JPH10148964A - Toner for developing electrostatic charge image and two-component developer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a developer preventing the lowering of image density and the increase of fog by stabilizing the quantity of electric charges on a toner independently of an environmental change over a long period of time and suppressing the charge-up of the toner especially in an environment at low temp. and humidity. SOLUTION: Colored resin particles contg. a colorant and polyester bonding resin are mixed with fine powder having a smaller average particle diameter than the colored resin particles to obtain the objective negative charge type toner for developing an electrostatic charge image. The fine powder is obtd. by multistage emulsion polymn. In a stage before the final stage, alkyl acrylate and/or alkyl methacrylate is polymerized or copolymerized. In the final stage, polymerizable carboxylic acid or polymerizable carboxylate is polymerized.

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 image and a two-component developer, and more particularly, to a developer for electrophotography which prevents deterioration in characteristics under a low-temperature and low-humidity environment.

[0002]

2. Description of the Related Art As a developing method applied to an electrophotographic method or an electrostatic recording method, a two-component developer composed of a toner and a carrier is used, and a toner is charged by frictional charging between the toner and the carrier. There is known a method of visualizing an electrostatic latent image with toner. The electrostatic latent image formed on the photoconductor or the electrostatic recording medium is visualized by toner,
Such a toner image is transferred to a transfer sheet and then fixed to form a copy. On the other hand, the toner remaining on the photoreceptor or the electrostatic recording medium after the transfer without being transferred is cleaned to prepare for the next copying process. In general, in the case of a two-component developing system including a toner and a carrier, a two-component developer charges a toner to a required charge amount and a charging polarity by friction with a carrier, and uses a photoreceptor using electrostatic attraction. Alternatively, the electrostatic latent image on the electrostatic recording medium is developed, and it is important that the toner has good triboelectric charging properties mainly determined by the relationship with the carrier.

Various studies have been made to ensure good charging characteristics of the toner. For example, Japanese Patent Publication No. 52-32
Japanese Patent Application Laid-Open No. 256-64352 discloses a method in which chargeable fine particles are added to a toner as a charging auxiliary, a method in which fine resin powder having a polarity opposite to that of the toner is added to Japanese Patent Application Laid-Open No. 56-64352. Japanese Patent Application Laid-Open No. -160760 proposes a method of adding a fluorine-containing compound to a toner. However, in the case of the above-described method, it is not easy to uniformly disperse the additive on the toner surface, and it is difficult to avoid that the additives that cannot completely adhere to the toner particles form aggregates. This tendency is due to the fact that the triboelectric charging ability of the
Also, the finer the particle size, the more noticeable. In such a case, the amount of frictional charge of the toner becomes unstable, the image density is not constant, the image becomes fogged, or the content of the charging auxiliary agent changes when a large number of copies are made,
There are various problems such as that the image quality at the initial stage cannot be maintained.

[0004] Japanese Patent Publication No. 2-3173, 317
Nos. 4 and 3175 disclose a method in which fine particles of resin having an average particle size of 0.05 to 5 μm are mixed with a toner. However, these resin fine powders have high triboelectric charging ability, but have poor hydrophilicity on the surface, so that when a large number of copies are made under low temperature and low humidity, the charge amount of the toner obtained by mixing the resin fine powders increases. And there is a problem that the image density is reduced. Further, under low temperature and low humidity, the charge amount of the resin fine powder is too large, the resin fine powder is likely to aggregate, the mixing property is reduced,
Alternatively, the resin fine powder is likely to adhere to the carrier, which is one of the causes of poor friction between the carrier and the toner. As a result, the charging state becomes unstable, and fog (the toner flies and adheres to the non-image portion) Phenomenon) increases, and the quality of the copied image deteriorates. In addition, the above-mentioned problem particularly remarkably appears in a negatively chargeable electrostatic image developing toner using a polyester resin, and the solution of the problem has been awaited.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of such circumstances, and the charge amount of the toner is stable for a long period of time due to environmental changes. It is an object of the present invention to provide a toner for developing an electrostatic image and a two-component developer in which a reduction in image density and an increase in fog are prevented by suppressing the toner density.

