JPH01962A - Method for manufacturing toner for electrophotography - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing an electrophotographic toner used in electrophotography.

(Prior Art) In electrophotography, after a photoconductive layer is charged, it is irradiated with a light image based on an original image to reduce or eliminate the electrostatic charge in the light-irradiated area to form an electrostatic latent image.

Next, a developer is applied to visualize this. Dry developers generally include an f-component developer consisting of fine powder called toner and a carrier for transporting it, and a single-component developer consisting only of magnetic toner containing magnetic powder. What are the typical toners mentioned above?

It is a mixture of coloring materials such as dyes and pigments and/or magnetic powder and binding materials such as thermoplastic resins.

Conventional dry toners are generally made by melting and kneading a pigment such as carbon black into a thermoplastic resin to form a -like dispersion.
Grinding into fine powder using suitable pulverizing equipment has been practiced. Although the toner obtained by this method has a number of excellent properties, it also has a number of drawbacks. For example, there are limitations in terms of materials. In other words, since it requires a process of melting and pulverization, it must be fluidized at an appropriate temperature.

It is required that pigments and the like be mixed uniformly, and that the grinding equipment used in the mixing system be capable of processing the desired particle size at a considerable speed. However, if a material that is easily crushed is used, it will be further crushed in the electrophotographic apparatus, and the resulting fine powder toner will cause problems such as staining the apparatus and capping the image. Furthermore, if a material that is easily melted is used, there is a risk that toner may block during storage or in an electrophotographic apparatus, or may cause filming on the surface of the photoconductor. In addition, the pigment that was buried in the resin appears on the surface during crushing, which may cause minute local unevenness in triboelectric charging characteristics, which deteriorates the electrophotographic image, and furthermore, In some cases, there may be problems with moisture resistance.

What is considered to be an even bigger drawback is the shape and particle size distribution of the toner. The shape of the toner produced by pulverization is amorphous and tends to cause entanglement (agglomeration) between toner particles, which affects the stability of the toner during storage.

This adversely affects the dispensing characteristics during toner supply and the sharpness of a good developed image, and also acts as an undesirable factor in the cleaning characteristics in the case of repeated use.

What is considered to be the biggest drawback is that it is extremely difficult to pulverize particles with the desired particle size into a desired particle size distribution during the pulverization process.

The average particle size of toner used as a dry electrophotographic developer is generally about KIO μm, but in the pulverization method, if the material is selected so that it can be pulverized at an economical speed, fine particles of υ of 1 μm or less are produced. Further, even in such a case, a small amount of coarse particles of several tens of Jtlpm or more remain and are mixed into the product. Generally, the image quality obtained, including elucidation power, sharpness, fog, etc., is strongly affected by these small particles and coarse particles, and is significantly degraded.

In addition to these pulverization methods, there are two other methods, such as the
Dry toner manufacturing methods using polymerization methods have been proposed as seen in Japanese Patent Publication No. 1 and Japanese Patent Publication No. 43-10799. The former is based on the so-called aqueous suspension polymerization method and uses a synthetic resin monomer dipolymerization initiator.

Dispersion Stabilizer 9 A process of suspending a mixture of coloring materials, etc. in water and polymerizing it to produce a toner, and a process of imparting an electrostatic charge by treating the polymer with a surfactant during the polymerization process or after the completion of polymerization. It has become. The latter method is based on the so-called emulsion polymerization method, in which a coloring material is added to the latex obtained by polymerizing an aqueous emulsion of synthetic resin monomers containing an emulsifier (surfactant), 9 polymerization initiators, and the resulting emulsion dispersion is sprayed. It is granulated in the drying process to produce toner. What these toners have in common is that they are all spherical in shape, contain pigments inside the toner, and use surfactants in the process. In the emulsion polymerization method, it is necessary to use a surfactant to finely and stably emulsify monomers in water, and this is called an emulsifier.

In addition, in the suspension polymerization method, a dispersion stabilizer is used to stabilize the fine particle dispersion of the monomer in water and to prevent the dipolymer from forming agglomerates. There is a method.

One method is to dissolve water-soluble polymers in water, which is easy to operate and requires only a relatively small amount of water-soluble polymers. However, there are drawbacks such as the fact that the water-soluble polymer is adsorbed onto the surface of the polymer particles or becomes kraft, contaminating the polymer. The other method is to use a slightly soluble inorganic salt powder in a cloudy state, and by improving the dispersion of the slightly soluble inorganic salt powder itself, it is possible to obtain a polymer with a uniform particle size distribution. If there was.

The dispersion is insufficient and unstable, so surfactants are used in combination to improve and stabilize the dispersion.

(Problems to be Solved by the Invention) However, the use of surfactants as described above is by no means desirable. In other words, when a surfactant is used, it is difficult to completely remove it due to its surfactant properties, and even if you spend a lot of time and effort cleaning it, it will leave some residue on the surface of the polymer particles. remain. On the other hand, the electrical properties of toner used in dry electrophotography mostly depend on the properties of its surface, and depending on whether water-soluble polymers or surfactants remain on the toner surface. If there is.

Even if it is only a small amount, it can cause various problems.

For example, the electrical conductivity and humidity dependence of the surfactant itself directly affect the electrical properties of the toner, making the triboelectric charging properties of the toner extremely unstable. Furthermore, if the surfactant remains on the surface of the toner, it will easily absorb moisture and will have poor stability under high humidity conditions. Further, surfactant from the toner transfers and adheres to the carrier used in combination and the surface of the photoreceptor when used repeatedly, reducing the life of the photoreceptor and making the electrophotographic characteristics extremely unstable.

Therefore, it is an object of the present invention to provide a method that eliminates the various drawbacks mentioned above and can produce an electrophotographic toner with excellent photographic properties without using a surfactant.

(Means for Solving the Problems) The present invention solves the above problems by carrying out suspension polymerization in a non-aqueous solvent.

That is, the present invention relates to a method for producing an electrophotographic toner, which comprises suspending and polymerizing monopolymerizable monomers in a non-aqueous solvent in the presence of a colorant and/or magnetic powder.

In suspension polymerization of a polymerizable monomer in a nonaqueous solvent, it is preferable to use a dispersion stabilizer that helps disperse the dipolymerizable monomer in the nonaqueous solvent. In the present invention, suspension polymerization in a non-aqueous solvent is possible without using a dispersion stabilizer, but using a two-dispersion stabilizer allows a wide selection of monopolymerizable monomers and stabilizes the polymerization. be converted into

For suspension polymerization of polymerizable monomers in non-aqueous solvents.

A chain transfer agent may be present as appropriate. In addition, toner property improvers such as charge control agents, anti-offset agents, i-dynamic agents, and cleaning/cleanability improvers may also be present as appropriate.

As a method for suspension polymerizing a polymerizable monomer in a non-aqueous solvent, a polymerization initiator 2, a colorant and/or magnetic powder, and if necessary a toner property improver are dissolved or dispersed in the polymerizable monomer in advance. Method 1 Polymerization initiator 9 Coloring agent and/or
Or, be sure to use a polymerizable monomer mixture in which magnetic powder and other auxiliaries are dissolved or dispersed as necessary! Depending on the situation, a dispersion stabilizer was added in advance and added dropwise over a predetermined period of time into a non-aqueous solvent kept at a predetermined temperature while stirring.

Examples include methods for polymerization. When dissolving or dispersing the colorant and/or magnetic powder, etc. in the above polymerizable monomer, stirring may be carried out at relatively high speed using an ordinary stirrer, but before the start of bipolymerization or at the beginning of polymerization. It is preferable to use a homomixer or the like to stir the mixture by high-speed shearing.

Suspension polymerization is preferably carried out with stirring at a temperature of 50 to 200°C, particularly preferably 80 to 150°C. This suspension polymerization is preferably carried out until the polymerization rate reaches 99% by weight or more. Preferably, it is particularly preferable to proceed until the weight reaches 99.9 weight or more.

If the polymerization rate is low and the amount of residual monomer is large, the toner properties tend to be poor.4? storage stability tends to be poor.

In addition, the polymer obtained by S turbidity polymerization preferably has a weight average molecular weight of 10,000 or more.
ooo or more is preferable. If the molecular weight is too low, cleaning properties and storage stability tend to deteriorate.

Furthermore, the obtained polymer has a glass transition point of 30 to 90°C.
, particularly preferably 50 to 80°C.

If the glass transition point is too low, storage stability tends to decrease, and if it is too high, fixability tends to decrease. The glass transition point can be adjusted mainly by selecting the type and ratio of the polymerizable monomers used.

The particle size distribution of polymer particles obtained by suspension polymerization in a non-aqueous solvent can be adjusted by adjusting the ratio of the polymerizable monomer to the non-aqueous solvent,
This is done depending on the type and amount of the non-aqueous solvent dispersion stabilizer, stirring efficiency, etc., but it is preferable to adjust the size to 1 to 50 μm, and in particular adjust it so that the main component is 5 to 25 μm. It is most preferable to do so. The average particle size is preferably adjusted to 9 to 15 μm.

Next, materials used for suspension polymerization in a nonaqueous solvent will be explained.

Examples of the polymerizable monomer that is a raw material for the binding resin of the toner include the following.

(1) Styrene, 0-methylstyrene, m-methylstyrene, p-methylstyrene, p-ethylstyrene,
2.4-dimethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene.

p-n-nonylstyrene, p-n-decylstyrene, p
-n-dodecylstyrene, n-methoxystyrene, p-
Styrene and derivatives thereof, such as phenylstyrene, p-chlorostyrene, and 3,4-dichlorostyrene.

