JPH04107567A - Polymerized toner and production thereof - Google Patents

Abstract

PURPOSE:To obtain the toner which has excellent low-temp. fixability and low-temp. offset resistance and a wide non-offset region by specifying the m. p. and heat of fusion of a release agent. CONSTITUTION:This toner is obtd. by subjecting a polymerizable monomer system contg. at least the release agent and coloring material to a suspension polymn. in an aq. medium. This release agent is the wax having >=75 deg.C and <=145 deg.C m. p. and <30cal/g heat of fusion. For example, grafted paraffin wax, a random copolymer of alpha-olefin and ethylene, etc., are usable as the wax. The lower-temp. fixing is possible in this way while the high-temp. offset resistance is imparted to the toner.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a toner for developing electrostatic images, and more particularly to a polymerized toner for developing electrostatic images formed in electrophotography and a method for producing the same.

[Prior Art] Many electrophotographic methods are known, as described in U.S. Pat. No. 2,297,691, etc.
Generally, a photoconductive substance is used to form an electrical latent image on a photoreceptor by various means, the latent image is developed using toner, and the toner image is transferred to a transfer member such as paper as necessary. After the image is transferred, it is fixed using heat, pressure, solvent vapor, etc. to obtain a copy. Furthermore, various methods have been proposed as methods for developing with toner or methods for fixing toner images, and methods suitable for each image forming process are adopted.

In recent years, high-speed copying and high image quality have been required for electrophotography, and with the shift to full color, there have been increasing demands for color mixing between toners. There is a need for lower melt viscosity and lower melt viscosity.

Generally, toner is manufactured by melt-mixing coloring agents such as dyes and pigments, charge control O agents, mold release agents, and other additives in thermoplastic resin, uniformly dispersing them, and then classifying them into a fine pulverizer. A method for producing toner having a desired particle size using a machine is known.

In order to achieve low-temperature fixing, it is necessary to use a thermoplastic resin with a low softening point in toner produced by these pulverization methods, but as a result, high-temperature offset phenomenon tends to occur, and it is difficult to add a release agent. Required. However, the addition of an excessive amount of release agent makes it impossible to perform sufficient melt mixing necessary for toner production, and even if the amount is adjusted, it is difficult to prevent high-temperature offset and improve kneading properties while maintaining low-temperature fixing properties. Furthermore, it is actually difficult to satisfy all the requirements for transparency when used as a color toner.

In contrast to these pulverized toners, polymerized toners have been proposed. For example, JP-A No. 56-87051 discloses a method for producing a polymerized toner in which polymerization is carried out in the presence of an offset inhibitor, and JP-A No. 59-218460 discloses
The hydrocarbon compound-containing polymerized toner is further disclosed in Japanese Patent Application Laid-Open No. 1986-
No. 46,955 discloses polymerized color toners. Toners produced by these polymerization methods are generally obtained by suspension polymerizing a polymerizable monomer system in an aqueous medium, and because they do not undergo a pulverization process, large amounts of low softening point substances such as wax can be added. Furthermore, since non-polar substances such as wax cannot exist on the particle surface and are encapsulated,
There is almost no effect on blocking performance. The polymerized toner thus obtained has high-temperature offset resistance due to the addition of wax, but low-temperature fixability and low-temperature offset resistance are still insufficient.

[Problems to be Solved by the Invention] An object of the present invention is to provide a toner that solves the above-mentioned problems and a method for manufacturing the same.

An object of the present invention is to provide a toner having excellent low-temperature fixability and low-temperature offset resistance and a wide non-offset area, and a method for producing the same.

An object of the present invention is to provide a toner having excellent color mixing properties, color reproducibility, and transparency, and a method for producing the toner.

An object of the present invention is to provide a toner with high image density, excellent fine line reproducibility, and highlight gradation, and a method for producing the toner.

[Means and effects for solving the problems] The present invention relates to a polymerized toner obtained by suspension polymerizing a polymerizable monomer system containing at least a release agent and a colorant in an aqueous medium, and a method for producing the same. The present invention relates to a polymerized toner and a method for producing the same, wherein the releasing agent is a wax having a melting point of 75° C. or more and 140° C. or less and a heat of fusion of less than 30 cal/g.

The present invention will be explained in detail below.

As a result of extensive studies, the present inventors found that the wax added to impart high-temperature offset resistance affects low-temperature fixing properties and low-temperature offset resistance.

