 1100 kg / m ³ , ρ _L is 1000 kg / m ³ , and η is 8.54 × 10 ⁻⁴ Pa. s, thus the A / B was 1.4. The polymerization step was continuously carried out for 48 hours, but during this period, the pressure in the tubular reactor did not fluctuate from beginning to end, and the narrowing and blockage of the pipeline due to the deposit did not occur. Dilute hydrochloric acid was added to the obtained polymer fine particle dispersion to dissolve Ca ₃ (PO ₄ ) ₂ covering the surface of the polymer fine particles, and after solid-liquid separation,
By washing with water, filtering and drying, toner particles which are fine particles of the polymerizable monomer were obtained.

(Evaluation of Toner) The particle size distribution of the toner particles was measured. As a result, the volume average particle size was 6.9 μm, the variation coefficient was 25%, and the particle size distribution was sharp. Neither large particles nor coarse particles were seen. The triboelectric charge amount was a good value of -47 mC / kg. It was found that the polymerization conversion rate was 100%, the molecular weight distribution was constant over time, and perfect plug flow property was achieved.

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, the fog was 0.8%, and the image density was not fluctuated from beginning to end, and a clear image having excellent fixability was stably obtained.

[0093]

[Comparative Example 1] The inner diameter of the reaction tube of the first tubular reactor was set to 0.0.
2 m, the pipe length was 135 m, the inner diameter of the reaction pipe of the second tubular reactor was 0.02 m, the pipe length was 108 m, and A / B was set to 0.8, and Example 1 was performed. Toner particles were manufactured in exactly the same manner. At 15 hours after the continuous operation of the polymerization step was started, the operation was stopped because the pressure inside the tubular reactor began to rise due to the accumulation of deposits in the reaction tube.

The volume average particle diameter of the obtained toner particles is 7.
The particle size distribution was 5 μm, the coefficient of variation was 32%, and the particle size distribution was larger on the coarse powder side than in Example 1, and irregular particles and coarse particles that were considered to be derived from the detached deposits were observed. The triboelectric charge amount was -35 μC / g. Polymerization conversion rate is 98%
It is considered that the substances discharged to the outside of the reactor without adhering to the predetermined residence time were mixed due to the adhesion and the retention occurring at.

Next, when an image output test of 20,000 sheets was conducted in the same manner as in Example 1, the fog was 1.9%, and white streaks and uneven density occurred from a relatively early stage.

[0096]

Example 2 A polymerization toner was manufactured by the following procedure. (Preparation of polymerizable monomer composition) ・ Styrene monomer 38.4 parts by mass * N-butyl acrylate monomer 10.8 mass parts ・ Silane coupling treatment magnetic iron oxide particles 44.3 parts by mass ・ Unsaturated polyester resin 2.0 parts by mass ・ Saturated polyester resin 0.5 parts by mass -Styrene-acrylic-sulfonic acid type copolymer 0.5 part by mass ・ Ester wax 2.0 parts by mass

Of the above components, the components other than the ester wax were put into a temperature-controllable stirring tank, and the T. K. Rotation speed 3000 using Homo Disper (Tokushu Kika Kogyo Co., Ltd.)
After stirring for 15 minutes at rotation / minute, this was heated to 60 ° C., ester wax was added, and stirring was continued for another 20 minutes to obtain a polymerizable monomer composition.

(Preparation of Aqueous Dispersion Medium) Water 97.8 parts by mass Na ₃ PO ₄ 1.2 parts by mass 10% aqueous hydrochloric acid solution 0.3 parts by mass The above components were charged into an aqueous dispersion medium tank and Na ₃ was added. Stir until PO ₄ is completely dissolved. Then, 0.7 part by mass of CaCl ₂ is added to the T. K. Homo Disper (Special Machine Industry Co., Ltd.)
The product was stirred for 30 minutes at a rotation speed of 1500 rpm to obtain an aqueous suspension of Ca ₃ (PO ₄ ) ₂ fine particles. Then, this was heated to 60 ° C. with gentle stirring to obtain an aqueous dispersion medium.

(Preparation of Polymerization Initiator Suspension) To 100 parts by mass of the polymerizable monomer composition, 1.5 parts by mass of benzoyl peroxide and 9.0 parts by mass of water were placed in a stirring tank. , T. K. Rotation speed 150 using a homodisper
Stirring was performed at 0 rpm for 10 minutes to prepare a polymerization initiator suspension.

