JP3028264B2 - Polymerization toner - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymerization toner used in a method for visualizing a latent image.

[0002]

2. Description of the Prior Art Electrophotography is disclosed in U.S. Pat. No. 2,297,6.
As described in, for example, US Pat. No. 91/91, a number of methods are known. Generally, a photoconductive substance is used to form an electric latent image on a photoreceptor by various means, and then the latent image is formed. The image is developed using toner, and if necessary, the toner image is transferred to a transfer member such as paper, and then fixed by heating, pressure, or solvent vapor to obtain a copy. Further, as a method of developing using a toner or a method of fixing a toner image,
Conventionally, various methods have been proposed, and a method suitable for each image forming process has been adopted.

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

[0004] Although this method can produce fairly good toners, it does have certain limitations, namely the choice of toner materials. For example, the resin colorant dispersion is brittle enough,
It must be able to be comminuted in an economically feasible production equipment. However, when the resin colorant dispersion is made brittle to satisfy these requirements, the particle size range of the particles formed when actually pulverized at a high speed tends to be widened, and in particular, a relatively large proportion of the fine particles The problem of inclusion occurs. Further, such a highly brittle material is liable to be further pulverized or powdered when used for development in a copying machine or the like. Further, in this method, it is difficult to completely and uniformly disperse solid fine particles such as a colorant in a resin,
Depending on the degree of the dispersion, fog may increase, the image density may decrease, or the color mixing / transparency may be poor. Therefore, care must be taken in the dispersion. Further, exposure of the coloring agent to the fracture surface may cause fluctuations in development characteristics.

On the other hand, in order to overcome the problems of the toner caused by these pulverization methods, Japanese Patent Publication Nos.
Nos. 10799 and 51-14895 propose a method for producing a toner by a suspension polymerization method. In the suspension polymerization method, a polymerizable monomer, a colorant, a polymerization initiator, and, if necessary, a crosslinking agent, a charge control agent, and other additives are uniformly dissolved or dispersed to form a monomer composition. A continuous phase containing the monomer composition containing a dispersion stabilizer,
For example, the toner particles are dispersed in an aqueous phase using a suitable stirrer, and simultaneously undergo a polymerization reaction to obtain toner particles having a desired particle size.

This method does not require any pulverizing step, so that the toner does not need to be brittle, a soft material can be used, and the classifying step can be omitted. Large cost reduction effects such as reduction of time and improvement of process yield.

Further, there is an advantage that a colorant is not exposed to the particle surface and uniform triboelectricity is obtained.

However, in recent years, the copier has become more sophisticated,
In view of the improvement of durability and the like, the phenomenon that the developing property is remarkably reduced when left in a low-humidity environment with the increase in reliability has occurred. This is considered to be due to a decrease in the fluidity of the toner and a deterioration in the chargeability.

As means for solving the above problem, Japanese Patent Laid-Open No.
JP-A-7-11354 discloses a method of obtaining a toner by polymerizing a monomer in the presence of a polysiloxane.
No. 9361 discloses a method for obtaining a toner by adding a silane coupling agent to a suspension polymerization reaction system.
In the former, the dispersion of the charge amount is smaller than that of the toner manufactured by the pulverization method because the solubility of the polysiloxane in the monomer is good, but satisfactory results are obtained when a durability test is performed under low humidity. Was not obtained. It is believed that this is because the polysiloxane was merely dispersed in the toner binder. For the latter,
By adding a silane coupling agent into the reaction system,
It is considered that it is difficult to perform a surface treatment sufficient for achieving the effect.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and to provide a stable and good image without lowering of the fluidity of the toner and deterioration of charging even under low humidity. An object of the present invention is to provide an obtained toner.

[0011]

The object of the present invention is to provide at least i) a polymerizable monomer, ii) 15 to 30 parts by weight of wax and 100 parts by weight of a polymerizable monomer.
ii) Styrene monomer, nitrile monomer, halogen-containing monomer, unsaturated carboxylic acid, unsaturated dibasic acid, unsaturated dibasic acid anhydride, nitro monomer and nitrogen-containing monomer A monomer selected from the group consisting of a polymer and a polymerizable monomer system containing a silicon-containing vinyl copolymer obtained by copolymerizing a silane compound having a vinyl group in an aqueous medium. This is achieved by a polymerization method toner obtained by suspension polymerization.

