JPH02275964A - Toner formed by suspension polymerization method and production thereof - Google Patents

Abstract

PURPOSE:To improve color tones by dispersing a monomer compsn. consisting of a polymerizable monomer soln. or dispersion, which is prepd. by dissolving or dispersing dyes or pigments treated by a mass polymn. method into a polymerizable monomer, and a polymn. initiator into an aq. dispersion medium and subjecting the mixture to a suspeision polymn. CONSTITUTION:The monomer compsn. is prepd. by mixing the polymerizable monomer soln. or dispersion, which is prepd. by treating the dyes or pigments having chromatic colors by the mass polymn. method into the polymerizable monomer, and the polymn. initiator. This compsn. is dispersed into the aq. dispersion medium and the medium is subjected to the suspension polymn. The dyes or pigments treated by the mass polymn. method do not substantially hinder the polymn. reaction by the polymn. initiator even when used for the process for production of the toner by the suspension polymn. method. The good execution of the suspension polymn. reaction is possible in this way and further, the polymn. initiator dissolves or disperses well in the polymerizable monomer and, therefore, the color tones and saturation of the resulted toner are improved.

Description

Detailed Description of the Invention [Technical Field] The present invention relates to a toner used for visualizing an electrical latent image in an image forming method such as electrophotography or electrostatic photography, and Concerning how to prepare legally.

[Background technology]

Toners for visualizing latent electrical or magnetic images are used in a variety of image forming and recording processes.

As one of such image forming processes, electrophotography, many methods are known, such as those described in US Pat. No. 2,297,691. This electrophotographic method generally uses a photoconductive substance to form an electrical latent image on a photoreceptor by various means, and then develops the latent image with toner to form a toner image. Then, if necessary, after transferring this toner image to a transfer material such as paper, the image is fixed to the transfer material using heat, pressure, heat and pressure, or solvent vapor. , obtain a copy. Various methods have been proposed in the past as methods for developing with toner or for fixing toner images, and methods suitable for each image forming process are adopted.

Conventionally, I-ners used for these purposes are generally prepared by melt-kneading a thermoplastic resin and a colorant consisting of a dye or/and a pigment, uniformly dispersing the colorant in the thermoplastic resin, and then
By cooling, pulverizing, and classifying, a toner having a desired particle size is produced.

Although this production method (pulverization method) can produce a fairly good toner, there are certain limitations (for example, limitations on the range of selection of materials for the l-toner). For example, the dispersion of resin and colorant must be sufficiently brittle (and capable of being pulverized by economically available manufacturing equipment). When the dispersion is actually pulverized at high speed, particles with a wide range of particle sizes are likely to be formed.

In particular, a relatively large proportion of excessively finely divided particles
A problem arises in that particles are likely to be included in this particle group. Furthermore,
Such brittle materials are more likely to be pulverized or powdered when actually used for development in an image forming apparatus such as a copying machine.

In the pulverization method, it is not easy to uniformly disperse solid fine particles such as magnetic powder or colorant into the resin, and depending on the degree of dispersion of the solid fine particles, it may cause an increase in fog and a decrease in image density. Therefore, sufficient attention must be paid to the degree of this dispersion. When the colorant is exposed on the fractured surface of the resin particles colored with the colorant, variations in toner development characteristics may occur.

On the other hand, in order to overcome the problems of toner produced by the pulverization method, a method for producing l-toner using a suspension polymerization method has been proposed (Japanese Patent Publication No. 36-1023, etc.). In this suspension polymerization method, polymerizable monomers and colorants (and, if necessary, polymerization initiators, crosslinking agents, charge control agents, and other additives) are uniformly dissolved or dispersed to form a monomer composition. After objectifying,
This monomer composition is dispersed in a continuous phase (for example, an aqueous phase) containing a dispersion stabilizer using a suitable stirrer, and a polymerization reaction is simultaneously carried out to obtain toner particles having a desired particle size. There is.