[0006]

Means for Solving the Problems A first invention comprises a colored resin particle containing a colorant and a polyester binder resin,
A negatively chargeable electrostatic image developing toner obtained by mixing a fine powder having an average particle size smaller than the average particle size of the colored resin particles, wherein the fine powder is obtained by multi-stage polymerization by emulsion polymerization. A powder which is obtained by polymerizing or copolymerizing an alkyl acrylate and / or an alkyl methacrylate in a polymerization step prior to the final step, and by polymerizing a polymerizable carboxylic acid or a polymerizable carboxylate in the final step of polymerization. The toner for developing electrostatic images is characterized by being a fine powder of:

According to a second aspect of the present invention, the fine powder is a fine powder obtained by converting a carboxylic acid derived from a polymerizable carboxylic acid into a salt after polymerization in the final stage. This is a developing toner.

A third invention is the toner for developing an electrostatic image according to the first invention, wherein the polymerizable carboxylate is a divalent metal salt of a polymerizable carboxylic acid.

A fourth invention is characterized in that the fine powder is a fine powder comprising a carboxylic acid derived from a polymerizable carboxylic acid as a divalent metal salt after the final stage of polymerization. Is a toner for developing an electrostatic image.

In a fifth aspect, the average particle size of the fine powder is 0.0
The toner for developing an electrostatic image according to any one of the first to fourth inventions, which has a thickness of 5 to 5 μm.

According to a sixth aspect of the present invention, there is provided a method according to any one of the first to fifth aspects, wherein 0.01 to 10 parts by weight of a fine powder is mixed with 100 parts by weight of the colored resin particles. This is a toner for developing a charge image.

According to a seventh aspect, there is provided a two-component developer containing the toner for developing an electrostatic image according to any one of the first to sixth aspects and a carrier coated with a silicone resin. is there.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the fine powder used as an external additive is a fine powder obtained by multi-stage polymerization by emulsion polymerization. In the final stage of polymerization, a polymerizable carboxylic acid or a polymerizable carboxylic acid is used. It is important that the powder is a fine powder obtained by polymerizing a salt. That is, a layer containing a relatively hydrophilic carboxylic acid or carboxylate is coated around the surface of the fine powder, and the carboxylic acid or carboxylate adsorbs and retains a suitable amount of water. Prevents excessive charge-up of fine powder and toner under low humidity, and suppresses / prevents image density reduction and fogging under low temperature and low humidity, and suppresses triboelectric charging under high temperature and high humidity It is considered that the increase in fogging can be suppressed.

The fine powder used in the present invention is a fine powder obtained by multi-stage polymerization by so-called emulsion polymerization. For example, in the case of two-stage polymerization, a dispersion containing the fine powder is obtained by the following method. . (1) By the first-stage emulsion polymerization, a dispersion of fine particles of a polymer of an acrylic acid ester and / or an alkyl methacrylate or a dispersion of fine particles of a copolymer (hereinafter abbreviated as a first-stage dispersion). Then, as a second stage emulsion polymerization, a polymerizable carboxylic acid monomer is added or dropped into the first stage dispersion to carry out emulsion polymerization. (2) In the method of (1), after completion of the second-stage emulsion polymerization, a carboxyl group derived from a polymerizable carboxylic acid present near the surface of the dispersed particles is converted into a salt. (3) In the method of (1), in the second-stage emulsion polymerization, instead of the polymerizable carboxylic acid monomer, a salt of a polymerizable carboxylic acid is added or dropped into the dispersion of the first stage to emulsify. Polymerizes. Although the above (1) to (3) have been described for the case of two-stage polymerization, similarly, in the case of multi-stage polymerization exceeding two stages, the polymerizable carboxylic acid or polymerizable The carboxylate may be polymerized, and the polymerization or copolymerization of the acrylate and / or the alkyl methacrylate may be any one of the stages prior to the final stage, and may be performed immediately before the final stage. Is not limited to this stage.

In the present invention, the polymer or copolymer produced in a step before the final step includes a polymer of an alkyl acrylate monomer, a polymer of an alkyl methacrylate monomer, an alkyl acrylate monomer and A copolymer of an alkyl methacrylate monomer or a copolymer containing at least 50% by weight of an alkyl acrylate monomer or an alkyl methacrylate monomer and containing one or more other copolymerizable monomers is provided. No.