Hereinafter, the present invention will be described in detail.

As a result of intensive studies, the present inventors have found that, in a polymerization toner obtained by suspension polymerization of a polymerizable monomer system in an aqueous medium, at least a silicon-containing vinyl copolymer is contained in the polymerizable monomer system. By including the polymer, even under low humidity, the fluidity of the toner does not decrease, and the deterioration of the chargeability does not occur.
It has been found that good images can be stably obtained.

This is because the presence of the silane compound in the toner binder not only lowers the surface energy of the toner and stabilizes the chargeability, but also enables the bonding of a group containing a Si atom in the molecular chain of the toner binder. This is considered to be due to the fact that the toner hardly deteriorates even in durability under low humidity.

The silicon-containing vinyl copolymer used in the present invention comprises a silane compound having a vinyl group, a styrene monomer, a nitrile monomer such as acrylonitrile, and a halogen-containing monomer such as vinyl chloride. Monomer, acrylic acid
With unsaturated carboxylic acids such as methacrylic acid, other unsaturated dibasic acids / unsaturated dibasic acid anhydrides, nitro monomers and the like,
Further, a copolymer with a nitrogen-containing monomer such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate may be used.

These copolymers may be those obtained by any of the commonly used methods such as bulk polymerization, suspension polymerization, emulsion polymerization and solution polymerization.

Since these silicon-containing vinyl copolymers have polar groups, they are easily localized near the toner surface.
An effect can be exhibited with a small amount to stabilize the fluidity and chargeability of the toner.

The molecular weight (M) of the silicon-containing vinyl copolymer
5000) to 500,000 are preferable as w). The content of the silicon-containing vinyl copolymer is 0.1% of the total amount of the monomers.
-10 wt% is preferred.

According to the present invention, the silane compound having a vinyl group is not used as a copolymer with the above-mentioned nitrogen-containing monomer.
The object of the present invention can be achieved even when a silane compound having a vinyl group itself is contained.

In this case, the silane compound having a vinyl group contains 0.01 to 10% by weight of the total amount of the monomers.

When the content exceeds 10% by weight, the glass transition point (Tg) is lowered, and the toner has insufficient blocking resistance. If less than 0.01 wt%,
Sufficient effects on toner fluidity and chargeability cannot be obtained.

As the silane compound having a vinyl group used in the present invention, allyltrimethylsilane, allylchloromethyldimethylsilane and vinyltrimethylsilane are used. This is because if the amount of the crosslinking component of the binder increases, the low-temperature fixability is impaired.

The polymerizable monomer constituting the polymerizable monomer system and the toner property imparting agent such as a colorant used in the present invention include the following.

Examples of the polymerizable monomer include styrene monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene and p-ethylstyrene, methyl acrylate and acrylic 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 and the like Acrylic esters, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, methacryl Phenyl, dimethylaminoethyl methacrylate, methacrylic acid esters other acrylonitrile such as ethyl methacrylate aminoethyl, methacrylonitrile, and the like monomers acrylamide.

These monomers can be used alone or as a mixture. Among the above-mentioned monomers, it is preferable to use styrene or a styrene derivative alone or in a mixture with another monomer, from the viewpoint of the developing characteristics and durability of the toner.

As the coloring agent used in the present invention, known coloring agents can be used. For example, carbon black, iron black, C.I. I. Direct Red 1, C.I. I. Direct Red 4, C.I. I. Acid Red 1, C.I. I. Basic Red 1, C.I. I. Modant Red 30, C.I.
I. Direct Blue 1, C.I. I. Direct Blue 2, C.I. I. Acid Blue 9, C.I. I. Acid Blue 15, C.I. I. Basic Blue 3, C.I. I. Basic Blue 5, C.I. I. Modant Blue 7, C.I. I.
Direct Green 6, C.I. I. Basic Green 4, C.I. I. Dyes such as Basic Green 6, graphite, cadmium yellow, mineral fast yellow, navel yellow, naphthol yellow S, Hanza yellow G, permanent yellow NCG, tartrazine lake, molybdenum orange, permanent orange GT
R, benzidine orange G, cadmium red, permanent red 4R, watching red calcium salt,
Brilliant Carmine 3B, Fast Violet B,
Pigments such as methyl violet lake, navy blue, cobalt blue, alkali blue lake, Victoria blue lake, quinacridone, rhodamine lake, phthalocyanine blue, fast sky blue, pigment green B, malachite green lake, final yellow green G and the like. In the present invention, in order to obtain a toner using a polymerization method, it is necessary to pay attention to the polymerization inhibitory and aqueous phase migration properties of the colorant, preferably, surface modification, for example,
It is better to perform a hydrophobic treatment with a substance that does not inhibit polymerization. In particular, attention must be paid to the use of dyes and carbon black since many of them have polymerization inhibitory properties. As a preferable method for surface-treating the dye system, there is a method in which a polymerizable monomer is polymerized in the presence of these dyes in advance, and the obtained colored polymer is added to the monomer system. In addition, regarding carbon black, in addition to the same treatment as the above-described dye, a graft treatment with a substance that reacts with the surface functional group of carbon black, for example, polyorganosiloxane or the like may be performed.