Colorants used in the toner manufacturing method using suspension polymerization include pigments and dyes. In the case of a toner manufacturing method using the pulverization method, even pigments and dyes that have polymerization inhibiting properties can be used as colorants, but in the toner manufacturing method using the suspension polymerization method, some colorants may have polymerization inhibiting properties. There are some that exhibit noticeable coloring, and the usable colorants are greatly limited. In particular, dyes have a remarkable tendency to inhibit polymerization, and in the case of a toner production method using a suspension polymerization method, it has been difficult to obtain a toner with a desired color and excellent development characteristics.

[Purpose of the invention]

An object of the present invention is to provide a manufacturing method for preparing a toner containing a dye having a chromatic color or a pigment having a chromatic color and having excellent development characteristics by a suspension polymerization method, and a toner obtained by the manufacturing method. There is a particular thing.

SUMMARY OF THE INVENTION An object of the present invention is to provide a manufacturing method for preparing a l-toner having excellent color tone by a suspension polymerization method, and a toner obtained by the manufacturing method.

An object of the present invention is to provide a manufacturing method for preparing a toner with excellent chroma by a suspension polymerization method, and a toner obtained by the manufacturing method.

An object of the present invention is to provide a manufacturing method for preparing a toner by a suspension polymerization method in which inhibition of polymerization by dyes or pigments is suppressed, and a l-toner obtained by the manufacturing method.

An object of the present invention is to provide a manufacturing method for preparing a color toner having good development characteristics by a suspension polymerization method, and a color toner obtained by the manufacturing method.

[Summary of the invention]

In the present invention, a dye having a chromatic color or a pigment having a chromatic color is treated by a bulk polymerization method, and the treated dye or pigment is dissolved or dispersed in a polymerizable monomer to form a polymerizable monomer solution or dispersion. A monomer composition is prepared by mixing a polymerizable monomer solution or dispersion with a polymerization initiator, and a suspension polymerization method is performed by dispersing the monomer composition in an aqueous dispersion medium. The present invention relates to a toner comprising toner particles prepared from the obtained polymer particles.

Furthermore, the present invention processes a dye having a chromatic color or a pigment having a chromatic color by a bulk polymerization method, and dissolves or disperses the treated dye or pigment in a polymerizable monomer to form a polymerizable monomer solution or dispersion. A monomer composition is prepared by mixing a polymerizable monomer solution or dispersion with a polymerization initiator, and the monomer composition is dispersed in an aqueous dispersion medium to perform a suspension polymerization method. The present invention relates to a method for producing a toner, which comprises the steps of: obtaining polymer particles, and preparing toner particles from the obtained polymer particles.

[Detailed description of the invention]

When a toner is prepared from a polymerizable monomer by a suspension polymerization method, the reaction state of the polymerizable monomer during suspension polymerization greatly influences the characteristics of the toner. For example, if the dye or pigment consumes a large amount of radicals generated from the polymerization initiator used during the suspension polymerization reaction, the polymerization reaction of the monomers will be inhibited. Specifically, as shown in the comparative example below, a suspension polymerization reaction was carried out in the presence of an anthraquinone dye having polymerization-inhibiting properties (for example, 1,4-diamino-2,3-diphenoxyanthraquinone). In this case, the polymerization reaction did not substantially proceed.

If the suspension polymerization reaction is carried out using the total amount of the polymerization initiator consumed by the dye having polymerization-inhibiting properties and the amount of the polymerization initiator used in the polymerization reaction, the polymerization A large amount of polymerization initiator is initially present in the reaction system, producing a large amount of low molecular weight polymer components, and as a result, the storage stability (e.g. blocking resistance) of the toner obtained by the suspension polymerization reaction is affected. ) or development characteristics (for example, multi-sheet durability) deteriorate.

In the present invention, a dye having a chromatic color (preferably a chroma of 0110 or more, more preferably 30 or more, still more preferably 40 or more) or a pigment having a chromatic color (preferably a chroma of C''), 0 or more. (preferably 30 or more, more preferably 40 or more) is treated by a bulk polymerization method to prepare a radically activated dye or pigment solution, which is used in the suspension polymerization reaction.