The alkyl acrylate monomer and alkyl methacrylate monomer used in the present invention include esterified products of acrylic acid or methacrylic acid with alcohols such as alkyl alcohol, alkoxy alcohol, aralkyl alcohol and alkenyl alcohol. Specific examples of the alcohol include methyl alcohol, propyl alcohol, butyl alcohol, amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, dodecyl alcohol, tetradecyl alcohol, alkyl alcohols such as hexadecyl alcohol; methoxyethyl alcohol, Alkoxy such as ethoxyethyl alcohol, methoxypropyl alcohol, ethoxypropyl alcohol Alcohol; benzyl alcohol, phenylethyl alcohol, such aralkyl alcohols phenylpropyl alcohol; allyl alcohol, include such alkenyl alcohols crotonyl alcohol, methyl acrylate, methyl methacrylate is preferable.

Other monomers that can be copolymerized with the above-mentioned alkyl acrylate monomer and methacrylic acid alkyl ester monomer include amides such as acrylonitrile, acrylamide, methacrylamide, N-dimethylacrylamide, N-dimethylmethacrylamide and nitriles. , Vinyl acetates, vinyl ethers; nitrogen-containing vinyl compounds such as vinyl carbazole, vinyl pyridine, vinyl pyrrolide; aliphatic monoolefins such as ethylene, propylene, butene, isobutylene; vinyl chloride, vinyl bromide, 1,2-dichloroethylene 1,3-dibromoethylene, halogenated aliphatic olefins such as isopropenyl chloride, isopropenyl bromide, allyl chloride, allyl bromide, vinylidene chloride, vinyl fluoride and vinylidene fluoride; Ene, 1,3-pentadiene, 2
Conjugated diene-based aliphatic olefins such as -methyl-1,3-butadiene; and styrenes such as styrene and α-methylstyrene.

The fine powder used in the present invention may be obtained by polymerizing a polymerizable carboxylic acid in the final polymerization step as described above, or by polymerizing a polymerizable carboxylic acid salt in the final polymerization step. good.

The polymerizable carboxylic acid used in the final polymerization step includes acrylic acid, methacrylic acid, α-
Ethyl acrylic acid, crotonic acid, α-methyl crotonic acid, α-ethyl crotonic acid, isocrotonic acid, tiglic acid, addition-polymerizable unsaturated aliphatic monocarboxylic acid such as ungeric acid, or maleic acid, fumaric acid, itaconic acid, Examples include addition-polymerizable unsaturated aliphatic dicarboxylic acids such as citraconic acid, mesaconic acid, glutaconic acid, and dihydromuconic acid. One or more of these can be used, and acrylic acid and methacrylic acid are preferred. As the polymerizable carboxylic acid salt used in the final polymerization step, various salts of the above-mentioned polymerizable carboxylic acid are used.

Salts used for forming carboxylic acid salts before or after polymerization include Na, Mg, K, Li, N
H ₄ , Ca, Ba, Zn, Fe, Cu, Al, Ni, C
hydroxides, oxides, inorganic acid salts, organic acid salts such as o, Cr, etc., among which Mg, Ca, Ba, Zn, Fe, N
Hydroxides, oxides, inorganic acid salts and organic acid salts of divalent metals such as i and Co are preferable, and Mg, Ca, Ba,
The hydroxide, oxide, inorganic acid salt and organic acid salt of Zn are preferable, and the hydroxide, oxide, inorganic acid salt and organic acid salt of Zn are most preferable. Organic acids include formic acid, acetic acid, propionic acid and the like. It is preferable to add these salt-forming agents in an amount equivalent to the carboxyl group of the used or used polymerizable carboxylic acid. Even if it is less than the equivalent, it is effective for improving the stability to the charging ability under low temperature and low humidity. Even if it is added in an equivalent amount or more, there is no problem because the excess portion can be removed by performing a water washing step later.