That is, the substance having a melting point of 75° C. to 140° C. functions as a mold release agent by melting when the toner is fixedly attached, and particularly contributes to preventing high temperature offset.

However, when wax is melted in this way, energy is required as heat of fusion.

The present inventors have discovered that the magnitude of this heat of fusion affects low-temperature fixability and low-temperature offset resistance. In other words, it has been found that when the heat of fusion is 30 c, a 12 /g or more, the low-temperature fixability of the toner is significantly inhibited.

On the other hand, if the melting point of the wax is lower than 75°C, the blocking resistance and shape retention of the toner will be insufficient;
If the temperature is higher than ℃, the releasability effect will be insufficient.

From the above, as a mold release agent, melting point of 75℃ or higher and 140℃ is recommended.
By using a wax with a heat of fusion of less than 3.0 caff/g, low-temperature fixing is possible while imparting high-temperature offset resistance.

The melting point of the wax in the present invention was determined from the top of the endothermic peak measured by a differential scanning calorimeter (DSC).

The wax that can be used in the present invention may be any wax with a melting point of 75°C or more and 140°C or less and a heat of fusion of less than 30 caff/g, such as grafted paraffin wax, random copolymer of a-olefin and ethylene, etc. Can be used.

Such a mold release agent is preferably used in an amount of 5 to 30 parts by weight per 100 parts by weight of the polymerizable monomer.

The polymerized toner used in the present invention can be obtained by the following method. That is, a monomer system in which release agents, colorants, charge control agents, polymerization initiators, and other additives are added to polymerizable monomers and uniformly dissolved or dispersed using a homogenizer, ultrasonic disperser, etc. It is dispersed in an aqueous phase containing a dispersion stabilizer using a conventional stirrer, homomixer, homogenizer, etc. Preferably, the stirring speed and time are adjusted so that the monomer droplets have the desired toner particle size, generally 30 μm or less, and after that, the particle state is maintained by the action of a dispersion stabilizer, and the particle size is It is sufficient to perform stirring to an extent that sedimentation is prevented.

The polymerization temperature is set to 40°C or higher, and for boat fishing, the polymerization is carried out at a temperature of 50 to 90°C. After the reaction is completed, the generated toner particles are collected by washing and filtration, and then dried. In the suspension polymerization method, 30 parts by weight of water is usually added to 100 parts by weight of the monomer system.
0-300 ONN group It is preferable to use it as a partial dispersion medium.

Examples of polymerizable monomers that can be used in the polymerized toner include styrene, ○-methylstyrene, m-methylstyrene, p-methylstyrene, and p-methylstyrene.
- Styrenic monomers such as methylstyrene, p-methoxystyrene, p-ethylstyrene, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, n-octyl acrylate , dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, etc., methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate , isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylamine ethyl methacrylate, diethylaminoethyl methacrylate, and other methacrylic acid esters and other acrylonitrile , methacrylonitrile, acrylamide, and the like.

These monomers may be used alone or in combination. Among the above-mentioned monomers, it is preferable to use styrene or styrene derivatives alone or in combination with other monomers from the viewpoint of the development characteristics and durability of the toner.

As the colorant used in the present invention, known colorants can be used, such as carbon black, iron black, C, 1,
Direct Red 1, C, 1, Direct Red 4, C
,1, Acid Red 1, C,1, Basic Red 1
, C,1, Modern Tread 30, C,1, Direct Blue 1, c,r, Direct Blue 2, C,1, Acid Blue 9, C,1, Acid Blue 15, C1■,
Basic Blue 3, C, 1, Basic Blue 5, C
, 1, Mordandbruer, C,I.