(Preparation of Preliminary Dispersion) The polymerizable monomer composition and the aqueous dispersion medium were put in a stirring tank so that the mass ratio was 1: 2, and the T.I. K. Homo Disper (Special Machine Industry Co., Ltd.)
(Preparation) was used to stir at a rotation speed of 3000 rpm for 5 minutes to prepare a preliminary dispersion liquid.

(Preparation of Polymerizable Monomer Composition Dispersion) The pre-dispersion liquid obtained in the above-mentioned step was added to CLEARMIX (M.
It was continuously introduced into Technic Co., Ltd. and stirred at 18,000 rpm. Simultaneously with this, the above-mentioned polymerization initiator suspension is continuously supplied to CLEARMIX at a flow rate of 16.8 ml / min, whereby a polymerizable monomer containing a polymerization initiator in the polymerizable monomer composition is added. A body composition dispersion was obtained.

(Polymerization Step) Obtained continuously from the above steps.
The polymerizable monomer composition dispersion prepared above is used to form an inner diameter of the reaction tube of 0.0
A pipe of the type shown in Fig. 1 with a length of 08 m and a pipe length of 1296 m.
Type reactor is continuously introduced as it is, and the polymerization temperature is 80 ° C.
Was polymerized to obtain a polymer fine particle dispersion liquid. This and
D_pIs 7 × 10^-6m, ρ_pIs 1500 kg / m³, Ρ_LIs
1000 kg / m³, Η is 8.54 × 10^-FourPa. in s
Yes, therefore the A / B was 3.4. The polymerization process is
Although it was carried out continuously for 48 hours, the tube reactor
The pressure does not fluctuate, and the narrowing and blockage of the pipeline due to adhered matter
It didn't happen. Dilute hydrochloric acid was added to the obtained polymer fine particle dispersion.
Added Ca to cover the surface of the polymer particles₃(PO_Four) ₂
Is dissolved, and after solid-liquid separation, it is washed with water, filtered, and dried.
Toner particles which are fine particles of a polymerizable monomer are obtained.

(Evaluation of Toner) The particle size distribution of the toner particles was measured. As a result, the volume average particle size was 7.2 μm, the coefficient of variation was 28%, and the particle size distribution was sharp. Neither large particles nor coarse particles were seen. The triboelectric charge amount was a good value of -47 mC / kg. It was found that the polymerization conversion rate was 100%, the molecular weight distribution was constant regardless of time, and perfect plug flow property was achieved.

Next, hydrophobic silica was externally added to the obtained toner particles to obtain a one-component developer. When an image output test of 20,000 sheets was carried out, the fog was 1.0%, and the image density was not fluctuated from beginning to end, and a clear image having excellent fixability was stably obtained.

[0105]

Example 3 The inner diameter of the reaction tube of the tubular reactor is 0.01 m,
Toner particles were produced in exactly the same manner as in Example 2 except that the pipe length was 864 m and A / B was 2.0. The polymerization step was continuously carried out for 48 hours, but during this period, the pressure in the tubular reactor did not fluctuate from beginning to end, and the narrowing and blockage of the pipeline due to the deposit did not occur.

The volume average particle diameter of the obtained toner particles is 7.
The particle size distribution was 3 μm and the coefficient of variation was 29%, which was almost the same as that in Example 2, but some irregular particles and coarse particles which were considered to be derived from the detached deposits were observed. The triboelectric charge amount was -43 μC / g. The polymerization conversion rate was 100%, and the molecular weight distribution was constant regardless of time.

Next, an image output test of 20000 sheets was carried out in the same manner as in Example 2. Fog was 1.3%, and the image density was stable and stable throughout the image, and the image was clear and excellent in fixing property. It was obtained.

[0108]

[Comparative Example 2] The inner diameter of the reaction tube of the tubular reactor was 0.013.
m, the tube length was 475.2 m, and A / B was 0.9, and toner particles were manufactured in exactly the same manner as in Example 2. 8 hours after the start of continuous operation of the polymerization process,
The operation was canceled because the pressure inside the tubular reactor began to rise due to the accumulation of deposits in the reaction tube.