In the present invention, a magnetic substance may be added.
This is also preferably used after performing a surface treatment.

In the present invention, for the purpose of improving the releasability at the time of fixing with a hot roll, waxes generally used as a releasing agent such as a hydrocarbon compound may be added to the toner. Examples of the waxes used in the present invention include paraffin / polyolefin waxes and modified products thereof, for example, oxides and grafted products, higher fatty acids, metal salts thereof, and amide waxes. These waxes have a softening point of 40 to 130 ° C, preferably 50 to 120 ° C according to the ring and ball method (JIS K2531).
C. is desirable. When the softening point is 40 ° C. or less, the blocking resistance and shape retention of the toner are insufficient.
If the temperature is higher than 30 ° C., the effect of the releasability becomes insufficient. Generally, it is preferable to use 1.0 to 100 parts by weight of the release agent per 100 parts by weight of the polymerizable monomer.
However, when a silicon-containing vinyl copolymer is contained in the polymerizable monomer, the release agent is used in an amount of 15 to 30 parts by weight per 100 parts by weight of the polymerizable monomer.

In the present invention, it is desirable to add a charge control agent to the toner material in order to control the chargeability of the toner. As these charge control agents, those having little polymerization inhibition and water phase transfer among known ones are used. For example, as positive charge control agents, nigrosine dyes, triphenylmethane dyes, quaternary ammonium salts, amines And polyamine compounds. Examples of the negative charge control agent include metal-containing salicylic acid compounds, metal-containing monoazo dye compounds, styrene-acrylic acid copolymers, and styrene-methacrylic acid copolymers.

As the polymerization initiator, any suitable polymerization initiator such as 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1'-azobis (cyclohexane-1-
Azo or diazo polymerization initiators such as carbonitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile, benzoyl peroxide, methyl ethyl ketone peroxide,
Peroxide-based polymerization initiators such as diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, and lauroyl peroxide are exemplified. These polymerization initiators are preferably added in an amount of 0.5 to 20% by weight of the polymerizable monomer.

In the present invention, a crosslinking agent may be added, and the preferable addition amount is 0.001 to 15% by weight.

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

1) Fluidity imparting agent: metal oxide (silicon oxide, aluminum oxide, titanium oxide, etc.), carbon black, carbon fluoride, etc. Those subjected to a hydrophobic treatment are more preferable.

2) Abrasives: metal oxides (such as strontium titanate, cerium oxide, aluminum oxide, magnesium oxide, and chromium oxide), nitrides (such as silicon nitride), carbides (such as silicon carbide), and metal salts (calcium sulfate) , Barium sulfate, calcium carbonate, etc.).

3) Lubricant: fluororesin powder (vinylidene fluoride, polytetrafluoroethylene, etc.), fatty acid metal salt (zinc stearate, calcium stearate, etc.).

4) Charge controllable particles: metal oxides (such as tin oxide, titanium oxide, zinc oxide, silicon oxide, and aluminum oxide) and carbon black.

These additives are used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the toner particles.
0.1 to 5 parts by weight are used. These additives may be used alone or in combination of two or more.

The aqueous medium used in the present invention includes:
Eventually a suitable stabilizer is added. For example, as an inorganic compound, calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide,
Examples include aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, and alumina. As an organic compound, polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salt of carboxymethylcellulose, polyacrylic acid and salts thereof, starch and the like can be used by dispersing them in an aqueous phase. This stabilizer is used in an amount of 0.2 parts based on 100 parts of the polymerizable monomer.
It is preferred to use ２０20 parts by weight.