Direct Green 6, C, 1, Basic Green 4
, C,1, basic green 6 dyes, yellow lead, cadmium yellow, mineral fast yellow, navel yellow, naphthol yellow S, banza yellow G1
Permanent Yellow NCG, Tartrazine Lake, Molybdenum Orange, Permanent Orange GTR, Benzidine Orange G, Cadmium Red, Permanent Red 4R, Watching Red Calcium Salt, Brilliant Carmine 3B, Fast Violet B, Methyl Violet Lake, Navy Blue, Cobalt Blue Alkali Blue Lake, Victoria Blue Lake, Quinacridone,
Pigments include Rhodamine B, Phthalocyanine Blue, Fast Sky Blue, Pigment Green B, Malachite Green Lake, and Final Yellow Green G. In the present invention, since the toner is obtained using a polymerization method, it is necessary to pay attention to the polymerization inhibiting property and aqueous phase migration property of the colorant. Preferably, surface modification, such as hydrophobicity using a substance that does not inhibit polymerization, is necessary. It is better to apply chemical treatment. In particular, many dyes and carbon blacks have polymerization inhibiting properties, so care must be taken when using them. A preferred method for surface treating the dye system includes a method in which a polymerizable monomer is polymerized in advance in the presence of these dyes, and the resulting colored polymer is added to the monomer system. Further, carbon black may be subjected to a grafting treatment with a substance that reacts with the surface functional groups of carbon black, such as polyorganosiloxane, in addition to the same treatment as the dye described above.

In the present invention, it is desirable to add a charge control agent to the toner material for the purpose of controlling the chargeability of the toner. As these charge control agents, among the known ones, those having almost no polymerization inhibiting property or water phase migration property are used. For example, positive charge control agents include nigrosine dyes, triphenylmethane dyes, quaternary ammonium salts, amines, etc. Examples of the negative charge control agent include metal-containing salicylic acid compounds, metal-containing monoazo dye compounds, styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, and the like.

The dispersion medium used in the present invention may include any suitable stabilizer, such as polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salt of carboxymethylcellulose, polyacrylic acid and its salts, starch, tricalcium phosphate, etc. , aluminum hydroxide, magnesium hydroxide, calcium metasilicate, barium sulfate, bentonite, etc. can be used by dispersing them in the aqueous phase. This stabilizer is
It is preferable to use 0.2 to 20 parts by weight per 100 parts by weight of the polymerizable monomer.

In addition, due to the fine dispersion of these stabilizers, the
11 parts by weight of O1 surfactant may be used. This is to promote the intended action of the above-mentioned dispersion stabilizers, and specific examples include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, and lauric acid. sodium, potassium stearate,
Examples include calcium oleate.

It is more preferable to add and polymerize a polymer/copolymer having a polar group as an additive to the monomer system. Furthermore,
In the present invention, a monomer system containing a polar group-containing polymer/copolymer or cyclized rubber is suspended in an aqueous phase in which a dispersant having an opposite charge to the polar polymer is dispersed, and polymerization is carried out. It is preferable to do so. That is, the cationic or anionic polymer/copolymer or cyclized rubber contained in the monomer system is polymerized with the oppositely charged anionic or cationic dispersant dispersed in the aqueous phase. The particles are electrostatically attracted to each other on the surface of the particles that become the toner, and the dispersant covers the particle surface to prevent the particles from coalescing and stabilize them, and the polar polymer added during polymerization gathers on the surface of the particles that become the toner. Therefore, it takes on a kind of shell-like shape, and the resulting particles become pseudo-capsules. A relatively high molecular weight polar polymer/copolymer or cyclized rubber is used to give the toner particles excellent blocking properties and development abrasion resistance, while a relatively low molecular weight internal material improves fixing properties. By carrying out polymerization in such a way that it contributes to the fixing properties, it is possible to obtain a toner that satisfies the contradictory requirements of fixing properties and blocking properties. Examples of polar polymers/copolymers and counterloading dispersants that can be used in the present invention are shown below.

(1) Examples of the cationic polymer include polymers of nitrogen-containing monomers such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate, or copolymers with styrene and unsaturated carboxylic acid esters.

(2) Examples of anionic polymers include nitrile monomers such as acrylonitrile, halogen-containing monomers such as vinyl chloride, unsaturated carboxylic acids such as acrylic acid and methacrylic acid,
Other examples include saturated dibasic acids, unsaturated dibasic acid anhydrides, polymers of nitro monomers, and copolymers with styrene monomers. Furthermore, cyclized rubber may be used instead of these polar polymers.

(3) As the anionic dispersant, silica fine powder is preferably used, especially with a BET specific surface area of 200 m"/g
The above colloidal silicas are suitable.

(4) As the cationic dispersant, aminoalkyl-modified colloidal silica (preferably has a BET specific surface area of 20
0 m2/g or more), hydrophilic positively chargeable silica fine powder, aluminum hydroxide, and the like.