The amount of the polymerizable carboxylic acid or polymerizable carboxylate used is preferably 0.05 to 20 parts by weight based on 100 parts by weight of the total amount of the monomers used up to the polymerization step before the final step. When the amount is less than 0.05 part by weight, the produced fine powder is added to the colored resin particles to form a toner, and the effect of improving the image density under low temperature and low humidity is poor. When the amount exceeds 20 parts by weight, the hydrophilicity of the surface of the fine powder becomes poor. As a result, the effect of absorbing moisture becomes too large, so that the triboelectric charging ability tends to decrease.

The polymerization initiator used in the emulsion polymerization of the fine powder used in the present invention includes a persulfate initiator, a redox initiator composed of a persulfate and a sulfoxy compound, and a water-soluble azo initiator. Initiators and the like. Examples of the persulfate initiator include potassium persulfate and sodium persulfate. Examples of the Redox initiator composed of a persulfate and a sulfoxy compound include the above-described persulfate and potassium thiosulfate or sodium thiosulfate. Further, water-soluble azo initiators include azobiscyanovaleric acid, 2,2 ′
-Azobis (2-amidinopropane) hydrochloride, 2, 2 '
-Azobis (2-amidinopropane) acetate, 2,2 '
-Azobis (N, N'-dimethyleneisobutylamidine) dihydrochloride and the like.

The emulsifier used in the emulsion polymerization of the fine powder used in the present invention includes sodium higher alcohol sulfate, sodium alkyldiphenyl ether disulfonate, sodium alkylbenzene sulfonate, sodium dialkyl sulfosuccinate, sodium fatty acid, and the like. Or anionic emulsifiers such as potassium, alkyl (or alkylphenyl) ether, sodium or ammonium sulfate: Nonionic such as alkylphenol ethylene oxide adduct, higher alcohol ethylene oxide adduct, polypropylene glycol ethylene oxide adduct, etc. Emulsifiers; cationic emulsifiers such as quaternary ammonium salts, etc .; and water-soluble polymers such as polyvinyl alcohol. Can be.

The fine powder to be used in the present invention is prepared by emulsification polymerization or after emulsification polymerization, converting the surface carboxylic acid into a salt using the above-mentioned salt-forming agent, and then removing water from the aqueous dispersion to obtain a fine powder. do it. As a means for removing water, various drying methods and pulverization methods / pulverization methods usually used for powder production can be applied. After spray-drying the aqueous dispersion, the dried product is pulverized / pulverized. Is preferred.

The fine powder used in the present invention may be prepared by emulsifying the surface carboxylic acid with the above salt-forming agent after emulsion polymerization or after the emulsion polymerization, and then subjecting the aqueous dispersion to an emulsifier by a cross-flow filtration method. Etc. can also be removed. For example, the emulsifier, unreacted substances and the like can be removed by placing the aqueous dispersion in a tabletop emulsion filter (manufactured by Soken Chemical Co., Ltd.), washing the aqueous dispersion by flowing water. After washing, water may be removed by the above method to obtain fine powder.

The fine powder used in the present invention can be obtained by various methods as described above.
The average particle diameter is preferably 5 μm, more preferably 0.1 to 2 μm. If the thickness is less than 0.05 μm, agglomeration is likely to occur under low temperature and low humidity, and the aggregates are liberated, and it is difficult to suppress or prevent a decrease in image density under low temperature and low humidity. On the other hand, if it exceeds 5 μm, the dispersion becomes non-uniform and it is difficult to integrate with the colored resin particles. Therefore, it is difficult to suppress and prevent the charge-up of the toner under low temperature and low humidity, and to suppress the decrease in image density under low temperature and low humidity.・ It tends to be difficult to prevent.
If the fine powder has a large number of sharp corners, the photoreceptor may be damaged. Therefore, the shape of the fine powder is preferably as small as possible with sharp edges and as round as possible, for example, spherical.