In order to finely disperse these stabilizers, 0.001 to 0.1 parts by weight of a surfactant may be used. This is to promote the intended action of the dispersion stabilizer, and specific examples thereof include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate,
Examples include sodium oleate, sodium laurate, potassium stearate, calcium oleate and the like.

When an inorganic compound is used among these dispersion stabilizers, a commercially available one may be used as it is, but in order to obtain finer particles, the inorganic compound may be formed in an aqueous medium.

For example, in the case of calcium phosphate, an aqueous solution of sodium phosphate and an aqueous solution of calcium chloride are preferably mixed under high stirring.

The polymerized toner used in the present invention is obtained by the following method. That is, a silicon-containing copolymer, a release agent, a colorant, a charge control agent, a polymerization initiator, and other additives are added to the polymerizable monomer, and the mixture is uniformly dissolved or dispersed by a homogenizer, an ultrasonic disperser, or the like. The resulting monomer system is dispersed in an aqueous medium containing a dispersion stabilizer using a conventional stirrer or homomixer / homogenizer. Preferably, the granulation is performed by adjusting the stirring speed and time so that the monomer droplets have a desired toner particle size, generally a particle size of 30 μm or less. After that, by the action of the dispersion stabilizer, stirring may be performed to such an extent that the particle state is maintained and the particles are prevented from settling or floating. After completion of the reaction, while adding an aqueous medium to the suspension, the aqueous medium is distilled off to remove the dispersion stabilizer, and the generated toner particles are collected by washing and filtration, and dried. In the suspension polymerization method, it is generally preferable to use 300 to 3000 parts by weight of water as a dispersion medium with respect to 100 parts by weight of the monomer system.

In the above process, the polymerization is carried out at a polymerization temperature of 40 ° C. or higher, generally 50 to 90 ° C. Further, the temperature may be raised in the latter half of the polymerization reaction.

The particle size distribution measurement in the present invention will be described.

As a measuring device, Coulter Counter T
A-II type (manufactured by Coulter), number average distribution,
Interface to output volume average distribution (made by Nikkaki)
And CX-1 personal computer (manufactured by Canon)
And the electrolyte is 1% Na using primary grade sodium chloride.
Prepare a Cl aqueous solution.

The measuring method is as follows.
In 50 ml, 0.1 to 5 ml of a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant, and 0.5 to 50 mg of a measurement sample is further added.

The electrolyte in which the sample was suspended was subjected to dispersion treatment for about 1 to 3 minutes by an ultrasonic disperser, and the particle size distribution of particles of 2 to 40 μm was measured using the Coulter Counter TA-II using an aperture of 100 μm as an aperture. Is measured to obtain a volume average distribution and a number average distribution. A weight average particle diameter is obtained from the obtained volume average distribution and number average distribution.

[0048]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below based on embodiments.

Example 1 450 g of an aqueous 0.1 M Na ₃ PO ₄ solution was added to 710 g of ion-exchanged water, heated to 60 ° C., and then used with a TK homomixer (manufactured by Tokushu Kika Kogyo) at 12,000 rpm.
And stirred. 1.0M-CaCl ₂ aqueous solution 68
g was gradually added to obtain an aqueous medium containing Ca ₃ (PO ₄ ) ₂ .

Styrene 180 g 2-ethylhexyl acrylate 20 g C.I. I. Pigment Yellow 17 10 g Paraffin wax (mp 80 ° C.) 30 g Styrene-methacrylic acid-vinyltrimethylsilane copolymer (90: 5: 5) Mw: 50,000 10 g The above formulation was heated to 60 ° C. It was uniformly dissolved and dispersed at 12,000 rpm using a homomixer (manufactured by Tokushu Kika Kogyo). Into this, a polymerization initiator, 10 g of 2,2′-azobis (2,4-dimethylvaleronitrile) and 1 g of dimethyl 2,2′-azobisisobutyrate were dissolved to prepare a polymerizable monomer system. The above-mentioned polymerizable monomer system is charged into the above-mentioned aqueous medium, and the mixture is heated at 9,000 rpm with a TK homomixer at 60 ° C. in an N ₂ atmosphere.
After stirring for minutes, the polymerizable monomer system was granulated. Then, after stirring at 60 ° C. for 5 hours while stirring with a paddle stirring blade,
The liquid temperature was set to 80 ° C., and the reaction was performed for 10 hours. Thereafter, the mixture was cooled, hydrochloric acid was added to dissolve Ca ₃ (PO ₄ ) ₂ , and filtration was performed.
After washing with water and drying, a polymerized toner was obtained. The obtained toner had a weight average particle diameter of 8.0 μm and a sharp particle size distribution.