The treatment of the dye or pigment is carried out by dissolving or dispersing the dye or pigment in a polymerizable monomer and bulk polymerizing the polymerizable monomer in the presence of a polymerization initiator. When the polymerizable monomer is bulk polymerized in the presence of a polymerization initiator, the radically active sites of the dye or pigment react with the polymerizable monomer to inactivate the radically active sites, and/or Alternatively, the radically active sites of the dye or pigment react with each other during bulk polymerization, thereby inactivating the dye or pigment.

Even when dyes or pigments treated by the bulk polymerization method are used in a toner production method using the suspension polymerization method, they do not substantially inhibit the polymerization reaction caused by the polymerization initiator, so the suspension polymerization reaction can be carried out well. can. Furthermore, if the same or the same type of polymerizable monomer as that used in the suspension polymerization method is used in the bulk polymerization method, the treated dye or pigment will be substantially free from polymerization light pollution. In addition, since it is well dissolved or dispersed in the polymerizable monomer, the resulting toner has good color tone and saturation.

In the treatment of dyes or pigments by bulk polymerization, the concentration of the dye or pigment having polymerization inhibiting properties is 5 to 50% by weight based on the polymerizable monomer ◇ Preferably 10 to 20% by weight
Shigesato% is good. If the concentration of the dye or pigment is higher than 50% by weight, it is difficult to carry out the bulk polymerization reaction efficiently, and there is a high tendency for dyes or pigments with residual radical active sites to be mixed in. The concentration of dye or pigment is 5
If the amount is less than % by weight, the large amount of polymer produced by bulk polymerization will make it difficult to dissolve or disperse uniformly in the polymerizable monomer, and the coloring power of the polymerizable monomer will also decrease. descend.

The chromatic dyes and pigments used in the present invention are preferably dyes that do not migrate into the aqueous phase and exhibit little change in hue and saturation when treated with a bulk polymerization reaction, such as:
Anthraquinone dye, xanthine (rhodamine)
Examples include dyes, azine dyes, anthraquinone pigments, and xanthine (rhodamine) pigments. In the present invention, carbon black and magnetic substances are excluded as pigments having chromatic colors used in the present invention.

Examples of anthraquinone dyes include C, 1, turben! shown in the following formula (1) and C, 1, turben! shown in the following formula (2). ...Red 52 (C, 1, 5 oevent Red 52
), [:1-(N-methylacetamido)-4-p-toluidinoanthraquinone ring-closed anthrapyridone compound], and the like.

Formula (2) As the xanthine dye, C,1 shown in the following formula (3)
, Solvent Red 49 (C, 1,5olven
tRed 4.9), [condensate of m-diethylaminoferrule and phthalic anhydride], and the like.

Formula (3) As the anthraquinone pigment, C, 1, pigment
Red 83 (C, T, Pigment Red
83 - Sanyo Carmine L2B, manufactured by Sanyo Shiki Co., Ltd.).

Examples of the xanthine pigment include lakes of xanthine dyes. For example, there is a laked product of xanthine dye represented by the following formula (4).

[In the formula, R1+ R3+ R6+ Ra and R7
are the same or different groups and represent hydrogen or a lower alkyl group, R2 and R4 are the same or different groups and represent a lower alkyl group, A○ represents an anion] Specifically, C, T, pigment・Retsu lj8] (C1, Pig
ment Red 8]) phosphotungsten molybdate, a condensate of 3-ethylamino-p-cresol and phthalic anhydride].

As the polymerization initiator used in the bulk polymerization reaction, an azo polymerization initiator described below is preferable.

As the polymerizable monomer used in the bulk polymerization reaction, vinyl monomers are preferred. Examples of vinyl monomers include styrene: 0-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-ethylstyrene and other styrene derivatives: methacrylic acid, methyl methacrylate, ethyl methacrylate, methacrylate. acid prohil,
α such as n-butyl methacrylate, isobutyl methacrylate, n-ocdyl methacrylate, F-decyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate −
Methylene aliphatic monocarboxylic acid esters; acrylic acid, methyl acrylate, ethyl acrylate 1, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate , stearyl acrylate,
Acrylic acid esters such as 2-chloroethyl acrylate and phenyl acrylate; acrylic acid derivatives or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide. These monomers can be used alone or in combination.