(2) Ethylenically unsaturated monoolefins such as ethylene, propylene, butylene, and isobutylene.

(31 Vinyl chloride, vinylidene chloride, vinyl bromide.

Vinyl halides such as vinyl fluoride, vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, and vinyl butyrate.

(4) Methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate,
2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate , methacrylic #In-octyl, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, acrylonitrile, methacrylonitrile, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate.

2-hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate
Acrylic acid or methacrylic acid derivatives such as hydroxypropyl.

(5) Dialkylaminoalkyl acrylates such as dimethylaminomethyl acrylate, dimethylaminoethyl acrylate, dimethylaminopropyl acrylate, dimethylaminomethyl methacrylate, dimethylaminoethyl methacrylate, dimethylamine propyl methacrylate, dialkylaminoalkyl methacrylate, aminomethyl acrylate, aminoethyl Acrylate.

Aminoalkyl acrylates such as aminomethyl methacrylate, aminoethyl methacrylate, aminoalkyl methacrylates, morpholinomethyl acrylate, morpholinoethyl acrylate.

2-morpholinopropyl acrylate, 3-morpholinopropyl acrylate, 2-morpholinopropyl acrylate, 4-morpholinobutyl acrylate, 3-morpholinobutyl acrylate.

Morpholinoalkyl acrylates such as 2-morpholinobutyl acrylate, 2-morpholinopentyl acrylate, 2-morpholinohexyl acrylate, and 2-morpholinooctyl acrylate.

Methacrylates having morpholinoalkyl similar to these, aziridyl alkyl acrylates, piperadylalkyl acrylates in which an aziridyl group, piperazyl group or piperidyl group is bonded in place of the morpholino group in the morpholinoalkyl acrylates as exemplified above. and biveridyl alkyl acrylate, aziridyl alkyl methacrylate, piperadylalkyl methacrylate and piperidyl alkyl methacrylate having an alkyl group similar to these, morpholinomethyl acrylamide, morpholinoethyl acrylamide, 3-morpholinopropylacrylamide, 2-morpholinopropylacrylamide, Morpholinoalkylacrylamide such as 4-morpholinobutylacrylamide, 3-morpholinobutylacrylamide, 2-morpholinobutylacrylamide, 2-morpholinopentylalkylacrylamide, 2-morpholinohexylacrylamide, 2-morpholinooctylacrylamide.

Morpholinoalkyl methacrylamides having morpholinoalkyl groups similar to these, aziridyl groups instead of two morpholino groups in morpholinoalkylacrylamides as shown above.

Aziridyl alkyl acrylamide, piperazyl alkyl acrylamide and piperidyl alkyl acrylamide to which a piperazyl group or a piperidyl group is bonded, aziridyl alkyl methacrylamide having an alkyl group similar to these, piperadylalkyl methacrylamide and piperidyl alkyl methacrylamide, morpholino Methylthioacrylate, morpholinoethylthioacrylate, 3-morpholinopropylthioacrylate.

Morpholinos such as 2-morpholinopropylthioacrylate, 4-morpholinobutylthioacrylate, 3-morpholinobutylthioacrylate, 2-morpholinobutylthioacrylate, 2-morpholinopentylthioacrylate, 2-morpholinohexylthioacrylate, 2-morpholinooctyl acrylate Alkylthioacrylate.

Morpholinoalkylthiomethacrylates having a morpholinoalkyl group similar to these, aziridylalkylthioacrylates in which an aziridyl group, piperazyl group or piperidyl group is bonded instead of one morpholino group in the morpholinoalkylthioacrylates exemplified above, piperazyl Amino group-containing addition-polymerizable monomers such as alkylthioacrylates and piperidylalkylthioacrylates, aziridylalkylthiomethacrylates having alkyl groups similar to these, piperidylalkylthiomethacrylates, and piperidylalkylthiomethacrylates.

(6) Acrylic acid, methacrylic acid, maleic acid.

7? carboxyl group-containing addition-polymerizable monomers such as acid and itaconic acid, and metal salts thereof such as sodium salts, potassium salts, and zinc salts.

(7) I)-Styrenesulfonic acid, 0-methylstyrenesulfonic acid 9m-methylstyrenesulfonic acid.

Styrene sulfonic acids such as chlorstyrene sulfonic acid,
Acrylic or methacrylic alkylsulfonic acids such as methylsulfonic acrylate, ethylsulfonic acrylate, propylsulfonic acrylate, methylsulfonic methacrylate, ethylsulfonic methacrylate, propylsulfonic methacrylate, and their sodium salts , potassium salts, zinc salts, and other metal salts.

+81 Vinyl ethers such as vinyl methyl ether, vinyl ethyl nityl ether, vinyl inobutyl ether, etc.

(9) Type 7 vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and methyl inopropenyl ketone.

(10) N-vinyl compounds such as N-hinylpyrrole, N-vinylcarbazole, N-vinylindole, and N-vinylpyrrolidone.

(1i) Vinylnaphthalene salt, etc.

These polymerizable monomers can be used alone or in combination of two or more. It is preferable to use styrene or a styrene derivative in an amount of 40 to 100% by weight among these polymerizable monomers because the toner has excellent fixing properties when copied onto paper using an electrophotographic copying device.

Further, as the polymerizable monomer of the present invention, a compound having two or more polymerizable double bonds that can serve as a crosslinking agent can also be used in part. aromatic divinyl compounds such as divinylbenzene, divinylnaphthalene and their derivatives;
Diethylene carboxylic acid esters such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol triacrylate, and trimethylolpropane triacrylate, divinyl compounds such as N,N-cyhinylaniline, divinyl ether, and divinyl sulfite, and 3 or more vinyl Compounds having groups can be used alone or as a mixture. The amount of crosslinking agent used is 0 to 20% by weight based on the total amount of polymerizable monomers.
is preferable, and particularly preferably 0 to 5 weight.

The nonaqueous solvent used in the present invention includes organic solvents such as linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and halogenated hydrocarbons.

Those that are incompatible or have low compatibility with the polymerizable monomer used are appropriately selected and used to the extent that the monomer is sufficiently dispersed.

Specifically, hexane, heptane, and octane.

Isopar E is a petroleum solvent based on long-chain aliphatic hydrocarbons such as inoctane, nonane, decane, isodecane, dodecane, and ilkane, and inparaffin.

Isopa 1-Q, Isopa +++ H, Isopa L (all trade names of Exxon Corporation), and Shell Silua 1 (trade name of Shell Oil Company).

Amsco OM8. Amsco 460 (all brand names of Spirits Inc.) and the like are preferred. These may be used alone or in combination of two or more.

If an appropriate amount of an organic solvent having high compatibility with other dipolymerizable monomers is mixed, the dispersibility of the heponepolymerizable monomer may be further improved. If mixed, 0 to 30% by weight in a non-aqueous solvent.
is preferable, and 0 to 15 weight is particularly preferable. Specifically, toluene, xylene, methanol, ethanol, butanol, ethyl acetate, butyl acetate, and cellosolve acetate.

Preferred examples include butyl cellosolve.

The ratio of the polymerizable monomer to the nonaqueous solvent is preferably 60/40 to 10/90 in weight ratio of the former/latter. If this ratio is too large, I! ! If it is too small, the yield tends to decrease because it is difficult to undergo turbid polymerization.

Next, 9 dispersion stabilizer will be explained.

A dispersion stabilizer that is soluble in a non-aqueous solvent and incompatible with the binder resin of the toner is selected and used, and the blending ratio is 2.
Although the dispersion stabilizer varies depending on the type of dispersion stabilizer and is not limited to general terms, it is generally used in amounts of 1 to 1 to 1 for all toner components.
20% by weight is preferred, particularly 2-15% by weight. In the present invention, the total toner component refers to the total amount of colorant and/or magnetic powder, dispersion stabilizer, polymerizable monomer as a binder resin component, and various toner property improvers.

If the amount of dispersion stabilizer is too small, the dispersion tends to become unstable, and if it exceeds 20% by weight, the toner tends to become soft and the blocking resistance tends to decrease.

Dispersion stabilizers include various rubbers, aminoplast resins such as butylated melamine resins, rubber graft resins, alkyd resins, polybutadiene, and acrylic esters and/or methacrylic esters having long carbon chains as essential components. Polymers and the like are used.

These dispersion stabilizers are partially absorbed into the resulting toner and therefore affect the toner properties.

Preferred dispersion stabilizers in the present invention will be explained below.

Rubber is preferable because it has a large internal cohesive force and is effective in improving offset resistance without impairing fixing properties. Further, when the rubber contains an unsaturated bond, it is preferable because the polymerizable monomer is grafted onto the rubber and is present in the toner. Rubbers include natural rubber (standard Malaysian rubber, abbreviated as various grades standardized by 8MR, etc.), styrene-butadiene rubber, acrylonitrile butadiene rubber, butyl rubber, chlorobutene rubber, butadiene rubber, imprene rubber, ethylene propylene rubber, Synthetic rubber such as urethane rubber, silicone rubber, acrylic rubber,
Examples include recycled rubber.

Polybutadiene has 9 usually 1,4-addition and/or 1,2
-It is obtained by addition, and in the case of 1.4-addition, it takes a cis structure and/or a trans structure. When focusing on improving offset resistance,
Polybutadiene, which has a high copolymerizability and has a large number of cis-type structures due to 1,4-addition, is preferred. Also, regarding the molecular weight of polybutadiene.