It is preferable to use such a dispersant in an amount of 0.2 to 20 parts by weight based on 100 parts by weight of the polymerizable monomer. More preferably, it is 0.3 to 15 parts by weight.

As the polymerization initiator, any suitable polymerization initiator such as 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile,
1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4
- Azo or diazo polymerization initiators such as dimethylvaleronitrile and azobisisobutyronitrile, peroxides such as benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxy carbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, etc. Examples include physical polymerization initiators. These polymerization initiators generally contain 0.0% of the polymerizable monomer.
An addition amount of 5 to 10% by weight is sufficient.

It is preferable that the toner according to the present invention has a substantially spherical shape and has minute irregularities on the surface. As a method for obtaining such a toner, fine particles are fused to the surface of spherical particles by any method, and the surface of the spherical particles may be made uneven at the stage of producing the spherical particles. Examples of methods for obtaining the toner having an uneven surface according to the present invention include the following methods.

1) Mechanochemical method After mixing the bispherical toner particles and fine resin particles, the fine resin particles are fused to the surface of the toner particles using a mechanochemical method.

2) Dry heat treatment method After mixing the bispherical toner particles and fine resin particles, the mixture is heated in a fluidized heating bed to fuse the fine resin particles to the surface of the toner particles.

3) Wet heat treatment method: After mixing spherical toner particles and fine resin particles in a liquid or gas, heat treatment is performed in the liquid to fuse the fine resin particles to the surface of the toner particles.

4) During toner particle polymerization, when obtaining toner particles by the resin fine particle twisting method, the resin fine particles are added to the monomer in advance, or the resin fine particles are added during the polymerization process, and the resin fine particles and the dispersion system are By controlling the physical properties, fine resin particles are transferred to the toner surface and polymerization is completed.

5) Drying method after swelling: Toner particles are once immersed in a solvent and swollen, and then dried in a heated air stream or under reduced pressure.

At this time, spheroidization processing may also be performed.

The fine resin particles used for providing unevenness in the present invention have a particle size in the range of 1/200 to 1/10, preferably 1/100 to 1/10, of the spherical toner particles, and the material thereof is, for example, Styrene resin, styrene/acrylic acid ester copolymer, styrene/methacrylic acid ester copolymer, copolymer of styrene and other vinyl monomers (e.g. acrylonitrile, butadiene, etc.), polyester resin, epoxy An appropriate resin is used. Among these resins, vinyl resins are particularly preferably used because resin fine particles can be easily obtained by emulsion polymerization or the like.

The additives used in the present invention for imparting various properties preferably have a particle size of 1/10 or less of the volume average diameter of the toner particles from the viewpoint of durability when added to the toner. The particle size of the additive means the average particle size determined by observing the surface of toner particles using an electron microscope. As additives for the purpose of imparting these characteristics, for example, the following are used.

1) Fluidity imparting agents such as dimetallic oxides (silicon oxide, aluminum oxide, titanium oxide, etc.), carbon black, carbon fluoride, etc. Each of them is more preferably subjected to hydrophobization treatment.

2) Abrasives Dimetallic oxides (strontium titanate, cerium oxide, aluminum oxide, magnesium oxide, chromium oxide, etc.), nitrides (silicon nitride, etc.), carbides (
silicon carbide, etc.) metal salts (calcium sulfate, barium sulfate, calcium carbonate, etc.), etc.

3) Lubricant: Fluorine resin powder (vinylidene fluoride, polytetrafluoroethylene, etc.), fatty acid metal salts (zinc stearate, calcium stearate, etc.), etc.

4) Charge controllable particles such as dimetallic oxides (tin oxide, titanium oxide, zinc oxide, silicon oxide, aluminum oxide, etc.), carbon black, etc.

These additives are added in an amount of 0.00 parts by weight per 100 parts by weight of toner particles.
1 to 10 parts by weight are used, preferably 0.1 to 5 parts by weight. Even if these additives are used alone,
Also, a plurality of them may be used together.

Differential scanning calorimetry (DSC) in the present invention is DSC
-7 (manufactured by PerkinElmer) at a heating rate of 10℃/
It was done at min.

Particle size distribution measurement in the present invention will be described.

The measuring device is a Coulter counter TA-II type (
(Manufactured by Coulter Inc.), an interface for outputting the number average distribution and volume average distribution (manufactured by Nikkaki) and a CX-1 personal computer (manufactured by Canon) were connected, and the electrolyte was a 1% NaCρ aqueous solution using primary sodium chloride. Prepare.