The negatively chargeable toner for developing an electrostatic image (hereinafter abbreviated as toner) of the present invention is obtained by adding the above-mentioned fine powder to colored resin particles and mixing them. The colored resin particles used in the present invention contain a polyester-based binder resin and a coloring agent. Examples of the polyester resin used include bisphenol A- in the diol component.
Ethylene oxide adducts, bisphenol A-bisphenol derivative represented by bisphenol A-alkylene oxide adducts such as propylene oxide adducts or substituted alone or ethylene glycol,
An aliphatic dialcohol such as diethylene glycol is used in combination, and the acid component includes, for example, fumaric acid, maleic acid, phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid,
Those obtained by co-condensing pyromellitic acid and the like are preferable. Also,
The polyester resin may be used alone, or the following resins may be used in combination if the polyester resin occupies 50% by weight. For example, styrenes such as styrene, chlorostyrene and vinylstyrene, monoolefins such as ethylene, propylene, butylene and isobutylene, vinyl acetates such as vinyl acetate, vinyl propionate, vinyl benzoate and vinyl butyrate, methyl acrylate and acrylic acid Alkyl acrylates and alkyl methacrylates such as ethyl, butyl acrylate, dodecyl acrylate, octyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, dodecyl methacrylate, and vinyl ethyl ether And homopolymers or copolymers of vinyl ethers such as vinyl butyl ether, and vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and vinyl isopropenyl ketone. Particularly typical binder resins include polystyrene, styrene-alkyl acrylate copolymer, styrene-alkyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride. Acid copolymers, polyethylene, polypropylene and the like can be mentioned. Further polyurethane,
Epoxy resins, silicone resins, polyamides, modified rosins, paraffins and waxes can be mentioned.

Colorants for obtaining the colored resin particles used in the present invention include carbon black, aniline blue, calcoil blue, ultramarine blue,
Quinoline yellow, methylene blue chloride, phthalocyanine blue, malachite green oxalate, lamp black, rose bengal, quinoline yellow, permanent yellow, chrome yellow, benzidine yellow, quinacridone, rhodamine lake, lake red,
Permanent red and the like can be exemplified as typical ones. Further, a charge control agent may be blended with the colored resin particles. For example, metal-containing azo dyes, quaternary ammonium salts,
Salicylic acid derivative metal complexes and the like.

The colored resin particles used in the present invention are used by subjecting a binder resin, a colorant and the like to melt kneading, cooling, pulverization, classification and the like according to a conventional method. The colored resin particles used preferably have an average particle size of less than about 30 μm, more preferably an average particle size of 3 to 20 μm. The toner of the present invention is preferably added with the fine powder in an amount of 0.01 to 10 parts by weight, more preferably 0.05 to 3.0 parts by weight, based on 100 parts by weight of the colored resin particles. .

The toner of the present invention may be obtained by adding various additives to the colored resin particles in addition to the fine powder having a carboxylic acid or a salt thereof on the surface. For example, silica, titania, and alumina each having a fine particle surface subjected to a hydrophobic treatment, a conductive fine powder, or the like can be used in combination with the fine powder.

The developer of the present invention is a so-called two-component developer having a carrier and a toner (hereinafter abbreviated as a developer). The carrier that can be used in the developer of the present invention has an average particle diameter substantially equal to the toner particle diameter, or
Particles of up to 00 μm, iron, nickel, cobalt,
Various known materials such as iron oxide, ferrite, glass beads, granular silicon, and magnetic powder-dispersed resin particles are used. In addition, it is necessary to coat the surface of these particles with a silicone resin coating agent. This is necessary to obtain a suitable triboelectric charge.

The developer of the present invention is most preferably obtained by first mixing a fine powder and colored resin particles to obtain a toner, and then mixing the toner with a carrier. In advance, fine powder may be added and mixed.

The developer of the present invention can develop an electrostatic latent image formed on a photoreceptor or an electrostatic recording medium. That is, selenium, zinc oxide, cadmium sulfide, an inorganic photoconductive material such as amorphous silicon, phthalocyanine pigment, an electrophotographic electrostatic latent image formed on a photoreceptor made of an organic photoconductive material such as bisazo face, or An electrostatic latent image is formed on an electrostatic recording medium having a dielectric material such as polyethylene terephthalate using a needle electrode or the like, and the electrostatic latent image is formed on the electrostatic latent image by a developing method such as a magnetic brush method, a cascade method, or a touch-down method. A toner image is formed by the developer of the present invention. This toner image is transferred to a transfer material such as paper and then fixed to form a copy,
The toner remaining on the surface of the photoreceptor or the like is cleaned. Various methods such as a blade method, a brush method, a web method, and a roll method can be used as the cleaning method.