Although there is no particular limit, it is preferably within 10,000 from the viewpoint of handling (mainly ease of dissolution in a solvent, etc.). From the viewpoint of dispersion stability, the molecular weight is preferably 000 or more. This polybutadiene disperses the toner components and polymerizes with the binder resin of the toner through the remaining unsaturated bond groups. Therefore.

Since the polymerizable monomer is grafted onto the polybutadiene and is present in the toner, the polybutadiene acts as a kind of intramolecular plasticizer and improves fixing properties. Further, by increasing or decreasing the molecular weight of polybutadiene and the amount of unsaturated bond groups, the crosslinking density can be increased or decreased, so that offset resistance can also be improved at the same time.

A polymer containing as an essential component an acrylic ester and/or a methacrylic ester having a long carbon chain is preferable because the toner has a good balance of various properties.

The above polymer is more preferably a polymer containing an alkyl acrylate ester and/or alkyl methacrylate having an alkyl group having 8 or more carbon atoms as an essential component, and an alkyl acrylate having an alkyl group having 12 to 17 carbon atoms. Particularly preferred are polymers containing esters and/or methacrylic acid alkyl esters as essential components. If the number of carbon atoms in the alkyl group, which is an essential core component, is too small, it will be difficult to sufficiently stably disperse the polymerizable monomer and its copolymer in a nonaqueous solvent.

Specifically, 2-ethylhexyl acrylate.

Examples include 2-ethylhexyl methacrylate, lauryl methacrylate, lauryl acrylate, stearyl methacrylate, and stearyl acrylate, and it is particularly preferable to use lauryl methacrylate as an essential component because the toner has a good balance of various properties.

Polymers containing these as essential components include homopolymers of the above monomers, copolymers of two or more of the above monomers,
Examples include copolymers of the above monomers and other monomers. When copolymerizing other monomers, it is preferable to copolymerize 70% by weight or more of the above monomers, which are essential components. If the amount of the above-mentioned monomers, which are essential components, is too small, the effect as a dispersion stabilizer tends to decrease.

Examples of other monomers include one or two of the nine listed above as polymerizable monomers that are raw materials for the binder resin, but excluding those listed as monomers that are essential components. The above can be used.

When producing a positively chargeable toner, this dispersion stabilizer may be used as other monomers among those exemplified as polymerizable monomers that are raw materials for the binder resin.

It is preferable to copolymerize the amino group-containing addition polymerizable monomer shown in (5) in the dispersion stabilizer in an amount of preferably 1 to 30% by weight. When this dispersion stabilizer is used, it is not necessary to use a positive charge control agent, or it is sufficient to use a charge control agent in an amount less than half of the usual amount. Therefore.

The disadvantages caused by using a positive charge control agent are eliminated or reduced, and a long-life toner with excellent moisture resistance, anti-blocking properties, and charge stability can be obtained. Also, if a charge control agent is not used.

Since the toner can be colored arbitrarily, it is also possible to make it into a colored toner.

(9) When producing a negatively chargeable toner, other monomers such as those shown in (6) and (7) among the nine examples of polymerizable monomers that are raw materials for the binder resin may be used. Polymerizable monomers having carboxyl groups and/or sulfone groups and/or metal salts thereof.

Preferably, 1 to 30% by weight of the dispersion stabilizer is copolymerized. When this dispersion stabilizer is used, it is not necessary to use a negative charge control agent, or it is sufficient to use a charge control agent in an amount less than half of the usual amount. Therefore, the same effects as in the case of producing the positively chargeable toner can be obtained.

In addition, in the polymer containing the long carbon chain acrylic ester and/or methacrylic ester as an essential component, an unsaturated bonding group reactive with the polymerizable monomer that is the raw material for the binder resin is introduced. It is further preferred to use a polymer as a dispersion stabilizer. This is because the polymerizable monomer is grafted onto the dispersion stabilizer No. 9 and is infiltrated into and around the toner particles, so the dispersion stabilizer No. 2 acts like an intramolecular plasticizer and improves the fixing properties of the toner. This is because offset resistance can also be improved by adjusting the crosslinking density.

The number of unsaturated bond groups that can be polymerized and crosslinked with the polymerizable monomer, which is a raw material for the binder resin, is 2. For example, as a component of a dispersion stabilizer, glycidyl methacrylate and/or glycidyl acrylate are preferably copolymerized in an amount of 1 to 30 mol. A method in which a carboxyl group-containing polymerizable monomer that reacts with an oxirane ring is added to glycidyl methacrylate and/or glycidyl acrylate in an approximately equivalent amount, and the carboxyl group-containing polymerizable monomer is preferably used as a component of a 1 to 30 mol chronic dispersion stabilizer. It can be introduced by a method of copolymerizing and then subjecting glycidyl methacrylate and/or glycidyl acrylate to an approximately equivalent addition reaction.

Examples of carboxyl group-containing polymerizable monomers include methacrylic acid, acrylic acid, maleic acid, and fumaric acid.

Examples include itaconic acid. In addition, an addition reaction between a hydroxyl group or an amino group and an incyanate-containing polymerizable monomer may be used, and there is no restriction on the method of introducing an unsaturated bonding group capable of polymerization and crosslinking into the two-dispersion stabilizer. Note that 1 is also used when producing the positively chargeable toner and negatively chargeable toner.
It is preferable to introduce an unsaturated bond group into the dispersion stabilizer,
in this case.

In addition to improving toner fixing properties and anti-offset properties, charging stability is further improved.

This dispersion stabilizer can be used for solution polymerization and bulk polymerization.

Emulsion polymerization, aqueous lI! ! It is produced by a known polymerization method such as suspension polymerization or non-aqueous solvent suspension polymerization using a known polymerization initiator. Among the above polymerization methods, non-aqueous suspension polymerization is particularly preferred in the present invention. These polymers preferably have a weight average molecular weight of 1,000 to 100,000, but are not limited thereto.

In the present invention, the polymerization initiators used for suspension polymerization in a non-aqueous solvent include benzoyl peroxide, perbenzoic acid tert.
- peroxides such as butyl, azobisisobutyronitrile,
An oil-soluble polymerization initiator such as an azo compound such as azobisin butylvaleronitrile is preferably used in an amount of 0.1 to 20% by weight, preferably 0.1 to 1% by weight, based on all polymerizable monomers.
By appropriately selecting the type and amount of the polymerization initiator and the temperature during the polymerization reaction, it is possible to adjust the molecular weight of the binder resin of 9) to 114.

Examples of chain transfer agents include alkyl mercaptans such as t-dodecyl mercaptan, lower alkyl xanthogens such as diisopropyl xanthogen, carbon tetrachloride, carbon tetrabromide, etc., and are used in amounts of 0 to 2 by weight based on the polymerizable monomer. Preferably.

Colorants preferably used in the present invention include:

Pigments or dyes such as various carbon blacks, nigrosine dyes (C,1,N150415
), Aniline Blue (C, L 50405).

Calco oil blue (C, LNaazoec Blu
e 3 ) s chrome ye”-(C, LNa1409
0), Ultramarine Blue (C, LNa77
103), DuPont Oillet' (C, L & 261
os), Orient Oil Redna 330 (C, 1,
N1160505)t Quinoline yellow (C, L 47005), methylene blue chloride (C, I, N
CL52015), Phthalocyanine Blue (C,
L Arashi 74160), malachite green oxalay)
(C,L&42000).

Lamp black (C, L magnetic 77266), rose bengal (C0LNa45435), oil black.

Azo oil black and the like can be used alone or in combination. These colorants can be used in any amount, but in order to obtain the required concentration and for economic reasons, they are preferably 1 to 30% by weight, particularly preferably 5 to 15% by weight, in the total toner components. used in proportions such that

The pigment or dye may be subjected to various treatments for the purpose of increasing its dispersibility in the double polymerization reaction system or in the toner of the present invention. The above processing is 9
For example, nigrosine dye, (C, LNllL50415)
There is a treatment using organic acids such as stearic acid and maleic acid.

Among these colorants, two particularly preferred for the toner of the present invention are various carbon blacks such as furnace black, channel black, thermal black, acetylene black, lamp black, and the like. Furthermore, the carbon black may be surface-treated. As for surface treatment.

Examples include oxidation treatment using various oxidizing agents such as oxygen, ozone, and nitric acid, and surface adsorption treatment with organic acid esters such as dibutyl phthalate and dioctyl phthalate.

Magnetic powder is used when manufacturing magnetic toner.

This can also serve as a coloring agent. Preferred magnetic powders include oxides or compounds of iron such as magnetite or ferrite, or ferromagnetic elements such as nickel and cobalt.

These magnetic powders are preferably in powder form with a particle size of 0.01 to 3 μm, and the surface of the magnetic powder may be treated with a resin, a titanium coupling agent, a silane coupling agent, a higher fatty acid metal salt, etc. . These magnetic powders are preferably used in an amount of 20 to 80% by weight 1*, particularly preferably 35 to 70% by weight, based on the total toner components. It may be used as a second coloring agent or in combination with a second coloring agent in an amount less than this amount.

An offset inhibitor is used as necessary. The anti-offset agent is present in the system in various forms during polymerization and can be incorporated into the toner product. Alternatively, the anti-offset agent can be added later to the toner of the present invention in which no anti-offset agent is present.

Various natural waxes such as carnauba wax, hardening and improving low molecular weight olefin polymers can be used as the anti-offset agent in the present invention, and low molecular weight olefin polymers are preferably used. This low molecular weight olefin polymer includes an olefin polymer,
A low molecular weight copolymer of an olefin and a monomer other than olefin is used. Here, olefins include ethylene, propylene, butene-1, etc., and monomers other than olefins include acrylic esters, methacrylic esters, etc. Examples of the low molecular weight olefin polymer include polyalkylene described in % 153944, Japanese Patent Application Laid-open No. 50-93.
The low molecular weight olefin copolymers described in Japanese Patent No. 647 can be used.