Preferably, using the same or the same kind of polymerizable monomer as the polymerizable monomer used in the suspension polymerization reaction in the subsequent step in the bulk polymerization reaction means that the dye or pigment is dissolved in the polymerizable monomer. It is preferable in terms of properties and dispersibility. If the dye or pigment to be treated does not dissolve in the polymerizable monomer used in the bulk polymerization reaction, thoroughly stir the dye or pigment with the polymerizable monomer using a stirrer that involves grinding, such as a hole mill. However, it is preferable to conduct the bulk polymerization reaction after pulverizing the dye or pigment and uniformly dispersing it in the polymerizable monomer.

It is preferable that the polymer lumps containing dyes and pigments treated by the bulk polymerization method are crushed and used in the form of powder.

The dyes and pigments treated by the bulk polymerization method are dissolved or dispersed in the polymerizable monomer used in the suspension polymerization reaction together with the polymer produced by the bulk polymerization reaction. From the viewpoint of solubility or dispersibility of the dye or pigment, it is preferable that the polymer produced by the bulk polymerization reaction dissolves well in the polymerizable monomer.

Therefore, as described above, it is preferable that the polymerizable monomer used in the bulk polymerization reaction and the polymerizable monomer used in the suspension polymerization reaction are the same or of the same type. For example, when using styrene as the polymerizable monomer used in a suspension polymerization reaction, the polymerizable monomer used in a bulk polymerization reaction is styrene, or styrene and acrylic ester (or methacrylic ester). ) is preferable, and when using styrene and n-butyl acrylate (or methacrylate ester) as the polymerizable monomers used in the suspension polymerization reaction, it is preferable to use a mixture with the polymerizable monomer used in the bulk polymerization reaction. As the monomer, it is preferable to use styrene or styrene and acrylic ester (or methacrylic ester).

The treated dye or pigment is preferably used in an amount of 0.5 to 10% by weight, based on the polymerizable monomer used in the suspension polymerization reaction.

As the polymerizable monomer used in the suspension polymerization method, vinyl monomers are preferred. Examples of vinyl monomers include styrene; styrene derivatives such as 0-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, and p-ethylstyrene: methyl methacrylate, ethyl methacrylate, propyl methacrylate; , n-butyl methacrylate, isobutyl methacrylate, n-methacrylate
-octyl, dodecyl methacrylate, methacrylic acid-2
- α-methylene aliphatic monocarboxylic acid ester acids such as ethylhexyl, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 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, and other acrylic acid esters; such as acrylonitrile, methacrylonitrile, and acrylamide. , acrylic acid derivatives or methacrylic acid derivatives.

These monomers can be used alone or in combination. Among the above-mentioned monomers, it is preferable to use styrene or a styrene derivative alone or in combination with other monomers as a polymerizable monomer in terms of the development characteristics and durability of the toner.

It is easier to polymerize the monomer by adding a vinyl polymer having a polar group, a vinyl copolymer having a polar group, or a cyclized rubber as an additive during the polymerization of the polymerizable monomer in suspension polymerization. preferable. It is preferable to use one having a polar group (up to 100,000).

In the present invention, during polymerization, a polymerizable monomer composition to which a vinyl polymer having a polar group, a vinyl copolymer having a polar group, or a cyclized rubber is added is mixed with the polar polymer in a reverse loading property. It is preferable to suspend and polymerize in an aqueous phase in which a dispersant is dispersed.

The cationic or anionic polymer, cationic or anionic copolymer or cyclized comb contained in the polymerizable monomer composition is a counterloadable anionic or cationic polymer dispersed in the aqueous phase. The dispersion stabilizer and the toner particle surface are electrostatically attracted to each other during the polymerization reaction, and the dispersion stabilizer covers the particle surface to prevent the particles from coalescing and stabilize them. Since the coalescence gathers on the surface layer of the particles that become toner, it takes on a kind of shell-like form, and the resulting particles become pseudo-capsules. By using a relatively high molecular weight polar polymer, copolymer or cyclized rubber, the toner particles have excellent blocking properties, developability, and abrasion resistance, while the interior is fixed with a relatively low molecular weight. By performing polymerization to contribute to improving properties,
It is possible to obtain a toner that satisfies the contradictory requirements of fixing properties and blocking properties. Examples of polar polymers (including polar copolymers) and anti-loading dispersion stabilizers that can be used in the present invention are shown below.

