JP3230027B2 - Toner for developing electrostatic images - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner for developing an electrostatic charge image, which is used in a method for visualizing an electrostatic charge latent image and is particularly excellent in fixability and durability.

[0002]

2. Description of the Related Art Electrophotography is disclosed in U.S. Pat.
As described in, for example, US Pat. No. 691 and the like, 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, various methods have been conventionally proposed, and a method suitable for each image forming process is 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 process can produce fairly good toners, it does have certain limitations, namely the range of choice of toner materials. For example, the resin colorant dispersion must be sufficiently brittle and capable of being pulverized in economically feasible manufacturing 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 susceptible to further pulverization or pulverization 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. Thereafter, 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 include a pulverizing step at all, so that the toner does not need to be brittle, a soft material can be used, and a colorant is not exposed on the surface of the particles. There is an advantage of having a triboelectric charging property. Further, since the classification step can be omitted, the cost reduction effect is large, such as saving energy, shortening the time, and improving the process yield.

[0007] Further, in the conventional pulverization method toner, the amount of the release agent to be added is restricted due to the characteristics of the production method. However, in the polymerization method toner, a large amount of the release agent can be contained, and the amount of the release agent can be increased. It is possible to produce a toner having excellent fixing properties.

However, from the standpoint of further image quality stability and fixability required of recent copying machines, sufficient ones have not yet been obtained.

As described above, the polymerization toner can contain a large amount of a releasing agent, and can provide extremely excellent fixing properties, but deteriorates image quality in long-term durability, and it is not possible to achieve both fixing properties and image stability. Was enough.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and to provide a toner for developing an electrostatic image having excellent fixability.

Another object of the present invention is to provide a highly stable electrostatic image developing toner which does not cause deterioration in image quality even in long-term durability.

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polymerizable monomer containing a long-chain acrylate and / or a long-chain methacrylate and a polymerizable monomer containing at least a release agent. A polymerized toner directly obtained by dispersing and polymerizing a monomer composition in an aqueous medium, wherein the acrylate and / or methacrylate ester portion is a hydrocarbon having 20 or more carbon atoms. This is achieved by a toner for developing an electrostatic image.

As a result of intensive studies, the present inventors have found that the toner for developing an electrostatic image containing the above-mentioned binder resin and release agent has excellent fixability and does not cause deterioration in image quality even in long-term durability. It has been found that high stability can be obtained.

Hereinafter, the present invention will be described in detail.

As described above, the polymerization toner can contain a large amount of a release agent inside the toner. Furthermore,
This release agent is encapsulated in the toner and forms a core-shell structure. Therefore, a low melting point release agent can be contained without impairing the blocking resistance of the toner.

As described above, the toner having the core-shell structure receives heat and pressure during fixing, so that the release agent in the core is melted and exudes to the interface between the fixing roller and the toner. Demonstrates offset resistance to

In other words, when considering the improvement of the fixing property, the point is how quickly the release agent of the core part is exuded to the interface between the fixing roller and the toner. Therefore, the present inventors focused on the compatibility between the release agent and the binder resin,
As a result of the investigation, it was found that the release agent in the core portion quickly exudes to the interface between the fixing roller and the toner by making the release agent in the core portion and the binder resin in the shell portion more easily compatible. .

The present invention is based on the above-mentioned idea,
Long-chain acrylate and / or as a binder resin
Or, by using a resin obtained from a polymerizable monomer containing a long-chain methacrylic acid ester, the release agent and the binder resin can be easily blended to some extent, and as a result, excellent fixability can be obtained. It is.

A feature of the present invention is that a long-chain acrylate or methacrylate ester having a hydrocarbon having 20 or more carbon atoms in the ester portion thereof is used as a long-chain ester and a release agent. It is to improve familiarity.

The number of carbon atoms in the ester portion is preferably 20 or more. If the number of carbon atoms is less than 20, the compatibility with the release agent becomes insufficient, and the excellent fixing property as the object of the present invention cannot be obtained. As for the upper limit of the carbon number, 100 is sufficient, and the use of more than 100 carbon atoms does not change the fixing property.