The molecular weight of the low molecular weight olefin polymer used in the present invention may be within the concept of low molecular weight in ordinary polymer compounds, but generally the weight average molecular weight (Mw) is 1.
,000~45,000. Preferably 2,000-0
00.

The low molecular weight polyolefin polymer that can be used in the present invention has a softening point of 100 to 180°C, particularly 130 to 160°C.
℃ is preferred.

There is no particular limit to the amount of the low molecular weight olefin polymer that can be used in the present invention, but it is preferably in the range of 0 to 30% by weight based on the total amount of toner.

Particularly preferably from 1 to 10% by weight are used. If the amount of the low molecular weight olefin polymer is too small, the anti-offset effect due to its addition will not be exhibited.

If the amount is too large, gelation may occur during the polymerization reaction.

Furthermore, a fluidity improver, a 17-Jung property improver, etc. can be used as necessary. These can be present in the polymerization reaction system and then present in the product toner, but preferably they are externally added to the product toner afterwards. The content of each of these is 0 to 0 for the toner of the present invention.
3% by weight is preferred. Fluidity improvers include silane, titanium, aluminum, calcium, magnesium, and magnesium oxides, or those obtained by hydrophobizing the oxides with a titanium coupling agent or a silane coupling agent. teeth.

These include metal salts of higher fatty acids such as zinc stearate, lithium stearate and magnesium laurate, or aromatic acid esters such as pentaerythritol benzoate.

In the present invention, a charge control agent can also be used in the toner of the present invention in order to adjust the charge amount and charge polarity to more desired values.

As the charge control agent preferably used in the present invention, nigrosine dyes such as alcohol soluble nigrosine dyes, fatty acid-modified nigrosine dyes, carboxyl group-containing resin-modified nigrosine dyes, Spiron black TRH, Subiron black TP
Azo dyes such as H (manufactured by Hodogaya Chemical Industry ■), p-fluorobenzoic acid.

Examples include aromatic acid derivatives such as p-nitrobenzoic acid and 2,4-di-t-butylsalicylic acid, and tin compounds such as dibutyl-tin oxide and dioctyl-tin oxide. These are 0 to 5 per polymerizable monomer.
Preferably, % by weight is used.

After suspension polymerization in a non-aqueous solvent is completed, the solvent is removed using a centrifuge and 't! i Dry and classify if necessary.

Toner particles can be obtained.

When the toner obtained according to the present invention is used as a two-component developer, iron oxide powder, manganese, cobalt, nickel, zinc, etc. in nine different shapes such as flat, cavernous, coin-shaped, spherical, etc. , 1m, ferrite such as magnesium, lead, strontium, barium, lithium, Teflon resin, acrylic resin.

Polyester resin, silicone resin, melamine resin.

It can be used in combination with a carrier such as iron oxide powder whose surface layer is coated with butadiene resin, butyral resin, etc., ferrite, or particles made of a mixture of various resins and magnetic powder.

The toner concentration of a two-component developer generally depends on the specific surface area of the carrier, and when the carrier used is amorphous or has a fine particle size, it is 3 to 10% by weight, and when the carrier is spherical or has a coarse particle size, it is 1 to 10% by weight. It is preferable that the quintuple is set to -.

The toners obtained according to the present invention can be used in various development processes, such as the cascade development method described in U.S. Pat. No. 2,618,552, and the magnetic brush method described in U.S. Pat. No. 2,874,065.

The powder cloud method described in U.S. Patent No. 2,221,776, the touchdown development method described in U.S. Pat. It can be used in a jumping method, a so-called microtoning method using magnetic toner produced by a pulverization method as a carrier, and a so-called bipolar magnetic method in which a necessary toner charge is obtained by frictional charging of magnetic toners.

Furthermore, the toner obtained according to the present invention can be fixed using various fixing methods, such as so-called oil-less and oil-coated heat roll methods,
It can be used in flash method, oven method, pressure fixing method, etc.

Furthermore, the toner of the present invention can be used in various cleaning methods, such as the fur brush method and the blade method.

(Function) In the present invention, since a non-aqueous solvent is used as the suspending solvent, there is no need to use a surfactant. Result 9
All problems caused by residual surfactant on the surface of polymer particles are eliminated, and a toner with excellent moisture resistance and various photographic properties can be obtained.

Furthermore, by selecting the type of dispersion stabilizer used in monopolymerization, a toner with excellent anti-offset properties and/or fixing properties can be obtained.

(Example) Next, an example of the present invention will be shown, but the present invention is not limited thereto. Hereinafter, "arrogant" means % by weight.

Example 1 (1) Synthesis of dispersion stabilizer A 4072 Sco was equipped with a stirring device, nitrogen inlet, M lower funnel, @ variable needle, and a condenser, and Aitzva-G (trade name of Ekun Corporation, Imparaffin) xooo
g was charged and stirred while keeping the temperature at 120° C. under a nitrogen stream.

Separately, a solution prepared by dissolving 25 volumes of 7zobisisobutyronitrile in lauryl methacrylate (methacrylate) 10009 was uniformly dropped into the flask over 2 hours, and the temperature was kept at 120°C for 6 hours while being careful not to generate heat. Cooled. A dispersion stabilizer solution consisting of a polylauryl methacrylate solution with a polymerization rate of 99.9% or more and a solid content of 50's was obtained.

(2) Production process of suspension polymerization solution A 4-bottle flask equipped with a stirrer, nitrogen inlet, 11 lower funnel, thermometer, and Hikontensa was charged with 100 ml of Isopar E (trade name of Ekun Corporation, isoparaffin).
09 and 140 g of the above dispersion stabilizer solution were charged and kept at 90° C. under a nitrogen stream.

Stirred. Separately, 630g of styrene as a dipolymerizable monomer
and butyl methacrylate 2709. As a coloring agent, 65 g of carbon black φ44 (manufactured by Mitsubishi Kasei Corporation, furnace black type carbon black), 15 g of Subiron Black TRH (trade name of nigrosine dye, manufactured by Hodogaya Chemical Industries, Ltd.) as a charge control agent, low molecular weight polypropylene (trade name) Viscole s s OP, manufactured by Sanyo Chemical Industries ■) 20
s*As a polymerization initiator, azobisin butyroni) IJ 1
89 was mixed and dispersed in a homomixer at 3000 cam for 30 minutes, and the mixture was uniformly dropped into the flask over 2 hours, kept warm for 6 hours while being careful not to generate heat, and then cooled to obtain a suspension polymerization liquid. The polymerization rate at this time was 99.9 or more. The molecular weight of the 9-polymer was measured by high-performance liquid chromatography using a standard polystyrene calibration curve, and the weight average molecular weight (hereinafter referred to as Mw) was 7200.
0. The number average molecular weight (hereinafter referred to as Mn) was 30,000.

(3) Drying process After removing the solvent from the cloudy polymer solution using a centrifuge.

It was dried in a dryer at 40°C to obtain a toner. When the particle size of the obtained toner was measured using a Coulter counter, the particle size distribution was 1 to 50 μm, and the average particle size was 13 μm. Further, the glass transition point (hereinafter referred to as Tg) was measured with a differential scanning calorimeter and was found to be 76°C.

(4) TF value This toner can be used in a plain paper copying machine using a commercially available insulating carrier (manufactured by Konishiroku Photo Industry ■, product name: U-Bix 1).
600) was used to test the electrophotographic properties. (toner concentration 5%). However, the toner contains hydrophobic silica (R-9 manufactured by Nippon Aerosil ■) as a fluidity improver and a hydrophobicity improver.
72) and zinc stearate were externally added to the above toner at a concentration of 0.6% and 0.11%, respectively. The test results are shown in Table 1.

Example 2 (1) Manufacturing process of suspension polymerization solution Isopar E10009 and the dispersion stabilizer solution 14 obtained in (1) of Example 1 were placed in the same flask as in Example 1.
09 was charged, kept at 90°C under a nitrogen stream, and stirred. Separately, 9 polymerizable monomers include 720 g of styrene, 180 g of butyl acrylate, and carbon black φ44 65
9. Subiron black TRH159, Viscole 550
P209, Perbutyl 0 (NOF ■) as a polymerization initiator
Co., Ltd., trade name of t-butyl peroxide (2-ethylhexanoate)) 189 in a homomixer at 300 or
, p, and m for 30 minutes, the mixture was uniformly dropped into the flask over 2 hours, kept warm for 6 hours while paying attention to heat generation, and then cooled to obtain a suspension polymerization liquid. The polymerization rate at this time should be 99.9 or higher.

The molecular weight of the specific polymer was determined in the same manner as in Example 1, and the Mw was 850.
00, and Mn was 38,000.

(2) Drying process The above M-filled solution was centrifugally desolvented and dried at 40° C. in a drier to obtain a toner. When the particle size of the obtained toner was measured using a Coulter counter, the particle size distribution was 1 to 50 μm, and the average particle size was 12 μm. Furthermore, Tg was measured using a differential scanning calorimeter.
When measured, it was 72°C.

(3) Evaluation The electrophotographic properties of this toner were evaluated in the same manner as in Example 1. The test results are shown in Table 1.