As a measuring method, 0.1 to 5 m of a surfactant, preferably an alkylbenzenesulfonate salt, is added as a dispersant to 100 to 150 mβ of the electrolytic aqueous solution, and 0.5 to 50 mg of a measurement sample is added.

The electrolyte in which the sample was suspended was dispersed for about 1 to 3 minutes using an ultrasonic disperser, and the particle size distribution of particles of 2 to 40 um was measured using the Coulter Counter TA-II model using a 100 μm aperture. to find the volume average distribution and number average distribution.

From these determined volume average distribution and number average distribution, the volume average particle diameter can be obtained.

[Examples] The present invention will be described in detail below based on Examples. Note that all parts are parts by weight.

Add 0.25 g of γ-aminopropyltrimethoxysilane to 1200 mρ of ion-exchanged water, and further add 5 g of hydrophilic colloidal silica (BET specific surface area 200 m / g),
The mixture was heated to 80° C. and dispersed for 15 minutes at 10,000 rpm using a TK homomixer M type (manufactured by Tokushu Kika Kogyo). Furthermore, add 1/10N-HCI2 aqueous solution to adjust the system pH.
was set as 6.

The above formulation was heated to 80° C. in a container, and dissolved and dispersed using a TK homomixer to obtain a monomer mixture. 8 more
While maintaining the temperature at 0°C, 10 parts of dimethyl 2,2'-azobisisobutyrate as an initiator was added and dissolved to prepare a monomer composition. The above monomer composition was put into a 2ρ flask containing the dispersion medium obtained above, and the monomer composition was heated under a nitrogen atmosphere for 8 hours.
Using a TK homomixer at 0°C, 12. OOOrpm
The mixture was stirred for 60 minutes to granulate the monomer composition. after that,
Polymerization was carried out at 80° C. for 20 hours while stirring with a paddle stirring blade. After the polymerization reaction was completed, the reaction product was cooled, an aqueous NaOH solution was added to dissolve the dispersant, and spherical particles were obtained by filtration, washing with water, and drying.

When the particle size of the obtained spherical particles was measured using a Coulter counter (aperture diameter: 100 μm), it was found that the volume average diameter was 6.5 μm, and the particles had a sharp particle size distribution.

Separately, put 150 parts of ion-exchanged water into a reaction container, and add 80 parts of ion-exchanged water.
℃, and with further stirring, 1 part and 1 part of a monomer system of styrene/n-butyl methacrylate = 90/10 (part/part)
10 parts of a 0% by weight ammonium persulfate aqueous solution was added, and 99 parts of the above monomer system were added dropwise over 3 hours to obtain a seed latex. Next, 10 parts of methacrylic acid was added dropwise, and the polymerization was continued for 3 hours. After polymerization, cool, wash with water, filter,
After drying, the volume average diameter measured by Coulter N4 was 0.
Spherical fine resin particles of 5 μm were obtained.

Add 5 parts of the above resin fine particles to 50 parts of the previously obtained spherical particles,
The mixture was dispersed and mixed using a Henschel mixer. Separately, add 0.25 g of γ-aminopropyltrimethoxysilane to 1200 mJ2 of ion-exchanged water, and further add hydrophilic colloidal silica (BET specific surface area 200 m''/g).
1 using TK homomixer M type (manufactured by Tokushu Kika Kogyo)
After dispersing for 15 minutes at 0, OOOrpm, 1/1ON-HC
I2 aqueous solution was added to adjust the pH in the system to 6.

Place this in an autoclave, add the mixed particles from above,
Immobilization treatment was performed for 30 minutes while heating and stirring at 110°C/1.2Kg/cm''. After the treatment, the dispersion system was cooled, and the dispersant was further removed using an alkali, followed by water washing, filtration, and
Drying was performed to obtain textured spherical particles. Coulter counter of the obtained particles (aperture diameter 100 μm)
The volume average diameter was 7.5 μm.

To 100 parts of the unevenness-imparting spherical particles, 0.6 parts of silica fine powder having a specific surface area of 200 m''/g by the BET method and hydrophobized with hexamethyldisilazane was externally added.
I used it as a toner. 90 parts of styrene-acrylic resin coated ferrite carrier are mixed with 10 parts of this toner,
It was used as a developer. Using the developer obtained in this way,
Images were printed using Canon CLC-500 at different fixing temperatures, and the fixing performance was evaluated.