The amount of the acrylate or methacrylate is preferably 1 to 20% by weight based on the total amount of the polymerizable monomers. If the amount is less than 1% by weight, excellent fixability cannot be obtained. On the other hand, if the content exceeds 20% by weight, the compatibility with the release agent becomes too good, and it is difficult to form a sufficient core-shell structure. As a result, in the long-term durability, toner fusion occurs on the drum. Problem occurs, and stable image quality cannot be obtained. Also,
The blocking resistance of the toner also decreases.

The long-chain acrylate and long-chain methacrylate used in the present invention may be used in combination with other acrylates and methacrylates.

The polymerizable monomers used to obtain the binder resin of the present invention include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p
Styrene monomers such as ethylstyrene, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, n-octyl acrylate, dodecyl acrylate, acrylic acid 2-
Ethylhexyl / stearyl acrylate / acrylic acid 2
Acrylates such as chloroethyl and phenyl acrylate, methyl methacrylate and ethyl methacrylate;
N-propyl methacrylate / n-butyl methacrylate
Isobutyl methacrylate, n-octyl methacrylate,
Dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate,
Examples thereof include methacrylates such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate, and monomers such as acrylonitrile, methacrylonitrile, and acrylamide. Among the above-mentioned monomers, it is preferable to use a mixture of styrene or a styrene derivative with another monomer from the viewpoint of the developing characteristics and durability of the toner.

The ester portion of the long-chain acrylate or long-chain methacrylate used in the present invention may be long-chain or branched as long as it has 20 or more carbon atoms. It may be unsaturated.

Specific examples of more preferable ones are as follows.

[0026]

Embedded image And the like. In the present invention, the number of carbon atoms in the ester moiety is defined as 28 to 36, which is obtained by adding one unterminated carbon to the repeating unit (n), taking the compound (I) as an example.

[0027] At least one of the peaks of the molecular weight distribution of the binder resin of the present invention by GPC is from 5,000 to 5
It is preferably in the range of 000. Peak 5
If it does not exceed 000, the blocking resistance decreases.
On the other hand, if there is a peak exceeding 50,000, the low-temperature fixability is inferior.

The toner of the present invention is produced by a polymerization method so that a large amount of a release agent can be included.

Examples of the release agent used in the present invention include paraffin, polyolefin wax, ester wax and modified products thereof, for example, a graft-treated product with a compound represented by an oxide or a reactive silicone compound. And higher fatty acids and their metal salts, amide waxes and the like. These release agents may be used alone or in combination.

The melting point of the release agent is preferably from 40 to 100.degree. When the melting point is less than 40 ° C., the blocking resistance and shape retention of the toner are insufficient, and when it exceeds 100 ° C., the releasing effect becomes insufficient.

The addition amount is preferably 5 to 50 parts by weight based on 100 parts by weight of the polymerizable monomer. When the addition amount is less than 5 parts by weight, the releasing effect becomes insufficient. If the amount exceeds 50 parts by weight, the toner has insufficient blocking resistance and shape retention, and as a result, a stable image cannot be obtained. The melting point in the present invention is defined as DSC
From the maximum endothermic peak temperature.

When the toner of the present invention is produced by a polymerization method, it is more preferable to polymerize a polymerizable monomer composition by adding a polymer / copolymer having a polar group as an additive to the polymerizable monomer composition. The polar polymer / copolymer gathers on the surface layer of the toner particles, so that it forms a kind of shell, which gives the toner particles excellent properties such as anti-blocking properties, while comparing inside the toner. By performing polymerization so as to contribute to improvement of fixing characteristics at a very low molecular weight, it becomes easy to obtain a toner satisfying conflicting requirements of fixing property and blocking resistance. The polar polymers and copolymers that can be used in the present invention are exemplified below.

Polymers of nitrogen-containing monomers such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate, copolymers with styrene / unsaturated carboxylic acid esters, etc., nitrile monomers such as acrylonitrile, vinyl chloride Halogen-containing monomers, unsaturated carboxylic acids such as acrylic acid and methacrylic acid, and other unsaturated dibasic acids
Unsaturated dibasic acid anhydrides, polymers such as nitro monomers or copolymers with styrene monomers, polyesters,
Epoxy resins and the like can be mentioned.

The amount of the polar polymer / copolymer added may be 0.1 to 100 parts by weight of the total polymerizable monomer.
10 parts by weight are preferred.