Comparative Example 1 (Production of toner by aqueous W!A turbidity polymerization) Styrene 70g, butyl methacrylate 309° grafted carbon (grafted carbon GP-E-2. Carbon black/polymer component/styrene monomer = 30/30
/40. Ryoyu Kogyo ■) 159 and benzoyl peroxide 2
Mix well with a homomixer, add 500g of a 1% aqueous solution of tricalcium phosphate, and mix with a homomixer for another 30g.
Dispersion was carried out for 30 minutes at 00r, p, m.

This dispersion was transferred to a flask and subjected to turbid polymerization at 90'IC for 7 hours. The polymerization rate was about 99%. This polymer was dehydrated, washed with an aqueous hydrochloric acid solution having a pH of 2 or less, and then dried to obtain a toner. The Mw of the resin in this toner is 97,000. Mn was 5oooo.

Comparative Example 2 (Production of toner by spray drying after emulsion polymerization) 31#),
009. 120 g of butyl acrylate and 0.6 g of t-dodecyl mercaptan as a chain transfer agent were mixed and dispersed in a homomixer at 300 m or 90 m for 30 minutes.

Next, ion exchange water 13009 was added to this carbon dispersion.
Sodium dodecylbenzenesulfonate 129, an anionic surfactant, and Noniball PE-68, a nonionic surfactant, are used as emulsifiers (trade name of Sanyo Chemical Industries' Oxypropylene-Oxyethylene Block Polymer).
3g, Neugen EA170 (trade name of polyoxyethylene glycol nonyl phenyl ether manufactured by Daiichi Kogyo Seiyaku ■) 3G and ammonium persulfate 129 as a polymerization initiator.
Add an aqueous solution of
Emulsify at 0 C, P, M for 30 minutes to obtain a black pre-emulsion.

Next, 3I! was equipped with a stirrer, nitrogen inlet, thermometer and condenser. The black pre-emulsion was transferred to a four-piece parallel flask, and the flask was polymerized at a temperature of 70° C. for 5 hours under a nitrogen stream, and then cooled to obtain an emulsion polymerization liquid. The polymerization rate at this time was 99.9% or more.

The molecular weight of the 9-polymer was determined by gel chromatography using a standard polystyrene calibration curve.
w was 86,000, and Mn was 30,000. The thus obtained round-hole polymerization liquid was spray-dried at a temperature of 110° C. to obtain a toner.

Comparative Example 3 (pulverization method) Styrene/butyl methacrylate = 70/30 (weight ratio) 2 molecular weight 1 Mw by solution polymerization using toluene as a solvent
Polymers of 70,000 and Mn of 30,000 were prepared, and the solvent was removed under reduced pressure to remove toluene to form a white solid.

65g of carbon black was added to this polymer 9009.

15 g of Spiron Black T Bottle H and 20 G of low molecular weight polypropylene (Viscol 550P) were kneaded with two rolls and pulverized with a jet mill to obtain a toner.

Particle size and average particle size of toners obtained in Comparative Examples 1 to 3, 5
The yield of ~25 μm particles, the glass transition temperature of the main resin component, and the electrophotographic properties tested in the same manner as in Examples 1 and 2 were determined in the first
Shown in the table.

The electrophotographic properties of Examples 1 and 2 and Comparative Examples 1 and 3 were evaluated as follows.

(a) Resolution: Electrophotography Society Test Chart Nl1
1, and each prepared developer was used to make copies on plain paper. The copied images were compared and evaluated to see if they could be read in detail.

(bl Image density: In the same manner as the resolution, the density of the black part of the copied paper was measured with a densitometer and determined.

(C) Gradation: Evaluated in the same way as the resolution using the 11-level gray area in the center of the test chart.

(d) Cleanability: Each of the prepared developers was continuously copied using a copying machine at a temperature of 30° C. and a humidity of 80.1 Ri, and the number of copies until cleaning failure occurred was evaluated.

(e) Blocking resistance: Examples 1-2. Comparative example 1
The toner prepared in steps 3 to 3 was left for 72 hours at 50° C. and humidity of 95° C., and it was determined whether the toner was blocked.

◎: Very good O: Excellent △: Slightly inferior ×: Inferior It was evaluated as

(f) Charge stability: The prepared developers were stirred in a copying machine, the amount of charge was measured at regular intervals, and the change in the amount of charge was determined.

0: Very good ○: Excellent △: Slightly inferior X: Inferior It was evaluated as

Example 3 (1) Production process of suspension polymerization solution A stirrer, 1 nitrogen inlet, dropping funnel, thermometer, and 4 condensers were placed in a flask. 30
%) prepare aaag.

The mixture was kept at 90° C. under a nitrogen stream and stirred. Especially.

Styrene 574g and butyl methacrylate 2469g as polymerizable monomers. Carbon blackener 4 as a coloring agent
4 659. Spiron black TRH as a charge control agent
159 and azobisinbutyronitrile 189 as a polymerization initiator in a homomixer + 300 Or, p, m for 30
The mixed and dispersed solution was uniformly dropped into the flask over 2 hours, kept warm for 6 hours while paying attention to heat generation, and then cooled to obtain a suspension polymerization solution. The polymerization rate at this time was 99.91
That's all for now. In addition, the molecular weight (excluding gel content) of the 9-polymer was measured by high-performance liquid chromatography using a standard polystyrene calibration curve, and the Mw was 72.
000. Mn was 30,000.

(2) Drying process After removing the solvent from the suspension polymerization solution using a centrifuge.

It was dried in a dryer at 40°C to obtain a toner. When the particle size of the obtained toner was measured using a Coulter counter, the result was 1.
The particle size distribution was 1 to 50 μm, and the average particle size was 13 μm. Furthermore, Tg was measured with a differential scanning calorimeter and was found to be 65°C.

Example 4 (1) Production process of suspension polymerization solution Isopar E100091 was placed in the same flask as in Example 3.
)' Styrene-Butagencom (II8P (International Institute of Synthetics Clubber Producers, Inc.)
Isopar G of product number 1002 given by
A solution (solid content: zss) is charged, kept at 90°C under a nitrogen stream, and stirred. Separately, 9 polymerizable monomers include styrene 6969. Butyl acrylate 1749, carbon black ◆44 asg, Spiron black T
A solution obtained by mixing and dispersing RH159 and Noku-butyl 0189 at 300 Orr and pm for 30 minutes using a homomixer was added dropwise uniformly to the above flask over 2 hours, and kept warm for 6 hours while being careful not to generate heat, and then cooled. A suspension polymerization solution was obtained. The polymerization rate at this time was 99.9% or more, and the molecular weight of the polymer (excluding gel content) determined in the same manner as in Example 1 was M
w is 65000. Mn was 32,000.

(2) Drying process The suspension polymerization solution was centrifugally desolvented and dried at 40° C. in a drier to obtain a toner. When the particle size of the obtained toner was measured using a Coulter counter, the particle size distribution was 1 to 50 μm.
The average particle size was 14.5 μm. Furthermore, Tg was measured with a differential scanning calorimeter and was found to be 70°C.

Example 5 (1) Production of suspension polymerization solution Isopar E 100 was placed in a four-lobe flask equipped with a stirring device, a dropping funnel with 9 nitrogen inlets, a thermometer, and a condenser.
0s and Polyoil 130 (polybutadiene manufactured by Zeon Corporation) Separately 9 Styrene 574 as a polymerizable monomer
g and butyl methacrylate 2469. Carbon blackener 44 659 as a coloring agent. Subiron Black T H159 as a charge control agent and 18 g of azobisisobutyronitrile as a polymerization initiator were mixed in a homomixer.
Mix at o o r, p, m for 30 minutes and disperse the resulting liquid dropwise uniformly into the above flask over 2 hours.

The mixture was kept warm for 6 hours while paying attention to heat generation, and then cooled to obtain a suspension polymerization liquid. The polymerization rate at this time was 99.9 or more. The molecular weight of the 9-polymer (excluding gel content) was measured by high performance liquid chromatography using a standard polystyrene calibration curve, and the Mw was 7200.
G and Mn were 30,000.

(2) Drying process After removing the solvent from the suspension polymerization solution using a centrifuge.

It was dried in a dryer at 40°C to obtain a toner. When the particle size of the obtained toner was measured using a Coulter counter, the result was 9.
The particle size distribution was 1 to 50 μm, and the average particle size was 13 μm. Further, Tg was measured using a differential scanning calorimeter and found to be 65°C.

Example 6 (1) Manufacturing process of suspension polymerization solution 50 g of Isopar E10009 and Polyoil 160 (trade name of polybutadiene manufactured by Nippon Zeon ■) were charged into a flask similar to that in Example 5, and kept at 90°C under a nitrogen stream. Stir. Separately, styrene 696 is used as a polymerizable monomer.
9 and butyl acrylate 1749. Carbon black φ4465g, Subiron Black T 几H1sg and Hibarbutyl 018g were mixed in a homomixer.
The dispersed liquid was mixed for 30 minutes at rpm and uniformly dropped into the flask over 2 hours, being careful not to generate heat.

After keeping the temperature for 6 hours, it was cooled to obtain a suspension polymerization liquid.

The polymerization rate at this time was 99.9% or more, Example 1
Molecular weight of the polymer determined in the same manner as (excluding gel content)
has Mw of 65000. Mn was 32,000.

(2) Drying process The suspension polymerization solution was subjected to centrifugal desolvation and dried at 40° C. in a drier to obtain a toner. The particle size of the obtained toner was measured using a Coulter counter.

The particle size distribution was 1 to 50 μm, and the average particle size was 14.5 μm. Further, the glass transition point was measured using a differential scanning calorimeter and was found to be 70°C.