As an evaluation method, the obtained fixed image was rubbed with Silbon paper with a load of 50 g/cm", and the temperature at which the image density reduction rate before and after rubbing was 5% or less was taken as the fixing start temperature. , offset was evaluated by observing the image.Furthermore, the transparency of the OHP sheet was evaluated at process speed 2.
Fixing was performed at a speed of 0 mm/sec at a fixing roller surface temperature of 150°C, and the light transmission spectrum was measured using a spectrophotometer U-3400.
(Rear made by Hitachi). The amount of toner on the unfixed image was 0.55±0.05 mg/cm''.

As a result, the fixing start temperature was as low as 110° C., and the non-offset area was 120 to 190° C., thus achieving low-temperature fixing. The chroma of the fixed image was 74.5, and the transparency of the image on the OHP sheet when fixed at 150°C was particularly good, 56.
The spectral transmittance at 0 nm was 85%. Table 1 shows the results.
Shown below. In addition, when we conducted a running test of 30,000 sheets, the image density was 1.4 or higher, there was no fog, and the resolution and two-tone performance were excellent. There were no toner cleaning defects, and there was no toner scattering inside the copying machine. It wasn't noticeable either. Furthermore, when the toner before and after durability was observed under an electron microscope, no deterioration of the silica particles was observed.

11 milk 480 parts of 0.1M sodium triphosphate aqueous solution was added to 650 mj2 of ion-exchanged water, heated to 80'C, and 72 parts of IM calcium chloride aqueous solution was added dropwise while stirring at high speed.

The above formulation was heated to 80° C. in a container, and dissolved and dispersed using a TK homomixer to obtain a monomer mixture. Furthermore, while maintaining the temperature at 80 DEG C., 10 parts of initiator dimethyl 2,2'-azobisisobutyrate was added and dissolved to prepare a monomer composition. The above monomer composition was put into a 2β flask containing the dispersion medium obtained above, and the mixture was heated under a nitrogen atmosphere for 8 hours.
The monomer composition was granulated by stirring at 0'C for 60 minutes at 9000 rpm using a TK homomixer. Thereafter, polymerization was carried out at 80° C. for 20 hours while stirring with a paddle stirring blade.

After the polymerization reaction was completed, the reaction product was cooled, an aqueous solution of H(12) was added to dissolve the dispersant, and spherical particles were obtained by filtration, washing with water, and drying.

The volume average diameter of the obtained particles was 8.2 μm as measured by a Coulter counter (aperture diameter: 100 μm).

To 100 parts of these spherical particles, 0.6 parts of fine silica powder having a specific surface area of 200 m''/g by the BET method and hydrophobized with hexamethyldisilazane was externally added to prepare a toner. 10 parts of this toner. Then, 90 parts of styrene-acrylic resin-coated ferrite carrier was mixed to prepare a developer.

Using the developer thus obtained, Canon C.
Images were printed by changing the fixing temperature of LC-500, and the fixing performance was evaluated.

When the same evaluation as in Example 1 was performed, the fixing start temperature was as low as 110°C, and the non-offset area was 120 to 190°C.
As a result, low-temperature fixing was achieved. The saturation of the fixed image is 4
7.2, and the transparency of the image on the OHP sheet when fixed at 150°C was particularly good, with a spectral transmittance of 83% at 460 parts m.
Met.

The results are shown in Table-1.

reach the land A dispersion medium was prepared in the same manner as in Example 2.

Granulation was carried out using the same formulation as in Example 2. Further, polymerization was carried out at 80° C. for 20 hours while stirring with a paddle stirring blade. After the polymerization was completed, an aqueous HCff solution was further added to dissolve the dispersant, followed by filtration, washing with water, and drying to obtain spherical particles.

The volume average diameter of the obtained particles was 7.9 μm as measured by a Coulter counter (aperture diameter: 100 μm).

For these spherical particles, the specific surface area according to the BET method is 200
m"/g, and 0.6 parts of silica fine powder hydrophobized with hexamethyldisilazane was added externally to prepare a toner. To 10 parts of this toner, 90 parts of styrene-acrylic resin-coated ferrite carrier was added. The mixture was mixed to form a developer. Using the thus obtained developer, Canon's CL
Images were printed by changing the fixing temperature of C-500, and the fixing performance was evaluated.