As the coloring agent used in the present invention, known coloring agents can be used. 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, when a toner is obtained using a polymerization method, it is necessary to pay attention to the polymerization inhibitory property and aqueous phase migration property of the colorant, and preferably, surface modification, for example,
It is better to perform a hydrophobic treatment with a substance that does not inhibit polymerization. In particular, dyes and carbon blacks require polymerization precautions because they often have polymerization inhibitory properties. As a preferable method of surface-treating the dye system, a method of previously polymerizing a polymerizable monomer in the presence of these dyes is mentioned, and the obtained colored polymer is added to the monomer composition. In addition, the carbon black may be treated with a substance that reacts with the surface functional group of the carbon black, for example, a polyorganosiloxane, in addition to the treatment similar to the above-described dye.

When the toner is used as a magnetic toner, it may contain a magnetic powder. As such magnetic powder, a substance that is magnetized when placed in a magnetic field is used.
There are powders of ferromagnetic metals such as iron, cobalt and nickel, or compounds such as magnetite and ferrite. In particular, in the present invention, when a toner is obtained using a polymerization method, it is necessary to pay attention to the polymerization inhibitory property and aqueous phase transfer property of the magnetic substance, and preferably, surface modification, for example, without polymerization inhibition It is better to carry out a hydrophobic treatment with a substance.

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. Examples of these charge control agents include, as positive charge control agents, nigrosine dyes, triphenylmethane dyes, quaternary ammonium salts, guanidine derivatives, imidazole derivatives, amine and polyamine compounds, and the like. Examples thereof include metal-containing salicylic acid compounds, metal-containing monoazo dye compounds, urea derivatives, styrene-acrylic acid copolymers, and styrene-methacrylic acid copolymers.

The addition amount of these charge control agents is preferably from 0.1 to 10 parts by weight based on 100 parts by weight of all polymerizable monomers.

As the polymerization initiator, any suitable polymerization initiator, for example, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1'-azobis (cyclohexane-1-
Azo-based or diazo-based polymerization initiators such as carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile and 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 all polymerizable monomers 1
The addition amount is preferably 0.5 to 20 parts by weight with respect to 00 parts by weight, and may be used alone or in combination.

In the present invention, a known crosslinking agent or chain transfer agent may be added to control the molecular weight. A preferable addition amount is 0 to 100 parts by weight of the total polymerizable monomer. 0.0001 to 15 parts by weight.

As an additive for imparting various toner properties, from the viewpoint of durability when added to the toner or when added to the toner, the particle diameter should be 1/10 or less of the volume average diameter of the toner particles. Is preferred. The particle size of this additive
The average particle diameter obtained by observing the surface of the toner particles with an electron microscope is meant. As additives for 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 (strontium titanate, cerium oxide, aluminum oxide, magnesium oxide, chromium oxide, etc.), nitrides (silicon nitride, etc.), carbides (silicon carbide, etc.), metal salts (calcium sulfate, etc.) , Barium sulfate, calcium carbonate, etc.

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

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

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 particle diameter of the toner of the present invention is preferably 3 to 10 μm in terms of weight average diameter in order to obtain a higher quality image. Furthermore, 3 to 8 μm is more preferable.

The above-mentioned toner having a small particle diameter particularly deteriorates fixability in a highlight portion and a halftone portion where the amount of toner on the paper is small, so that the toner having the constitution of the present invention can be particularly preferably applied.

When the toner of the present invention is produced by a polymerization method, any suitable stabilizer is used as a dispersion medium. For example, as inorganic oxides, tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, and sulfuric acid barium·
Bentonite, silica, alumina and the like can be mentioned. As organic compounds, polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose,
Ethyl cellulose / carboxymethyl cellulose sodium salt / polyacrylic acid and its salts / starch and the like can be used by dispersing them in an aqueous phase. These stabilizers are preferably used in an amount of 0.2 to 20 parts by weight based on 100 parts by weight of the total polymerizable monomers.

When an inorganic compound is used among these stabilizers, a commercially available one may be used as it is, but in order to obtain fine particles, the inorganic compound may be formed in a dispersion medium. For example, in the case of tricalcium phosphate, an aqueous sodium phosphate solution and an aqueous calcium chloride solution may be mixed under high stirring.