Example 7 (1) Production of dispersion stabilizer Isopar u7oog was placed in a four-loaf flask equipped with a stirring device, a dropping funnel with one nitrogen inlet, a thermometer, and a condenser.
9. Prepare the mixture, keep it warm at 120℃ under a nitrogen stream, and stir.9.

Separately, lauryl methacrylate) 8689. 24g of glycidyl methacrylate.

A mixture of 85 g of butyl methacrylate and 259 g of benzoyl peroxide (polymerization initiator) was uniformly dropped into the flask over 2 hours.

The temperature was raised to 140°C and kept at this temperature for 4 hours. After keeping warm.

The temperature was lowered to 50°C, and cation M! was used as a reaction catalyst between glycidyl groups and methacrylic acid. -100 (trade name of quaternary ammonium salt made by NOF ■) &59 and Isopar H 150g
was added. Incubate at 50°C for 1 hour to convert the cation Ms −
After confirming the dissolution of 100.

Methacrylic acid 239 and Isopar H1509 are added dropwise over 1 hour. During the dropping, the temperature was increased at a rate of 15°C per 10 minutes, and the temperature was kept at 140°C for 7 to 8 hours. When the acid value became 45 or less, cooling was performed as the end point. As a result, a reddish-brown dispersion stabilizer solution with a non-volatile content of SOS and an acid value of 4.2 was obtained.

(2) Production of suspension polymerization solution Isopar E100O
s and 200 g of the dispersion stabilizer obtained in (1) were charged,
Insulated at 90°C under nitrogen flow.

Stirred. Separately, 574g of styrene as a polymerizable monomer
and butyl methacrylate 2469. Carbon black φ44 ssg as a coloring agent, Subiron black TRH159 as a charge control agent, and azobisin butyronitrile 189 as a polymerization initiator were mixed in a homomixer at 300 ml.
Mix with Or, p, and m for 30 minutes and disperse the 9 liquid dropwise uniformly over 2 hours into the above flask. 9 Keep warm for 6 hours while being careful not to generate heat, then cool! ! ! The turbid and heavy turbid liquid was mixed.

The polymerization rate at this time was 99.9 or more. Also 9
The molecular weight of the polymer (excluding gel content) was measured by high performance liquid chromatography using a standard polystyrene calibration curve, and found to be Mw 72000°Mn 30
It was 000.

(3) Drying process After removing the solvent from the suspension polymerization solution using a centrifuge.

Dry in a dryer at 40°C to obtain toner. When the particle size of the obtained toner was measured using a Coulter counter, the result was 1.
The particle size distribution was 1 to 50 μm, and the average particle size was 13 μm. Furthermore, Tg was measured with a differential scanning calorimeter and was found to be 65°C.

Example 8 (1) Manufacturing process of suspension polymerization solution Isopar E10009 and 100 g of the dispersion stabilizer obtained in Example 7 (1) were charged into a flask similar to that in Example 7, and heated to 90°C under a nitrogen stream. Keep warm and stir. Separately, 696 g of styrene and 1749 g of butyl acrylate were used as polymerizable monomers. Carbon Plakna 44 659.
Subiron Black TRH159 and Perbutyl 0 18
9 with a hoso mixer so 'o o r-p-m 3
The dispersion solution obtained by mixing for 0 minutes was uniformly dropped into the above flask over 2 hours, kept warm for 6 hours while paying attention to heat generation, and then cooled to obtain a suspension polymerization solution. What is the polymerization rate at this time?

99.9% or more, and the molecular weight of the polymer determined in the same manner as in Example 1 (excluding gel content) was Mw65000, M
It was n30,000.

(2) Drying process The suspension polymerization solution was subjected to centrifugal desolvation and dried at 40° C. in a drier to obtain a toner. The particle size of the obtained toner was measured using a Coulter counter.

The particle size distribution was 1 to 50 μm, and the average particle size was 14.5 μm. Further, the glass transition point was measured using a differential scanning calorimeter and was found to be 70°C.

Comparative Example 4 (pulverization method) Styrene/butyl methacrylate-70/30 (weight ratio) 2 molecular weight Mw 70 by solution polymerization using toluene as a solvent
Polymers of 000 and Mn 30,000 were prepared, and the solvent was removed under reduced pressure to remove toluene to produce a white solid.

920 g of this polymer was kneaded with 4465 g of Carpon Blackna and Subiron Black T Bottle H159 using two rolls, and the mixture was pulverized using a jet mill and classified into two to obtain a toner.

When the particle size of the obtained toner was measured using a Coulter counter, the particle size distribution was 1 to 50 μm, and the average particle size was 12 μm.
Met. Furthermore, Tg was measured with a differential scanning calorimeter and was found to be 73°C.

The evaluation of electrophotographic properties in Examples 3 to 8 and Comparative Example 4 was performed in the same manner as in Examples 1 to 2 and Comparative Examples 1 to 3, and the fixing properties and offset resistance were further evaluated by the method shown in (g) below. did.

(g) Fixing characteristics: The heat roll temperature control device of the plain paper copying machine was cut off so that the heat roll temperature could be controlled from the outside, and IX 1 1nch black solid was fixed at each temperature.

At that time, visually check the offset (call) The presence or absence of hot and cold was determined.

In addition, the heat roll temperature should not exceed 220℃. I couldn't keep my temperature up, so I tried The temperature was up to 220°C.

Examples 3 to 8 and comparative example 40 bond value results are shown in Table 2. Example 9 (1) Production of dispersion stabilizer Isopar H7009 was placed in a four-bottle flask equipped with a stirring device, a dropping funnel with two nitrogen inlets, a thermometer, and a condenser.
was charged, kept at 120°C under a nitrogen stream, and stirred.

Separately 2 acrylic methacrylate) 8539. 24g of glycidyl methacrylate.

A mixture of dimethylamine ethyl methacrylate 1009 and benzoyl peroxide 259 as a polymerization initiator was uniformly dropped into the above flask over 2 hours, and then the temperature was raised to 140° C. and kept for 4 hours. After keeping warm 50
The temperature was lowered to °C, and cation spacing -100s, sg and Aituba-Hxsog were added. Stir at 50°C for 1 hour,
Cation M! -After confirming the dissolution of 100, methacrylic acid 2
39. Drop Isopar H1509 over 1 hour.9.

During the dropping, the temperature was increased at a rate of 15°C per 10 minutes and kept at 140°C for 7 to 8 hours. Cooling was carried out with the end point being the point where the acid value became 4.5 or less.

This gave a red colored dispersion stabilizer solution with a cine rare fraction of 50% and an acid value of 4.2.

(2) II! ! Production process of cloudy polymerization liquid Isopar H10009 and the dispersion stabilizer 2009 obtained in (1) were charged into a four-bottle flask equipped with a stirring device, a dropping funnel with 9 nitrogen inlets, a thermometer, and a condenser, and the mixture was heated to 90°C under a nitrogen stream.
Keep warm at ℃.

Stir. Separately, 9 styrene 5749 as a polymerizable monomer
and butyl methacrylate 2469. Carbon blackener 44 sog as a coloring agent and azobisin butyronitrile xsg as a polymerization initiator were mixed in a homomixer at 30
0 Or, I) The solution mixed and dispersed at 0 m for 30 minutes was uniformly dropped into the above flask over 2 hours, kept warm for 6 hours while paying attention to heat generation, and then cooled to obtain a suspension polymerization solution. The polymerization rate at this time was 99.91 or more. ``!The molecular weight of the 92 polymer (excluding gel content) was measured by high performance liquid chromatography using a standard polystyrene calibration curve, and the Mw was 72,000.Mn was 30,000.
Met.

(3) Drying process After removing the solvent from the suspension polymerization solution using a centrifuge.

It was dried in a dryer at 40°C to obtain a toner. When the particle size of the obtained toner was measured using a Coulter counter, the result was 1.
The particle size distribution was 1 to 50 μm, and the average particle size was 13 μm. Furthermore, Tg was measured with a differential scanning calorimeter and was found to be 65°C.

Example 1O (1) Production of dispersion stabilizer Isopar H7009 was placed in a four-loop flask equipped with a stirrer, two dropping funnels, a thermometer and a condenser.
was charged, kept at 120°C under a nitrogen stream, and stirred.

Separately, lauryl methacrylate ssag, glycidyl methacrylate 24g.

A mixture of 100 g of morpholinoethyl methacrylate and 259 g of benzoyl peroxide as a polymerization initiator was uniformly added dropwise to the flask over 2 hours, and then 1
The temperature was raised to 40°C and kept for 4 hours. After incubation, the temperature was lowered to 50°C, and the cation spacing was -1008.5g and the isopar His
og was added. After stirring at 50° C. for 1 hour and confirming the dissolution of cation f4-100, 23 g of methacrylic acid and 150 g of Isopar H were added dropwise over 1 hour. During the dropping, the temperature was increased at a rate of 15°C per 10 minutes and kept at 170°C for 7 to 8 hours. When the acid value became 45 or less, cooling was performed as the end point.

As a result, a red and colored dispersion stabilizer solution with a cine-reduced content of 50 yen and an acid value of 40 was obtained.

(2) Manufacturing process of suspension polymerization solution Isopar E10009 and the dispersion stabilizer 3009 obtained in (1) are charged into a flask similar to that in Example 9, kept at 90° C. under a nitrogen stream, and stirred. Separately, 616 g of styrene was used as a single polymerizable monomer.

Butyl acrylate) 1549. Carbon black φ44
3. Sog and barbutyl 018g in a homomixer
The liquid mixed and dispersed at 00 Or, p, and m for 30 minutes was uniformly dropped into the flask over 2 hours.