With respect to 100 parts by weight of the obtained toner, B
0.5 parts by weight of a hydrophobic silica having a specific surface area of 200 m ² / g by the ET method was externally added. To 5 parts by weight of this toner, 95 parts by weight of an acryl-coated ferrite carrier were mixed to prepare a developer. Using this developer and externally added toner, a full-color copier CLC-500 manufactured by Canon
When the image output was evaluated in a low-temperature, low-humidity environment (15 ° C./10%) using a remodeled machine, stable and good images were obtained without deterioration in developability even after 20,000 sheets of durability.

Example 2 In Example 1, the styrene-methacrylic acid-vinyltrimethylsilane copolymer was replaced with styrene-methacrylic acid-
Polymerized toner was obtained in the same manner except that γ-methacryloxypropyltrimethoxysilane copolymer (93: 5: 2) Mw: 40,000 was used. The particle size of the obtained toner was 8.5 μm in weight average diameter and had a sharp particle size distribution. A developer was prepared in the same manner as in Example 1, and the image output was evaluated.
A stable and good image was obtained.

Example 3 Styrene 170 g n-butyl acrylate 30 g C.I. I. Pigment Blue 15: 3 10 g Paraffin wax (mp 70 ° C.) 60 g Styrene-methacrylic acid-γ-methacryloxypropyl trimethoxysilane copolymer (93: 5: 2) except that Mw: 45 g was used. A polymerized toner was obtained in the same manner as in Example 1. The particle size of the obtained toner was 7.9 μm in weight average particle size, and had a sharp particle size distribution. A developer was prepared in the same manner as in Example 1, and the image output was evaluated. As a result, a stable and good image was obtained without a decrease in developability even after 20,000 sheets had been run.

Comparative Example 1 A polymerized toner was prepared in the same manner as in Example 1, except that a styrene-methacrylic acid copolymer (95: 5) Mw 50,000 was used instead of the styrene-methacrylic acid-vinyltrimethylsilane copolymer. I got The obtained toner had a weight average particle size of 8.3 μm and a sharp particle size distribution. A developer was prepared in the same manner as in Example 1, and the evaluation of image output was performed. As a result, the developability was reduced after 20,000 sheets of durability, and a good image could not be obtained.

Example 4 450 g of a 0.1 M Na ₃ PO ₄ aqueous solution was added to 710 g of ion-exchanged water, heated to 60 ° C., and then heated to 12,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo). And stirred. 68 g of 1.0 M CaCl ₂ aqueous solution
Was gradually added to obtain an aqueous medium containing Ca ₃ (PO ₄ ) ₂ .

170 g of styrene 25 g of 2-ethylhexyl acrylate 5 g of allyltrimethylsilane 5 g of C.I. I. Pigment Blue 15: 3 10 g Paraffin wax (mp 70 ° C.) 50 g Styrene-methacrylic acid copolymer (95: 5, Mw 50,000) 5 g Di-tert-butylsalicylate metal compound 5 g Heat the above formulation to 60 ° C. Then, using a TK homomixer (manufactured by Tokushu Kika Kogyo), the mixture was uniformly dissolved and dispersed at 12,000 rpm. Into this, a polymerization initiator, 10 g of 2,2′-azobis (2,4-dimethylvaleronitrile) and 1 g of dimethyl 2,2′-azobisisobutyrate were dissolved to prepare a polymerizable monomer system. The above-mentioned polymerizable monomer system was charged into the above-mentioned aqueous medium, and the mixture was heated at 8,000 rpm using a TK homomixer at 60 ° C. in an N ₂ atmosphere.
After stirring for minutes, the polymerizable monomer system was granulated. Then, after reacting at 60 ° C. for 3 hours while stirring with a paddle stirring blade,
The liquid temperature was set to 80 ° C., and the reaction was performed for 10 hours. Thereafter, the mixture was cooled, hydrochloric acid was added to dissolve Ca ₃ (PO ₄ ) ₂ , and filtration was performed.
After washing with water and drying, a polymerized toner was obtained.