(1) As the cationic polymer, a polymer of a nitrogen-containing monomer such as dimethylaminoethyl methacrylate or diethylaminoethyl acrylate, or a copolymer of styrene, an unsaturated carboxylic acid ester, and the nitrogen-containing monomer There is.

(ii) Anionic copolymers include nitrile monomers such as acrylonitrile, halogen monomers such as vinyl chloride, unsaturated carboxylic acids such as nialic acid, unsaturated dibasic acids, and unsaturated dibasic acids. Anhydride ÷←H-7FF-:
There are polymers of nitro monomers.

(iii) As the anionic dispersion stabilizer, Aerosil #200. #300. There are hydrophilic colloidal silicas such as #380 (manufactured by Nippon Aerosil Co., Ltd.).

(iv) Examples of the cationic dispersion stabilizer include hydrophilic positively charged silica fine powder such as aluminum oxide and aminoalkyl-modified colloidal silica. Cyclized rubber may be used instead of the polar polymer.

The amount of such a dispersion stabilizer is preferably 0.2 to 20 parts by weight, more preferably 0.2 to 20 parts by weight per 100 parts by weight of the polymerizable monomer.
．． It is preferable to add 3 to 15 parts by weight to the aqueous medium.

On the other hand, as the charge control substance added as necessary, generally known substances can be used. Examples include metal complex salts of salicylic acid and metal complex salts of dialkyl salicylic acid. The charge control agent (J) is preferably blended into the toner in an amount of 0.1 to 5% by weight.

For the purpose of improving mold release properties during hot roll fixing, waxes that are generally used as mold release agents, such as hydrocarbon compounds, may be blended into the l.chie. As the hydrocarbon compound that can be used in the present invention, paraffin wax is preferably used, and it is preferable to use one having a softening point of 55 to 75°C. More specifically, the hydrocarbon compounds include, for example, paraffin wax (manufactured by Kuchimoto Ishiura),
There are paraffin wax (manufactured by Hiki Seiro), micro wax (manufactured by Nippon Oil), and microcrystal wax (manufactured by Nippon Seiro).

Examples of the polymerization initiator include azo polymerization initiators. For example, 2,2'-azohisisobutyronitrile, 2,2'
-Azobis(2,4-dimethylvaleronitrile), (I
-Phenylethyl)azodipheny is produced. In general,
It is preferred to use a polymerization initiator in an amount of 0.5 to 10% by weight of the polymerizable monomer.

During suspension polymerization, the following crosslinking agent may be present to produce a crosslinked polymer. For example, divinylbenzene, divinylnaphthalene, divinyl ether, divinyl sulfone, diethylene glycol dimethacrylate, I-lyethylene glycol dimethacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate 1 note , ]
.

3-butylene glycol dimethacrylate, 16-hegizan glyconyl dimethacrylate-1, neopentyl glycol dimethacrylate, cypropylene glycol dimethacrylate-1, polypropylene glycol dimethacrylate, 2,2'-bis(4-methacrylate) Synethoxyphenyl)propane, 2,2'-his(4-acryloxyjethoxyphenyl)propane, trimethylolpropane trimethacrylate-1, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, dibromneopentyl Crosslinking agents such as glycol dimethacrylate and diallyl phthalate can be used as appropriate.

If these crosslinking agents are used in large amounts, the toner becomes difficult to melt, resulting in poor heat fixing properties. If the amount used is small, properties such as anti-blocking and durability required for toner will deteriorate, and during hot roll fixing, some of the toner will not completely adhere to the paper and will stick to the roller surface (=1, It becomes difficult to prevent the offset phenomenon of transfer to the next paper.Therefore, the amount of these crosslinking agents to be used is from o.ooi to 15% by weight (more preferably from 0.00 to 15% by weight, based on the total amount of monomers).
1 to 10% by weight).

The toner according to the present invention can be obtained by the following method.