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, and the like.
Examples include sodium oleate, sodium laurate, potassium stearate, calcium oleate, and the like.

The polymerized toner used in the present invention is obtained by the following method. That is, a releasing agent, a coloring agent, a charge control agent, a polymerization initiator, and other additives are added to a polymerizable monomer containing a long-chain acrylate and / or methacrylate, and a homogenizer / ultrasonic wave is added. The monomer composition uniformly dissolved or dispersed by a disperser or the like is dispersed in an aqueous phase containing a dispersion stabilizer by a conventional stirrer or a homomixer / homogenizer. Preferably, the monomer droplets are of the desired toner particle size, generally 3
The stirring speed and time are adjusted so as to have a particle size of 0 μm or less, and granulation is performed. Thereafter, by the action of the dispersion stabilizer, the particles may be stirred to such an extent that the particle state is maintained and the particles are prevented from settling. The polymerization temperature is 40 ° C. or higher, generally 5
The polymerization is carried out at a temperature of 0 to 90 ° C. Further, the temperature may be raised in the latter half of the polymerization reaction, and further, in order to remove unreacted polymerizable monomers and by-products which cause odor at the time of fixing the toner, the second half of the reaction, or the end of the reaction. Later, a part of the aqueous medium may be distilled off. After completion of the reaction, the generated toner particles are collected by washing and filtration, and dried. In the suspension polymerization method, usually, 300 parts by weight of water is added to 100 parts by weight of the monomer composition.
It is preferable to use 3000 parts by weight as the dispersion medium.

[0053]

The method for measuring each physical property value according to the present invention will be described below.

(1) Molecular Weight Distribution The molecular weight distribution of a chromatogram by GPC using THF (tetrahydrofuran) as a solvent for the toner resin component is measured under the following conditions.

That is, the column is stabilized in a heat chamber at 40 ° C., THF as a solvent is flown into the column at this temperature at a flow rate of 1 ml per minute, and about 100 μl of a THF sample solution is injected to measure. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of a calibration curve prepared from several kinds of monodisperse polystyrene standard samples and the count number. As a standard polystyrene sample for preparing a calibration curve, for example, one having a molecular weight of about 10 ² to 10 ⁷ manufactured by Tosoh Corporation or Showa Denko KK, and it is appropriate to use a standard polystyrene sample having at least about 10 points. is there. An RI (refractive index) detector is used as the detector. As a column, it is better to combine a plurality of commercially available polystyrene gel columns,
For example, Shodex GPC KF-8 manufactured by Showa Denko KK
01,802,803,804,805,806,80
7,800P combinations and TSKge manufactured by Tosoh Corporation
_{lG1000H (H XL), G2000H (} H XL), G3
_{000H (H XL), G4000H (} H XL), G5000
H (H _XL ), G6000H (H _XL ), G7000H (H
_XL ), TSK guard column.

A sample is prepared as follows. The sample is put in THF, left for several hours, shaken sufficiently, mixed well with THF (until the sample is no longer united), and left still for 12 hours or more. At this time, the time of being left in THF is set to be 24 hours or more. After that, the sample passed through a sample processing filter (pore size: 0.45 to 0.5 μm, for example, available from Maishoridisk H-25-5 Tosoh Corporation, Exikurodisc 25CR German Man Science Japan, or the like) can be used. GPC sample. The sample concentration is adjusted so that the resin component is 0.5 to 5 mg / ml.

(2) Particle size distribution A Coulter counter TA-II type (manufactured by Coulter Inc.) was used as a measuring device, and an interface (manufactured by Nikkaki) for outputting a number average distribution and a volume average distribution and a CX-
1 A personal computer (manufactured by Canon Inc.) is connected, and a 1% aqueous NaCl solution is prepared using primary grade sodium chloride as an electrolyte.

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

(3) Fixability / Offset Commercially available electrophotographic copying machine CLC-500 (manufactured by Canon Inc.)
An unfixed image was obtained by a modified machine, and a test was performed using a temperature-variable heat roller external fixing machine using a Teflon coat as an upper roller and a silicone rubber as a lower roller. The temperature was controlled every 5 ° C. in a temperature range of 100 to 230 ° C. with a nip of 5.0 mm, a linear pressure of 0.6 kg / cm, and a process speed of 100 mm / sec. The test transfer paper contains 6
Evaluation was performed using 4 g / m ² recycled paper. The fixability was determined by applying a load of 50 g / m ² to the fixed image and using Lenz cleanani.
ng paper “dasper” (Ozu Pap
aer Co. Ltd.), and the temperature at which the rate of decrease in density before and after rubbing was less than 10% was defined as the fixing start point. For the offset, the temperature was raised, and the highest temperature at which there was no offset visually was taken as the high-temperature offset-free end point.