When the same evaluation as in Example 1 was performed, the fixing start temperature was as low as 110°C, and the non-offset area was 120 to 180°C.
As a result, low temperature fixing was achieved. The saturation of the fixed image is 66
．． 7, and the transparency of the image on the HP sheet fixed at 150°C was particularly good, with a spectral transmittance of 83% at 660 parts m.
Met. The results are shown in Table-1.

11 Wataru A Using the developer obtained in Examples 1 to 3, CLC manufactured by Canon Co., Ltd.
-500, three full-color images were produced, and the same fixing test as in Example 1 was conducted.

In particular, as a full-color image, the saturation of the mixed color portion and the transparency of the OHP sheet were evaluated. As a result, the fixing start temperature was 110 for each red, green, and blue image area.
℃, the non-offset area was 120 to 180°C, and low-temperature fixing was achieved even in full color images. In addition, the saturation of the red, green, and blue image areas at 150°C was 55.5, 47.8, and 51.4, respectively, indicating excellent color mixing. The transparency of the image on the OHP sheet during fixation is particularly good, and the spectral transmittance of each wavelength in the red part (660 parts m), green part (560 parts m), and blue part (460 nm) is 71%. (660 copies),
75% (560 parts m) and 67% (460 parts m). The results are shown in Table-1.

Spherical particles with irregularities having a volume average diameter of 8.1 μm as measured by a Coulter counter (aperture diameter 100 μm) were obtained in the same manner as in Example 1, except that the formulation in Example 1 was changed as follows.

A developer was prepared using the uneven spherical particles in the same manner as in Example 1, and the fixability was evaluated.

As a result, the fixing start temperature was 120°C, and the non-offset area was 130 to 190°C. The saturation of the fixed image is 73
．． 8, and the transparency of the image on the OHP sheet when fixed at 150° C. was good, and the spectral transmittance at 560 nm was 59%. Also, the results of the running test of 30,000 sheets were as good as in Example 1.

A cyan developer was obtained in the same manner as in Example 2, except that the grafted paraffin wax in Example 2 was replaced with a paraffin wax having a melting point of 80° C. and a heat of fusion of 38 cal/g. Also, in the toner formulation in Example 3, instead of high melting point paraffin wax (melting point 75°C),
A magenta developer was obtained in the same manner as in Example 2 using the following paraffin wax. Using the yellow developer obtained in Comparative Example 1 and the cyan and magenta developers described above, a three-color full-color image was evaluated in the same manner as in Example 4.

As a result, the fixing start temperature was 120°C for each red, green, and blue image area, and 130°C for the non-offset area.
The temperature was 180°C. In addition, the saturation of each red, green, and blue image area at 150°C is 1.53.0.
45.7, 49.5, and when fixed at 150°C using a reflective overhead projector, the image on the OHP sheet can be recognized in color, but it lacks transparency and has a blackish tinge, with red parts ( 660 nm), green part (56
The spectral transmittance of each wavelength is 54% (660 nm) and 56% (5
60 nm) 52% (460 nm). The results are shown in Table-1.

School! In Example 2, the same operation as in Example 2 was carried out except that the grafted paraffin wax used as the mold release agent was changed to paraffin wax with a melting point of 50°C and a heat of fusion of 37 Caρ/g. Got toner.

When the same evaluation as in Example 1 was performed, the fixing start temperature was 120°C and the non-offset area was 130°C to 180°C.

Furthermore, the toner had a problem with blocking properties and had poor fluidity, and the images obtained were rough.

(The following is a margin) [Effects of the Invention] As explained above, the toner C and J1 offset areas of the present invention are wide, and it is possible to provide high-quality images and images with excellent transparency for OHP use. can.

Claims (2)

[Claims] (1) A polymerized toner obtained by suspension polymerizing a polymerizable monomer system containing at least a release agent and a colorant in an aqueous medium system, wherein the release agent has a melting point of 75°C or more and 140°C or less, and A polymerized toner characterized by being a wax having a heat of fusion of 30 cal/g or less. (2) Contains at least a mold release agent and a coloring agent, and the mold release agent has a melting point of 75°C or higher and 140°C or lower and a heat of fusion of 30 cal/g.
A method for producing a polymerized toner, comprising suspension polymerizing the following polymerizable monomer system, which is a wax, in an aqueous medium system.