A monomer in which dyes or pigments treated by bulk polymerization, a crosslinking agent, a polymerization initiator, and other additives are added to a polymerizable monomer and uniformly dissolved or dispersed using a dispersion machine such as an ultrasonic dispersion machine or a homogenizer. The polymer system is dispersed in the aqueous phase (ie, continuous phase) containing the suspension stabilizer using a conventional stirring blade stirrer or a high shear stirrer such as a homomixer or homogenizer. In the suspension polymerization method, 3 parts by weight of water is usually added to 100 parts by weight of the monomer composition.
00 to 3000 parts by weight is used as a dispersion medium. The droplets of monomer composition have the desired toner particle size (-generally 30
Size below μm (preferably volume average particle size 3 to 15 μm)
(m)) The stirring speed and stirring time may be adjusted so that the dispersion stabilizer maintains this state by the action of the dispersion stabilizer, and the stirring is continued to such an extent that sedimentation of the particles is prevented. The polymerization temperature is set at 40°C or higher, and - for boat fishing, the temperature is set at 50 to 90°C. After the reaction is completed, the generated toner particles are collected by washing, filtration, and dried. The fluidity modifier may be used by being mixed (externally added) with the toner particles. Examples of the fluidity modifier include colloidal silica, hydrophobic colloidal silica, fatty acid metal salts, and Teflon fine powder.

Hereinafter, the present invention will be explained in more detail based on Examples.

Example 1 Dye treatment: ``1. The prescription ingredients were heated to 60°C in a container, and a polymerization initiator (2,2'-azobis(2,4-dimethylvaleronitrile), Wako Pure Chemical Industries, Ltd. V 2 parts by weight of styrene-2 containing anthraquinone magenta dye from which the polymerization inhibiting property has been removed is dissolved by adding 2 parts by weight of the anthraquinone magenta dye and maintaining the solution at a temperature of 60°C for 10 hours to complete bulk polymerization. A lump of a copolymer of -ethylhexylacrylate-1 was obtained.The obtained lump was crushed to obtain a copolymer powder containing a treated dye.

Toner manufacturing method: 0.5 parts by weight of γ-aminopropyltrimethoxysilane was added to 1200 parts by weight of ion-exchanged water, and 10 parts by weight of Aerosil 200 (manufactured by Nippon Aerosil), which is a hydrophilic colloidal silica, was added and heated to 70°C. Warm and mix at 10,000 rpm using a TK homomixer M type (manufactured by Tokushu Ki Kakogyo).
The mixture was dispersed for 15 minutes. Furthermore, 1/10 N-H (l) was added to adjust the pH of the aqueous dispersion medium to 6. Due to the action of γ-aminopropyltrimethoxysilane, the colloidal silica exhibited positive chargeability.

The above mixture was heated to 70°C in a container to dissolve the copolymer powder and form a monomer mixture. Further, while maintaining the temperature at 70°C, parts by weight of a polymerization initiator (dimethyl 2,2'-azohisisobutylene-1; Wako Tsumugi V-601)] were added and dissolved to give a negatively charged property in water. A monomer composition exhibiting the following was prepared. The prepared monomer composition was put into a No. 21 flask containing the above-mentioned aqueous dispersion medium, and the mixture was heated under a nitrogen atmosphere for 7 hours.
7. Using a TK homomixer at 0°C. OOOrpm
The mixture was stirred for 60 minutes to suspend and granulate the monomer composition.

Thereafter, the polymerization reaction was carried out for 700 C1]O hours while stirring with a paddle stirring blade. After the polymerization reaction was completed, the reaction product was cooled, sulfur and lithium hydroxide was added to dissolve the dispersion, and a toner was obtained by filtering, washing with water, and drying.

The particle size of the obtained toner was measured using a Coulter counter TA-II.
Mold (measured with aperture diameter 101007l,
It had a sharp particle size distribution with a volume average diameter of 11.8 μm. The amount of triboelectric charge of this toner against iron powder (200/300 mesh) by blow-off method is -22.4μc
/g. To 100 parts by weight of the obtained toner, 0.8 parts by weight of hydrophobic colloidal silica (Talanox 500, manufactured by Talco) was mixed.