[0062]

EXAMPLES The present invention will be described more specifically with reference to the following examples.

Example 1 460 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 subjected to 12000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo).
And stirred. A 1.0M-CaCl ₂ aqueous solution 70
g was gradually added to obtain an aqueous medium containing Ca ₃ (PO ₄ ) ₂ .

On the other hand, 170 g of styrene 30 g of long-chain acrylate 30 g (compound I, having 28 to 36 carbon atoms in the ester portion) Phthalocyanine pigment 10 g Di-t-butylsalicylic acid metal compound 1 g Styrene-methacrylic acid copolymer 8 g (molar ratio 90 : 10, M _w = 45,000) 40 g of paraffin wax (mp 70 ° C.)

The above formulation was heated to 60 ° C. and uniformly dissolved and dispersed at 12,000 rpm using a TK homomixer. The polymerization initiator 2,2'-azobis (2,4
8 g of (dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition. The polymerizable monomer composition is charged into the aqueous medium, and the mixture is heated at 60 ° C. in an N ₂ atmosphere.
The mixture was stirred at 10,000 rpm for 20 minutes with a K-type homomixer to granulate the polymerizable monomer composition. Thereafter, the temperature was increased to 70 ° C. while stirring with a battle stirring blade, and the reaction was performed for 10 hours.

After the completion of the polymerization reaction, a part of the aqueous medium was distilled off under reduced pressure, the mixture was cooled, hydrochloric acid was added to dissolve the calcium phosphate, and the mixture was filtered, washed with water and dried to obtain a weight average particle diameter of 7.5.
μm colored suspension particles were obtained. 0.8 parts by weight of hydrophobic silica was externally added to 100 parts by weight of the obtained particles to obtain a suspension polymerization toner.

Table 1 shows the physical properties of the obtained toner.

Next, 5 parts by weight of the obtained toner was mixed with 100 parts by weight of the acrylic-coated ferrite carrier to obtain a developer.

Using a developer and a toner, a full-color copier CLC-500 modified from Canon was used for 10,000.
After performing the durability test of the sheet, the image quality is evaluated in three stages (○, △, ×)
evaluated.

The results of the evaluation are shown in Table 1.

Example 2 A toner was obtained in the same manner as in Example 1 except that the polymerizable monomer composition was changed to the following formulation. Table 1 shows the physical properties and the evaluation results.

Styrene 170 g Long-chain acrylate 10 g (Compound I, having 28 to 36 carbon atoms in the ester portion) n-butyl acrylate 20 g Phthalocyanine pigment 10 g Di-t-butylsalicylate metal compound 1 g Styrene-methacrylic acid copolymer 8 g ( molar ratio 90: 10, M _W = 4.5 50,000) paraffin wax (m.p.60 ℃) 40g 2,2'- azobis (2,4-dimethylvaleronitrile) 10 g

Example 3 A toner was obtained in the same manner as in Example 1 except that the polymerizable monomer composition was changed to the following formulation. Table 1 shows the physical properties and the evaluation results.

Styrene 180 g Long-chain methacrylic acid ester 20 g (Compound IV, having 26 to 36 carbon atoms in ester portion) Phthalocyanine pigment 10 g Di-t-butylsalicylic acid metal compound 1 g Styrene-methacrylic acid copolymer 8 g (Molar ratio 90:10) , M _W = 45,000) 30 g of paraffin wax (mp 70 ° C.)

[0075] Comparative Example 1 Styrene 90 parts by weight long-chain methacrylic acid ester 100 g (compound IV, wherein the number of carbon atoms in the ester moiety 26-36) copolymer obtained from 10 parts by weight (M _W = 25 50,000) phthalocyanine pigment 5g di After preliminarily mixing 0.5 g of -t-butylsalicylic acid metal compound and 5 g of paraffin wax (mp 70 ° C.), the mixture was melt-kneaded by a roll mill set at 120 ° C. After cooling the kneaded material, it was roughly pulverized, finely pulverized by a pulverizer using a jet stream, and further classified using an air classifier, and subjected to the same external addition operation as in Example 1 to obtain a toner.