The mixture was kept warm for 6 hours while being careful not to generate heat, and then cooled to obtain a suspension polymerization liquid. The polymerization rate at this time was 99.9% or more and 2
The molecular weight of the polymer (excluding gel content) is Mw 650.
00. Nine with Mn of 32,000.

(3) Drying step The suspension polymerization solution was centrifugally desolvented and dried at 40° C. in a drier to obtain a toner. When the particle size of the obtained toner was measured using a Coulter counter, the particle size distribution was 1 to 50 μm.
The average particle size was 14.5 μm. Furthermore, Tg was measured with a differential scanning calorimeter and was found to be 70°C.

Example 11 (1) Production process of suspension polymerization solution Isopar Eiooog and the dispersion stabilizer 2009 obtained in (1) of Example 9 were placed in the same flask as in Example 9.
9. Prepare and keep warm at 90°C under nitrogen stream, stir. Separately, styrene 7199 is used as a dipolymerizable monomer. 10 g of butyl acrylate 1809.7 talocyanine puri and barbutyl 018 were mixed in a homomixer,
Mix and disperse at pm for 30 minutes and transfer the 9 liquids to the above flask.
Drop it evenly over a period of time and keep it warm for 6 hours while being careful not to generate heat, then cool to obtain a suspension polymerization liquid. The polymerization rate at this time was 99.9 S or more, and the Mw of molecule 1 of the dipolymer (excluding gel content) was 63,000. Mn is 31000, 6 nine.

(2) Drying process The suspension polymerization solution was centrifugally desolvented and dried at 40° C. in a drier to obtain a toner. When the particle size of the obtained toner was measured using a Coulter counter, there were two particle size distributions: 1 to 50 μm;
The average particle size was 14.3 μm. Further, the Tg was measured using a differential scanning calorimeter and was found to be 71°C.

Comparative Example 5 Dimethylaminoethyl methacrylate/styrene/butyl methacrylate-1 was produced by solution polymerization using toluene as a solvent.
/69/30 (weight ratio) 1 A polymer with a molecular weight of 70,000 Mw and 3,000 G of Mn was prepared.

The solvent was removed under reduced pressure to remove toluene and a white solid was produced.

Carbon black 809 was kneaded with this polymer 9209 using two rolls, and the mixture was pulverized using a jet mill.

The toner was obtained by classification.

The particle size of the obtained nine toners was measured using a Coulter counter, and the particle size distribution was 1 to 50 μm, with an average particle size of 12 μm.
And nine. Furthermore, Tg was measured with a differential scanning calorimeter and was found to be 73°C.

Comparative Example 6 In Comparative Example 5, the weight ratio of dimethylaminoethyl methacrylate/styrene/butyl methacrylate was 1/69/30.
A toner was prepared in exactly the same manner except that the toner was changed from 30/69/1 to 30/69/1.

The molecular weight Mw of the polymer is 70,000. Mn was 30,000. In addition, the obtained toner has a particle size distribution of 1 to 59 μm.
, the average particle size was 12 μm, and the Tg was 71°C.

Comparative Example 7 Styrene/butyl methacrylate-70/30 (weight ratio) 1 molecular weight Mw 700 by solution polymerization using toluene as a solvent
Polymers of 00 and Mn 30,000 were prepared, and the solvent was removed under reduced pressure to remove toluene to produce a white solid. This polymer 8709 was mixed with carbon black φ44 aog and oil black 80 (nigea manufactured by Orient Chemical Industry ■).
Add 50g of Shin dye (product name) and knead with two rolls.
It was pulverized with a jet mill and classified into 9 parts to obtain a toner.

The obtained toner had a particle size distribution of 1 to 50 μm and an average particle size of 12
It was measured in μm and Tg was 71'C.

Example 12 (11 Production of dispersion stabilizer) A 94-hole flask was equipped with an Isopar 8700 stirrer, two nitrogen inlets, a dropping funnel, a thermometer, and a condenser.
9 was charged, the temperature was kept at 120°C under a nitrogen stream, and the mixture was stirred. Separately lauryl methacrylate 8539. A mixture of 23 g of methacrylic acid, 100 g of p-styrenesulfonic acid, and 259 g of benzoyl peroxide as a polymerization initiator was uniformly dropped into the flask over 2 hours.

The temperature was raised to 140'C and kept at this temperature for 4 hours. After keeping warm, the temperature was lowered to 50° C., and 5 g of cation Fdx-100a and 150 g of Isopar H were added. After stirring at 50° C. for 1 hour and confirming the solution of cation Mx-100.

Glycidyl methacrylate 24g, Isopar H150
9 was added dropwise over 1 hour. 15 per 10 minutes during dripping
The temperature was raised at a rate of 140° C., kept at 140° C. for 8 hours, and then cooled.

As a result, a red and colored dispersion stabilizer solution containing 50% non-rare fraction was obtained.

(21! Production process of greenhouse mixture
1i1 and the dispersion stabilizer 2'009 obtained in (1) were charged and kept at 90°C under a nitrogen stream.

Stirred. Separately, 574 g of styrene as a single polymerizable monomer
and butyl methacrylate 2469. Carbon blackener 44 sog as a coloring agent and azobisisobutyronitrile 189 as a polymerization initiator were mixed in a homomixer at 30°C.
A solution mixed and dispersed for 30 minutes at 0 Or, p, and m was added dropwise to the above flask over 2 hours, and the mixture was kept warm for 6 hours while being careful not to generate heat.

It was cooled to obtain a suspension polymerization liquid. The polymerization rate at this time was 99.
It was 9- or more. The molecular weight of the i92 polymer (excluding gel content) was measured by high-speed chromatography using a standard polystyrene calibration curve, and the Mw was 72.
000. Mn was 30,000.

(3) Drying process After removing the solvent from the suspension polymerization solution using a centrifuge.

It was dried in a dryer at 40°C to obtain a toner. When the particle size of the obtained toner was measured using a Coulter counter, the result was 9.
The particle size distribution was 1 to 50 μm, and the average particle size was 13 μm. Furthermore, Tg was measured with a differential scanning calorimeter and was found to be 65°C.

Example 13 (1) Production of dispersion stabilizer Isopar H700 was placed in a four-bottle flask equipped with a stirring device, nitrogen inlet, @ lower funnel, thermometer and condenser.
s was charged, kept at 120°C under a nitrogen stream, and stirred. Separately lauryl methacrylate) 8539. Methacrylic #
1123g and polymerization initiator benzoyl peroxide 2
A mixed solution in which 59 was dissolved was uniformly dropped into the flask over 2 hours, and then the temperature was raised to 140° C. and kept at that temperature for 4 hours.

After insulating, the temperature was lowered to 50℃, and the cation bh-100asg
and Isopar Hisog were added. After stirring at 50° C. for 1 hour and confirming the dissolution of the cation Ml-100, 150 g of glycidyl methacrylate 249° Isopar H was added dropwise over 1 hour.

During the dropping, the temperature was increased at a rate of 15°C per 10 minutes, kept at 140°C for 8 hours, and then cooled.

As a result, a red and colored dispersion stabilizer solution of SOW was obtained.

(2) Production process of suspension polymerization solution Isopar E10009 was added to the same flask as in Example 12.
Then, the dispersion stabilizer 3009 obtained in (1) is charged, kept at 90° C. under a nitrogen stream, and stirred. Separately, one polymerizable monomer is styrene 6169°butyl acrylate 15
49. Carbon Blackna 44 AOG and Barbutyl 0189 were mixed and dispersed in a homomixer at 300 Orr and pm for 30 minutes, and the liquid was added dropwise into the above flask over 2 hours. A suspension polymerization solution was obtained. The polymerization rate at this time was 99.9 S
The molecular weight (excluding gel content) of the above-mentioned ASI 1 polymer is Mw of 65,000. Mn was 32,000.

(3) Drying step The suspension polymerization solution was centrifugally desolvented and dried at 40° C. in a drier to obtain a toner. The particle size of the obtained toner was measured using a Coulter counter, and the particle size distribution was 1 to 50 μm.
The average particle size was 14.5 μm. Furthermore, Tg was measured with a differential scanning calorimeter and was found to be 70°C.

Example 14 (1) @Manufacturing process of liquid
and 200 g of the dispersion stabilizer obtained in Example 12 (1)
was charged, kept at 90°C under a nitrogen stream, and stirred. Separately, 9 polymerizable monomers include styrene 7199. Butyl acrylate) 1809. Phthalocyanine blue 10 g and Uha = 7'fko 18 g in a homomixer at 300O
A liquid mixed and dispersed for 30 minutes using r-p-ffl was added dropwise to the flask over 2 hours, kept warm for 6 hours while being careful to avoid heat generation, and then cooled to obtain a suspension polymerization liquid. The polymerization rate at this time was 99.9 inches or more, and the molecular weight of one polymer (excluding gel content) was 63,000. Mn was 31,000.

(2) Drying process The above suspension polymerization solution was centrifugally desolvented and dried at 40° C. in a drier to obtain a toner. When the particle size of the obtained toner was measured using a Coulter counter, the particle size distribution was 1 to 50 μm.
The average particle size was 14.3 μm. Furthermore, Tg was measured with a differential scanning calorimeter and was found to be 71°C.

Comparative Example 8 Solution polymerization using toluene as a solvent p-styrene sulfonic acid/styrene/butyl methacrylate = 1/69/30
(Weight ratio) 9 Molecular weight Mw 70000 and Mn 30
000 polymer was prepared, the solvent was removed under reduced pressure, and toluene was removed to produce a white solid.

Carbon black 809 was kneaded with this polymer 9209 using two rolls, and the mixture was pulverized using a jet mill.