The volume average particle diameter of the obtained toner particles is 7.
The particle size distribution was 6 μm, the coefficient of variation was 35%, and the particle size distribution was larger on the coarse powder side than in Example 2, and irregular particles and coarse particles that were considered to be derived from the detached deposits were observed. The triboelectric charge amount was -35 μC / g. Polymerization conversion rate is 99%
It is considered that the substances discharged to the outside of the reactor without adhering to the predetermined residence time were mixed due to the adhesion and the retention occurring at.

Next, when an image output test of 20,000 sheets was conducted in the same manner as in Example 2, fog was 2.2% and white streaks and density unevenness were generated from a relatively early stage.

[0111]

INDUSTRIAL APPLICABILITY According to the present invention, a tubular reactor is used in which the inner diameter of the reaction tube, the physical properties of the polymerizable monomer composition dispersion liquid flowing through the reaction tube, and the flow linear velocity satisfy specific conditions. By continuously carrying out the polymerization process, it is possible to obtain a toner with a sharp particle size distribution and a uniform molecular weight distribution regardless of time, and with excellent image characteristics. Polymerization toner that does not adversely affect the product properties due to a large amount of contaminants in the polymer and that can be continuously operated without the need to remove deposits in the polymerization device, thus achieving high production efficiency. A method of manufacturing the same is provided.

[Brief description of drawings]

FIG. 1 is a diagram illustrating a tubular reactor used in the present invention.

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

[Explanation of symbols]

1 torso 2 reaction tubes 3 baffles 4 liquid inlet 5 liquid outlet 6 Heat transfer medium inlet 7 Heat transfer medium outlet 11 suction machine 12 Measuring container 13 screens 14 Lid 15 Vacuum gauge 16 Air flow control valve 17 Suction port 18 condenser 19 electrometer

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Kiyuki Kimura             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation F-term (reference) 2H005 AB06 CA02                 4J011 AA08 AB07 AB08 BA01 BA08                       BB02 BB04 BB18 DA01 DA03                       DB13 DB17

Claims (5)

[Claims] 1. A polymerization step in which a polymerizable monomer composition containing at least a polymerizable monomer is dispersed in an aqueous dispersion medium to obtain a polymerizable monomer composition dispersion, which is then polymerized. In the method for producing a toner, the polymerization device used in the polymerization step is a tubular reactor having a reaction tube, and the inner diameter of the reaction tube constituting the tubular reactor and the polymerizable monomer composition dispersion liquid The distribution linear velocity and its physical properties are expressed by the following formula (1),
A and B represented by (2) are set so that A / B ≧ 1, and the tubular reactor continuously introduces the polymerizable monomer composition into one end of the reaction tube, A method for producing a polymerization toner, which has a structure in which a liquid that has undergone a polymerization process is continuously discharged from the other end of a reaction tube. [Equation 1] (However, u is the flow velocity of the polymerizable monomer composition dispersion (m
/ S), d is the inner diameter (m) of the reaction tube constituting the tubular reactor, d _p is the droplet diameter (m) of the polymerizable monomer composition droplets,
ρ _p is the density (kg / m ³ ) of the polymerizable monomer composition droplets, ρ
_L is the density of the aqueous dispersion medium (kg / m ³ ), η is the viscosity (Pa.s) of the polymerizable monomer composition dispersion, and φ is the polymerizable monomer amount with respect to the entire polymerizable monomer composition dispersion. It represents the volume fraction of the body composition. ) 2. An inner diameter of a reaction tube constituting the tubular reactor, a linear flow velocity of a dispersion liquid of a polymerizable monomer composition and physical properties thereof are represented by the above formulas (1) and (2): A and B. Is A
2. The method for producing a polymerized toner according to claim 1, wherein / B ≧ 3 is set. 3. The reaction tube constituting the tubular reactor has a single or a plurality of static mixing elements arranged in its pipeline. Polymerization method of producing toner. 4. A polymerizable monomer composition containing at least a polymerizable monomer is preliminarily dispersed in an aqueous dispersion medium by a batch method to obtain a polymerizable monomer composition preliminary dispersion liquid, The method for producing a polymerized toner according to any one of claims 1 to 3, characterized in that the polymerizable monomer composition dispersion liquid is obtained by dispersing it again with a dispersing means. 5. A batchwise method of preliminarily dispersing a polymerizable monomer composition preliminarily dispersed at the same time as introducing a polymerization initiator into the dispersing means through an independent route. The method for producing a polymerization toner according to claim 4, wherein the toner is introduced into the dispersion unit at a predetermined ratio with respect to the liquid.