Thereafter, a developer was obtained and evaluated in the same manner as in Example 1. Table 1 shows the physical properties of the toner and the evaluation results.

Comparative Example 2 A toner was obtained in the same manner as in Example 1 except that the polymerizable monomer composition was changed to the following formulation. Table 1 shows the physical properties and the evaluation results.

Styrene 170 g n-butyl acrylate 30 g (acrylate ester having 4 carbon atoms in the ester portion) Phthalocyanine pigment 10 g Di-t-butylsalicylic acid metal compound 1 g Styrene-methacrylic acid copolymer 8 g (molar ratio 90:10, M _W = 45,000) 40 g of paraffin wax (mp 70 ° C.)

Comparative Example 3 A toner was obtained in the same manner as in Example 1 except that the polymerizable monomer composition was changed to the following formulation. Table 1 shows the physical properties and the evaluation results.

Styrene 170 g Long-chain acrylate 30 g (Compound I, 26 to 36 carbon atoms in ester portion) Phthalocyanine pigment 10 g Di-t-butylsalicylate metal compound 1 g Styrene-methacrylic acid copolymer 8 g (Molar ratio 90:10) , M _W = 45,000)

Comparative Example 4 A toner was obtained in the same manner as in Example 1 except that the polymerizable monomer composition was changed to the following formulation. Table 1 shows the physical properties and the evaluation results.

170 g of styrene 30 g of stearyl acrylate 30 g (acrylic acid ester having 18 carbon atoms in the ester portion) Phthalocyanine pigment 10 g Metal compound of di-t-butylsalicylate 1 g 8 g of styrene-methacrylic acid copolymer (molar ratio 90:10, _MW = 45,000) 40 g of paraffin wax (mp 70 ° C.)

[0083]

[Table 1]

[0084]

As described above, according to the present invention, it is possible to obtain a toner having good fixability without deteriorating the image quality even in long-term durability.

────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tatehiko Chiba 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (56) References JP-A-6-59503 (JP, A) JP-A-5 JP-A-257318 (JP, A) JP-A-5-273787 (JP, A) JP-A-7-181726 (JP, A) JP-A-7-286047 (JP, A) JP-A-63-228172 (JP, A) JP-A-5-331238 (JP, A) JP-A-6-148936 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03G 9/08-9/087

Claims (4)

(57) [Claims] 1. A water-based polymerizable monomer composition containing at least a polymerizable monomer and <br/> releasing agent containing a methacrylic acid ester of an acrylic acid ester and / or long-chain long chain
A polymerization method toner directly obtained by dispersing and polymerizing in a medium , wherein the ester portion of the acrylate and / or methacrylate is a hydrocarbon having 20 or more carbon atoms. A toner for developing electrostatic images, characterized in that: 2. The method according to claim 1, wherein the content of the acrylate and / or methacrylate is 1 to the total polymerizable monomer.
The toner for developing an electrostatic charge image according to claim 1, wherein the amount is from 20 to 20% by weight. 3. The release agent has a melting point of 40 to 100 ° C. and a content of 5 to 5 parts by weight per 100 parts by weight of the polymerizable monomer.
0 The toner according to claim 1 or 2, characterized in that a part by weight. 4. The polymerizable monomer is styrene, o-methyl
Styrene, m-methylstyrene, p-methylstyrene
, P-ethylstyrene, methyl acrylate, 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, methyl methacrylate, methacrylate
Ethyl acrylate, n-butyl methacrylate, methacrylic acid
Isobutyl, n-propyl methacrylate, methacrylic acid
n-octyl, dodecyl methacrylate, methacrylic acid 2
-Ethylhexyl, stearyl methacrylate, methacrylic acid
Phenyl acrylate, dimethylaminoethyl methacrylate,
Diethylaminoethyl acrylate, acrylonitrile,
Glue composed of methacrylonitrile and acrylamide
At least one polymerizable monomer selected from
The electrostatic device according to any one of claims 1 to 3, wherein
Toner for image development.