The toner was obtained by classification.

The particle size of the obtained nine toners was measured using a Coulter counter, and the particle size distribution was 1 to 50 μm, with an average particle size of 12 μm.
Met. Furthermore, Tg was measured with a differential scanning calorimeter and found to be 73°C.

Comparative Example 9 In JIL Example 8, the weight ratio of p-styrene sulfonic acid/styrene/butyl methacrylate was changed from 1/69/30 to 30/
A toner was produced in exactly the same manner except that 69/1 was used. Particle size distribution is 1-50 μm, average particle size IL5 μm, '
l'g is 81℃ and 9. Also, Mw is 72000. Mn
is 3000G and nine.

Examples 9 to 14 and Comparative Examples 5 to 9 were evaluated using 5% by weight of each toner and iron oxide powder (manufactured by Nippon Iron Powder ■, trade name EFV).
A developer was prepared by mixing 95% by weight of 20G/300). The amount of blow-off charge of this developer was measured and the results are shown in Table 3.

The actual machine copying test of the developer was conducted in Examples 9 to 11 and Comparative Example 5.
Examples 12 to 14 and Comparative Examples 8 to 9 were carried out using a copying machine model 8F-755 manufactured by Sharp ■, and Copier ■ reverse copying machine model NC-3000 for Examples 12 to 14 and comparative examples 8 to 9.

Evaluation of electrophotographic properties was carried out in Examples 1 to 2 and Comparative Examples 1 to 3.
I did the same thing. Table 3 shows the evaluation results.

Example 15 (1) l! ! Isopar E 100 in a 4-bottle flask equipped with a stirring device, a nitrogen inlet with 9 dropping funnels, a thermometer, and a condenser.
09 and natural rubber (SM 几-5) Isopar H solution (
Prepare solid content 3os) aaag and heat at 90℃ under nitrogen stream.
The mixture was kept warm and stirred.

Separately, 574 g of styrene and 2469 g of pool methacrylate were used as polymerizable monomers. MG-WF (
Mitsui Kinzoku Kogyo ■, -1 Gnetite) 11659, Spiron black TRH (Hodogaya Chemical Industry ■) as a charge control agent, low molecular weight polypropylene (Viscol 660 F, Sanyo Chemical Industries ■) zog and polymerization initiation A solution prepared by mixing and dispersing azobisinbutyronitrile 189 as an agent for 30 minutes at a o o o r, p, m using a homomixer was added dropwise uniformly into the above flask over 2 hours. After keeping it warm for 90 minutes, cool it and make a suspension polymerization liquid. The polymerization rate at this time was 99.91 or more. The molecular weight of the dipolymer (excluding gel content) was measured by high performance liquid chromatography using a standard polystyrene calibration curve.

Mw is 72000. Mn was 30,000.

(2) Drying process After removing the solvent from the suspension polymerization solution using a centrifuge.

It was dried in a dryer at 40°C to obtain a magnetic toner. The particle size of the obtained good magnetic toner was measured using a Coulter counter, and the particle size distribution was 1 to 50 μm, with an average particle size of 13 μm. Furthermore, when Tg was measured with a differential scanning calorimeter,
The temperature was 65°C.

(3) Evaluation This magnetic toner is used for plain paper copying machines (manufactured by Konishiroku Photo Industry),
Electrophotographic properties were tested using U-Bix 1200). However, the toner contains hydrophobic silica (R-972 manufactured by Nippon Aerosil ■) and zinc stearate as fluidity improvers at 0.6 and 0.1%, respectively, for the above toner.
Excellent external additive treatment was applied.

Example 16 (1) Production of suspension polymerization solution Isopar E 100 was placed in a four-lobe flask equipped with a stirring device, a dropping funnel with 9 nitrogen inlets, a thermometer, and a condenser.
09 and polyoil 130 (polybutadiene manufactured by Nippon Zeon@) 1009 were charged, kept at 90° C. under a nitrogen stream, and stirred. Separately 9 Styrene 574 as a polymerizable monomer
static and butyl methacrylate) 2469. M as magnetic powder
G-WFitasg, Spiron black TRH (manufactured by Hodogaya Chemical Industry ■) 159e low molecular weight polypropylene/(Viscol 660P) 209 as a charge control agent, and azobisin butyronitrile 189 as a polymerization initiator were mixed in a homomixer. The dispersion solution was mixed for 30 minutes at rpm and was uniformly dropped into the above flask over 2 hours. After keeping the temperature for 6 hours while paying attention to heat generation, the suspension was cooled to obtain a suspension polymerization solution. . The polymerization rate at this time was 99.9 or more. The molecular weight of the dipolymer (excluding gel content) was measured by high performance liquid chromatography using a standard polystyrene calibration curve, and the Mw was 7.
2000, Mn was aooooo.

(2) Drying process After removing the solvent from the suspension polymerization solution using a centrifuge.

It was dried in a dryer at 40°C to obtain a magnetic toner. When the particle size of the obtained magnetic toner was measured using a Coulter counter, the particle size distribution was 1 to 50 μm, and the average particle size was 13 μm. Furthermore, when Tg was measured with a differential scanning calorimeter,
The temperature was 65°C.

Example 17 Isopar E100o was placed in a four-lobe flask equipped with a stirrer, nitrogen inlet, M lower funnel, thermometer and condenser.
g and dispersion stabilizer 2009 obtained in Example 7 (1)
was charged, kept at 90°C under a nitrogen stream, and stirred. Separately, 9 polymerizable monomers were styrene 5749 and butyl methacrylate 2469, and magnetic powder was MG-WF 11.
659. Subiron Black TRH15 as a charge control agent
G, low molecular weight polypropylene (Viscol 660P)
209 and 18 g of azobisisobutyronitrile as a polymerization initiator were mixed for 30 minutes at 3,000 cpm using a homomixer, and the dispersed liquid was uniformly dropped into the above flask over 2 hours.2 While being careful of heat generation, the mixture was kept warm for 6 hours. After that, it was cooled to obtain a suspension polymerization liquid. The polymerization rate at this time was 99.9
-That's all. Also.

The molecular weight of the polymer (excluding gel content) was measured by high performance liquid chromatography using a standard polystyrene calibration curve, and found to be Mw72000, Mn30.
It was 000.

After removing the solvent from the suspension polymerization solution using a centrifuge.

It was dried in a dryer at 40°C to obtain a magnetic toner. When the particle size of the obtained magnetic toner was measured using a Coulter counter, the particle size distribution was 1 to 50 μm, and the average particle size was 13 μm. Furthermore, when Tg was measured with a differential scanning calorimeter,
The temperature was 65°C.

Comparative Example 10 Styrene/butyl methacrylate - 70/30 (weight ratio) 9 molecular weight Mw 700 by solution polymerization using toluene as a solvent
Polymers of 00 and Mn 30,000 were prepared, and the solvent was removed under reduced pressure to remove toluene to produce a white solid.

MG-WF1165 was added to 920 g of this polymer as magnetic powder.
g, low molecular weight polypropylene (Viscol 660P) 2
09 and Subiron Black TRH159 were kneaded with two rolls, pulverized with a jet mill, and classified into two to obtain a magnetic toner.

When the particle size of the obtained magnetic toner was measured using a Coulter counter, the particle size distribution was 1 to 50 μm.

The average particle size was 12 μm. Furthermore, Tg was measured with a differential scanning calorimeter and was found to be 73°C.

The electrophotographic properties of Examples 16 and 17 and Comparative Example 1O were evaluated using the same apparatus as in Example 15. In addition,
Evaluation tests for electrophotographic properties of Examples 16 to 18 and Comparative Example 10 were conducted in the same manner as Examples 3 to 8 and Comparative Example 4. The test results are shown in Table 4.

Table 4 Evaluation (Effect of the invention) According to the present invention, a non-aqueous suspension polymerization method is utilized.

In particular, it is possible to obtain an electrophotographic toner which is suitable for dry development and has excellent single-resolution image density and gradation properties under high humidity, as well as particularly excellent cleaning properties, charging stability, and blocking resistance.

Furthermore, by selecting the dispersion stabilizer 9, it is possible to obtain a toner with excellent fixing properties and/or offset resistance.

Claims (1)

[Claims] 1. A method for producing an electrophotographic toner, which comprises suspending and polymerizing a polymerizable monomer in a non-aqueous solvent in the presence of a colorant and/or magnetic powder. 2. The method for producing an electrophotographic toner according to claim 1, further comprising a dispersion stabilizer. 3. The method for producing an electrophotographic toner according to claim 2, wherein the dispersion stabilizer is rubber. 4. The method for producing an electrophotographic toner according to claim 2, wherein the dispersion stabilizer is polybutadiene. 5. The method for producing an electrophotographic toner according to claim 2, wherein the dispersion stabilizer is a polymer containing as an essential component an acrylic ester and/or a methacrylic ester having a long carbon chain. 6. The method for producing an electrophotographic toner according to claim 5, wherein the long carbon chain is an alkyl group having 8 or more carbon atoms. 7. The method for producing an electrophotographic toner according to claim 5 or 6, wherein the polymer has an amino group-containing addition polymerizable monomer as a copolymerizable component. 8. The electron according to claim 5 or 6, wherein the polymer has a polymerizable monomer having a carboxyl group and/or a sulfone group and/or a metal salt thereof as a copolymerization component. Method of manufacturing photographic toner. 9. The electrophotographic toner according to claim 5, 6, 7, or 8, wherein the polymer further has an unsaturated bond group reactive with the polymerizable monomer. manufacturing method.