An acrylic resin-coated ferrite carrier was added to 8 parts by weight of the toner having hydrophobic colloidal silica on the surface of the toner particles.

Using the obtained developer, 20,000 images were continuously printed using a Canon color laser copying machine (CLC-1), and the copies were clear and had no fog. It exhibited a magenta color with good reflective properties. When the toner image was transferred to a transparent plastic sheet for an overhead projector and fixed, the toner image on the obtained sheet had good color tone and transparency.

Although the toner was left in an environment at a temperature of 50° C. for one day, substantially no formation of aggregates was observed, and 1.S of Example 1 had good blocking resistance.

Example 2 Anthraquinone magenta dye as a dye having polymerization inhibiting properties 14. A toner was obtained by carrying out a bulk polymerization reaction and a suspension polymerization reaction in the same manner as in Example 1, except for using Red 3005 (manufactured by Sumitomo Chemical).

When the particle size of the obtained l·ner was measured using a Coulter counter (aperture diameter: 100 μm), it was found to have a volume average diameter of 10.9 μm and a sharp particle size distribution. The amount of triboelectric charge of this toner against iron powder (200/300 mesh) by the blow-off method was -20.5 μc/g. To 100 parts by weight of the obtained toner, 0.8 parts by weight of hydrophobic colloidal silica (Talanox 5001 Talco) was mixed, and to 8 parts by weight of the toner containing self-hydrating colloidal silica, acrylic resin coated ferrite Gearia 92 was added. Parts by weight were mixed to prepare a developer.

Using the developer obtained in this way, a continuous 20,000 yen copy was made using a Canon Color Laser Copying Machine (CLC-1).
When 0 images were printed, the copies were clear and had no fog, and exhibited a magenta color with good spectral reflection characteristics.

Furthermore, the toner image on the transparent plastic sheet had good color tone and transparency.

The obtained toner exhibited good blocking resistance even under high temperature conditions.

Example 3 A xanthene (rhodamine) magenta pigment (C.T. Pigment Re
A toner was obtained by performing bulk polymerization reaction and suspension polymerization reaction in the same manner as in Example 1 except that d81) was used.

When the particle size of the obtained toner was measured with a Coulter counter (aperture diameter 100 μm), the volume average diameter was 1
It had a sharp particle size distribution of 1.2 μm. The triboelectric charge amount of this toner against iron powder (200/300 mesh) by the blow-off method was -18.9 μc/g. Got it!・A developer was prepared in the same manner as in Example 1 using a developer.

Using the developer thus obtained, a color laser copying machine (CLC-1) manufactured by Canon Co., Ltd. was used to continuously print 20,000 copies.
When a copy was printed, the copy was clear, had no fog, and had a magenta color with good spectral reflection characteristics. Even when a toner image was formed on the trapene, the transparency was good.

The obtained toner exhibited good blocking resistance even under high temperature conditions.

Comparative Example 1 10 parts by weight of γ-aminopropyltrimethoxysilane Aerosil 200 (manufactured by Nippon Aerosil) was added to 1200 parts by weight of ion-exchanged water, heated to 70°C, and heated to 70°C. The mixture was dispersed for 15 minutes at 10,000 rpm. Furthermore, add 1/ION hydrochloric acid to adjust the pH of the aqueous dispersion medium.
was set as 6.

The above mixture was heated to 70°C in a container to dissolve the dye and form a monomer mixture. Further, while maintaining the temperature at 70°C, 10 parts by weight of a polymerization initiator (V-601 manufactured by Wako Tsumugi Pharmaceutical Co., Ltd.) was added and dissolved to prepare a monomer composition. The above monomer composition was put into a No. 21 flask containing the above aqueous dispersion medium, and stirred at 7,000 rpm for 60 minutes using a TK homomixer at 7,000 rpm under a nitrogen atmosphere. The composition was suspended and granulated. After that, while maintaining 700C,
Although the mixture was stirred with a paddle stirring blade, the polymerization reaction did not proceed sufficiently, and polymer particles usable as solid toner particles were not obtained.