[0034]

【Example】

Production Example 1 100 parts of methyl methacrylate, 200 parts of distilled water, 0.4 part of potassium persulfate were placed in a 1 L four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube, and reflux condenser.
Parts, 4 parts of polyoxyethylene nonylphenol and 1 part of sodium lauryl sulfate.
Emulsion polymerization was performed at 0 ° C. for 4 hours. After 4 hours, 3 parts of acrylic acid were added, and the polymerization was further continued for 1 hour. After completion of the polymerization, the reaction solution was cooled to 20 ° C., and 1.2 parts of calcium oxide was added to form a salt. The obtained emulsion was filtered and washed using a desktop emulsion filter (manufactured by Soken Chemical Co., Ltd .: cross flow filtration device), dried using a spray drier in the same manner as in Production Example 1, and dissolved in a jet mill. Crush,
A fine powder having an average particle size of 0.3 μm was obtained. When the fine powder thus obtained was observed with a scanning electron microscope (SEM), it was almost spherical. Table 1 shows the water content of the obtained fine powder under each environment.

[0035]

Production Example 2 A fine powder having an average particle diameter of 0.2 μm was obtained in the same manner as in Production Example 1 except that calcium oxide was not used.

[0036]

Production Example 3 A fine powder having an average particle diameter of 0.4 μm was obtained in the same manner as in Production Example 1, except that 2 parts of zinc acetate was used instead of 1.2 parts of calcium oxide.

[0037]

Production Example 4 The procedure of Production Example 3 was repeated, except that 0.4 parts of azobiscyanovaleric acid was used instead of 0.4 part of potassium persulfate, and no zinc acetate was used.
A fine powder of 4 μm was obtained.

[0038]

Production Example 5 A fine powder having an average particle diameter of 0.4 μm was obtained in the same manner as in Production Example 3 except that 2 parts of magnesium acetate was used instead of 2 parts of zinc acetate.

[0039]

Production Example 6 The same procedure as in Production Example 1 was repeated except that 5 parts of sodium methacrylate was used instead of 3 parts of acrylic acid, and no calcium oxide was used after emulsion polymerization.
A fine powder of μm was obtained.

[0040]

Production Example 7 100 parts of methyl methacrylate, 200 parts of distilled water, 0.4 parts of potassium persulfate were placed in a 1 L four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a reflux condenser.
Parts, 2 parts of polyoxyethylene nonylphenol and 0.5 part of sodium lauryl sulfate, and reacted at 80 ° C. for 4 hours in a nitrogen stream. After the completion of the polymerization, the reaction solution was cooled to 20 ° C., and the emulsion obtained by polymerization in the same manner as in Production Example 1 was washed by filtration with a cross-flow filtration device, dried and pulverized to obtain fine particles having an average particle diameter of 0.3 μm. As in Production Example 1, the particles were substantially spherical.

[0041]

Production Example 8 60 parts of methyl methacrylate, 40 parts of acrylic acid, 200 parts of distilled water, 0.4 part of potassium persulfate were placed in a 1 L four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a reflux condenser. 2 parts of polyoxyethylene nonylphenol and 0.5 parts of sodium lauryl sulfate were added and reacted at 80 ° C. for 4 hours in a nitrogen stream. After the completion of the polymerization, the reaction solution was cooled to 20 ° C., and the emulsion polymerized in the same manner as in Production Example 1 was filtered and washed with a crossflow filtration device, dried and pulverized to obtain fine particles having an average particle size of 0.2 μm. As in Production Example 1, the particles were substantially spherical.