The particle diameter of the obtained toner was 8.5.
It had a sharp particle size distribution at μm.

BE per 100 parts by weight of the obtained toner
0.7 parts by weight of hydrophobic silica having a specific surface area of 200 m ² / g by T method was externally added. 93 parts by weight of an acryl-coated ferrite carrier was mixed with 7 parts by weight of this toner to prepare a developer.

Using this developer and externally added toner, a full-color copying machine CLC-500 modified from Canon was evaluated for image formation under a low-temperature and low-humidity environment (15 ° C./10%). Even after the endurance of the sheet, a stable and good image was obtained without lowering the developability.

Example 5 A polymerized toner was obtained in the same manner as in Example 4 except that allyltrimethylsilane was replaced with allylchloromethyldimethylsilane. The particle size of the obtained toner is
It had a weight average diameter of 8.1 μm and a sharp particle size distribution.

A developer was prepared in the same manner as in Example 4, and the image formation was evaluated. As a result, a stable and good image was obtained without a decrease in the developability even after 20,000 sheets of durability.

Reference Example 1 A polymerized toner was obtained in the same manner as in Example 4 except that allyltrimethylsilane was replaced with allyltrimethoxysilane. The obtained toner had a weight average particle size of 8.3 μm and a sharp particle size distribution.

A developer was prepared in the same manner as in Example 4, and the image output was evaluated. As a result, a stable and good image was obtained without a decrease in developability even after 20,000 sheets of durability. However, the fixing temperature range of the obtained toner is different from that of Example 4.
5 and 5 were shifted to the higher temperature side.

Comparative Example 2 A polymerized toner was obtained in the same manner as in Example 4 except that allyltrimethylsilane was not used. The obtained toner had a weight average particle diameter of 7.9 μm and a sharp particle size distribution. However, a developer was prepared in the same manner as in Example 4 and image evaluation was performed.
After the endurance of 10,000 sheets, the developability deteriorated and good images could not be obtained.

Comparative Example 3 In Example 4, 25 g of allyltrimethylsilane was added.
The same operation was performed except that the amount of 2-ethylhexyl acrylate was changed to 5 g to obtain a polymerized toner. The obtained toner had a weight average particle diameter of 8.3 μm and had a sharp particle size distribution, but had poor blocking resistance and could not be put to practical use.

[0066]

As described above, the toner of the present invention is stable in fluidity and chargeability even under low humidity, and a good image can be stably obtained.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tatehiko Chiba 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Kazuyuki Miyano 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon (56) References JP-A-4-163464 (JP, A) JP-A-57-11354 (JP, A) JP-A-62-108262 (JP, A) JP-A-63-103265 (JP, A) A) JP-A-63-139362 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03G 9/08 CA (STN)

Claims (4)

(57) [Claims] (1) at least i) a polymerizable monomer;
15 to 30 parts by weight of wax per 100 parts by weight of the compatible monomer
And iii) styrene-based monomer, nitrile-based monomer
Isomer, halogen-containing monomer, unsaturated carboxylic acid, unsaturated
Basic acids, unsaturated dibasic acid anhydrides, nitro monomers and
A monomer selected from the group consisting of nitrogen monomers and
Copolymerized with a silane compound having a benzyl group.
Heavy to heavy <br/> polymerizable monomer system containing a silicon-containing vinyl copolymer obtained, wherein the resulting Turkey <br/> by suspension polymerization in an aqueous medium Te Legal toner. 2. The molecular weight (M) of a silicon - containing vinyl copolymer.
w) is 5,000 to 500,000, and is a silicon-containing vinyl copolymer.
The content of coalescence, 0.1-10 polymerizable monomer total
%. 2. The polymerization toner according to claim 1, wherein 3. i) allyltrimethylsilane, allylc
Loromethyldimethylsilane and vinyltrimethylsilane
A polymerizable monomer selected from the group consisting of: ii)
Polymerized toner to a polymerizable monomer system which contains at least a wax, wherein the obtained Turkey by suspension polymerization in an aqueous medium. 4. Allyltrimethylsilane, allylchloro
From methyldimethylsilane and vinyltrimethylsilane
The polymerizable monomer selected from the consisting group, polymerization toner according to claim 3, characterized in Rukoto used 0.01-10 wt% of the total amount of monomers.