Comparative Example 2 Red 3005 (manufactured by Sumitomo Chemical) was used as the dye and the same operation as in Comparative Example 1 was carried out, but the polymerization reaction did not proceed sufficiently and polymer particles usable as solid toner particles were not obtained. I couldn't.

Comparative Example 3 C.I. 1. The same operation as in Comparative Example 1 was carried out using Pingmet Red 81, but the polymerization reaction did not proceed sufficiently and polymer particles usable as solid toner particles were not obtained.

Example 4 As an anthraquinone colorant (pigment) having polymerization inhibiting properties, C.I. 1. Pigment Red 83 (
Using Sanyo Carmine L 2 B (manufactured by Koju Shiki Co., Ltd.), a bulk polymerization reaction and a suspension polymerization reaction were carried out in the same manner as in Examples below to obtain a polymerized toner.

When the grain boundaries of the obtained toner were measured with a Coulter counter (aperture diameter 100 μm), the volume average diameter was 1
It had a sharp particle size distribution of 0.3 μm and was excellent in development characteristics and blocking resistance.

Furthermore, the amount of triboelectric charge of this toner against iron powder (200/300 mesh) by the blow-off method is -2]
, 5 μc/g.

To 100 parts by weight of the obtained toner, 08 parts by weight of hydrophobic colloidal silica (Talanox 500, manufactured by Talco) was mixed. The l containing hydrophobic colloidal silica
- 92 parts by weight of acrylic coated ferrite carrier was mixed with 8 parts by weight of Qi to prepare a developer. Using the developer obtained in this way, 20,000 images were printed continuously on a Canon color laser copying machine (CLC-1), and the copies were clear and had no fog. Also,
It exhibited a magenta color with good spectral reflection characteristics. Moreover, the transparency of Trapen was also good.

Example 5 As a xanthine colorant (dye) having polymerization inhibiting properties, C.I. 1. Basic Red] (Rhodamine F5G.

BASF) and the same operations as in Example I were carried out to obtain a polymerized toner. When the particle size of the obtained L-ner was measured with a Coulter counter (aperture diameter 1.00 μm), it had a volume average diameter of 10.7 μm and a sharp particle size distribution, and had excellent blocking resistance and development characteristics. was. In addition, the amount of triboelectric charge of this toner against iron powder (200/300 mesh) by the blow-off method is -
It was 20.0 μc/g.

0.8 parts by weight of hydrophobic colloidal silica (Talanox 500, Talco) was mixed with 100 parts by weight of the obtained toner. A developer was prepared by mixing 92 parts by weight of an acrylic coated ferrite carrier with 8 parts by weight of the l-chi mixed with hydrophobic colloidal silica. Using the developer obtained in this way, 20,000 images were printed continuously on a Canon color laser copying machine (CLC-1), and the copies were clear and had no fog. It also exhibited a magenta color with good spectral reflection characteristics. Moreover, the transparency of Trapen was also good.

As described above, the method of the present invention makes it possible to use chromatic dyes or organic pigments that could not be used in the suspension polymerization method for producing L-ner because of their polymerization-inhibiting properties. A toner having a hue and saturation of

Claims (2)

[Claims] (1) A dye having a chromatic color or a pigment having a chromatic color is treated by a bulk polymerization method, and the treated dye or pigment is dissolved or dispersed in a polymerizable monomer to form a polymerizable monomer solution or dispersion. A monomer composition is prepared by mixing a polymerizable monomer solution or dispersion with a polymerization initiator, and a suspension polymerization method is performed by dispersing the monomer composition in an aqueous dispersion medium. A toner comprising obtaining polymer particles and toner particles prepared from the obtained polymer particles. (2) A dye having a chromatic color or a pigment having a chromatic color is treated by a bulk polymerization method, and the treated dye or pigment is dissolved or dispersed in a polymerizable monomer to form a polymerizable monomer solution or dispersion. A monomer composition is prepared by mixing a polymerizable monomer solution or dispersion with a polymerization initiator, and a suspension polymerization method is performed by dispersing the monomer composition in an aqueous dispersion medium. A method for producing a toner, comprising obtaining polymer particles and preparing toner particles from the obtained polymer particles.