[0042]

Example 1 100 parts of a polyester resin obtained by condensing propoxylated bisphenol with terephthalic acid and trimellitic acid 100 parts Charge controller (Bontron E84: Orient Chemical) 4 parts Phthalocyanine pigment 3 parts , Melt-knead with an extruder, crushed with a hammer mill after cooling,
Then finely pulverized with an air jet mill pulverizer, classified,
Colored resin particles were obtained. To 100 parts of the obtained colored resin particles having an average particle diameter of 8 μm, 0.5 part of the resin fine powder obtained in Production Example 1 was mixed as an external additive to obtain a negatively chargeable toner for developing an electrostatic image. Then, 5 parts of the above toner was mixed with 95 parts of a carrier obtained by coating a silicone-based resin on spherical ferrite powder having an average particle diameter of 50 μm to obtain a two-component developer.
Using this two-component developer, a continuous copying test of 10,000 copies was conducted with a commercial copying machine. As shown in Table 2, the charge amount and image density under low temperature and low humidity were 10,000 copies at the beginning of copying. Hardly changed even after the continuous copying test. In addition, fog hardly occurred under low temperature, low humidity and high temperature, high humidity.

[0043]

Examples 2 to 6 100 parts of the same colored resin particles as in Example 1 were mixed with 0.5 part of the fine powder obtained in Production Examples 2 to 6 using a Henschel mixer to form an electrostatic charge of the present invention. An image developing toner and a two-component developer of the present invention were obtained and evaluated in the same manner as in Example 1. Table 2 shows the results.

[0044]

Comparative Examples 1 and 2 To 100 parts of the same colored resin particles as in Example 1, 0.5 part of the fine powder obtained in Production Examples 7 to 8 was mixed using a Henschel mixer, and the toner for developing an electrostatic image was mixed. , And a two-component developer were obtained and evaluated in the same manner as in Example 1. Table 2 shows the results.

[0045]

[Table 1]

[0046]

[Table 2]

[0047]

The effects obtained by the present invention are as follows. 1. Even if a large number of copies are made in a low-temperature and low-humidity environment, the fine powder coated with the carboxylic acid or its salt added to the colored resin particles can remove a suitable amount of water even when a large number of copies are performed in a low-temperature and low-humidity environment. As a result, the excessive charge-up is suppressed, so that a suitable charge amount can be maintained, and even if a large number of copies are made in a low-temperature and low-humidity environment, a decrease in image density can be prevented. 2. An increase in fog at high temperature and high humidity can be prevented. Even if a large number of copies are made in a high-temperature and high-humidity environment, the fine powder coated with the carboxylic acid or its salt added to the colored resin particles adsorbs a suitable amount of water and suppresses a decrease in triboelectricity. By doing so, a suitable charge amount is maintained, and even when a large number of copies are made, an increase in fog can be prevented.

Claims (7)

[Claims] 1. A negatively-chargeable resin obtained by mixing colored resin particles containing a colorant and a polyester-based binder resin with fine powder having an average particle size smaller than the average particle size of the colored resin particles. A toner for developing an electrostatic image, wherein the fine powder is a fine powder obtained by multi-stage polymerization by emulsion polymerization, and a polymerization of an alkyl acrylate and / or an alkyl methacrylate is carried out in polymerization at a stage prior to the final stage. Alternatively, the toner for developing an electrostatic image is a fine powder obtained by copolymerizing and polymerizing a polymerizable carboxylic acid or a polymerizable carboxylate in the final stage of polymerization. 2. The electrostatic image developing toner according to claim 1, wherein the fine powder is a fine powder obtained by converting a carboxylic acid derived from a polymerizable carboxylic acid into a salt after polymerization in the final stage. 3. The toner according to claim 1, wherein the polymerizable carboxylic acid salt is a divalent metal salt of a polymerizable carboxylic acid. 4. The electrostatic image development according to claim 2, wherein the fine powder is a fine powder obtained by converting a carboxylic acid derived from a polymerizable carboxylic acid into a divalent metal salt after polymerization in the final stage. For toner. 5. The toner according to claim 1, wherein the fine powder has an average particle size of 0.05 to 5 μm. 6. The electrostatic image developing toner according to claim 1, wherein 0.01 to 10 parts by weight of a fine powder is mixed with respect to 100 parts by weight of the colored resin particles. 7. A two-component developer comprising the toner for developing an electrostatic image according to claim 1 and a carrier coated with a silicone resin.