JPH0311467B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an electrostatic image developing toner having stable charge controllability and a method for producing the same. Generally, in electrostatic recording, electrostatic printing, electrophotography, etc., electrostatic charge images are visualized using electrodetectable colored particles called toners, which are charged with a polarity opposite to the latent image charge of the electrostatic charge image by triboelectric charging. This is accomplished by electrostatically depositing an electrostatic charge image. Such toner contains a coloring agent such as carbon black in a binder resin such as styrene resin or acrylic resin, and a charge control agent is added so that a desired charge is imparted to the toner by the frictional electrification. Known examples of such charge control agents include dyes and pigments such as oil black, lamp black, nicrosin, aniline blue, calco oil blue, chrome yellow, ultramarine blue, methylene blue chloride, phthalocyan blue, and rose bengal. In addition to being generally extremely expensive, these dyes and pigments are composed of complex organic compounds that have chromophores or auxochromes in their molecular structures.
Because it is easily decomposed or altered by temperature, humidity, light, electric shock, mechanical shock, etc., when it is used in a toner, the triboelectric charging properties of the toner change.
Therefore, there were drawbacks such as poor developability. As a result of extensive research to solve this problem, we have developed an organic compound with a simple molecular structure that can be used to control temperature, humidity,
They have discovered a compound that does not decompose or change in quality when exposed to light, etc., and have completed the present invention. The content of the above compound is 0.1 in the binder resin.
-15% by weight, preferably 0.1-5% by weight. If the content is less than 0.1% by weight, there is no effect on charging, and if it is more than 15% by weight, the amount of charge will be saturated, and if the content is too large, it will adversely affect other electrophotographic properties. The toner used in the dry development method is manufactured by mixing a natural or synthetic resin with a coloring agent, melting and kneading it at a high temperature, cooling the resulting compound to room temperature, and further forming fine particles with the particle size required for the toner. In addition to the usual method of manufacturing by pulverizing and then subjecting it to a classification step, there is also a method for directly obtaining colored polymer fine particles without a pulverizing step, for example,
Publication No. 10231, Special Publication No. 1983-51830, Special Publication No. 1971
-14895 Publication, JP-A-53-17735, JP-A-Sho
A polymerization method has been proposed as described in Japanese Patent Application Laid-Open No. 53-17736 and Japanese Patent Application Laid-Open No. 53-17737. These methods are based on a suspension polymerization method, in which a polymer composition containing a polymer monomer, a polymerization initiator, and a colorant is suspended in an aqueous dispersion medium and then polymerized to directly produce a toner. It is something. This polymerization method has the advantage that the toner particles produced are spherical and have excellent fluidity, and the manufacturing process is simple and the cost is low. However, in this polymerization method, a charge control agent cannot be used because it affects the polymerization reaction, and even if it can be used, it is difficult to uniformly disperse it in the resin and the quantity is limited, so it is difficult to achieve satisfactory charge control. It is not possible to produce toner that has Also,
As described in Japanese Patent Publication No. 36-10231, when charge control is carried out by treatment with a surfactant, the temperature dependence of the surfactant directly affects the charging characteristics of the toner. This has the disadvantage that triboelectric charging becomes extremely unstable. Also,
As described in Japanese Patent Publication No. 51-14895, when a toner adhesive resin is made of a monomer polymer into which a polar group has been substituted, and charge control is performed using the polar group, the toner binding resin has a special property. This has the disadvantage that it is expensive, and that it is difficult to control the softening point and glass transition point, which affect fixing properties and blocking. An object of the present invention is to provide a new toner for developing electrostatic images that eliminates the drawbacks of conventional toners. Another object of the present invention is to provide a toner for developing electrostatic images with excellent charging characteristics. Furthermore, another object of the present invention is to provide a method for producing a toner for developing an electrostatic image, which can achieve the above-mentioned objects. Still another object of the present invention is to provide a method for producing a toner for developing electrostatic images that is inexpensive to produce. In order to achieve these objectives, the present invention was completed as a result of intensive research. The present invention resides in a toner for developing electrostatic images characterized by containing one or more compounds selected from the following general formulas [], [], and []. l represents an integer from 0 to 3, m represents an integer from 0 to 2, and n represents an integer from 0 to 3. In the formula, X, Y and Z may be the same or different and each represents a halogen atom, a nitro group, a cyano group, an aldehyde group or an alkoxycarbonyl group. However, when l in the formula is 2 or more, X may be a different group. When m is 2 or more, Y may be a different group. When n is 2 or more, Z may be a different group. The compound of the general formula is as shown below, but is not limited thereto. The toner of the present invention is prepared by polymerizing the monomers constituting the binder resin by emulsion polymerization, suspension polymerization, solution polymerization, etc. to obtain a polymer resin, and adding a coloring agent (usually 3 to 20 wt. If the particle size is less than 1μ, it will cause fogging, and if it exceeds 50μ, it will cause image quality problems. Further, the monomers of the binder resin are dispersed and subjected to suspension polymerization in an aqueous medium by adding a polymerization initiator (lauroyl peroxide, benzoyl peroxide, 2,2'-azobisisobutyronitrile, etc.), a coloring agent, etc. A toner composed of colored polymer particles may be formed by this process, and this may be further crushed and classified to obtain a toner having a desired particle size. As the binder resin used in the present invention,
Any conventionally known resin such as polystyrene resin, acrylic resin, epoxy resin, polyester resin, etc. can be used. The softening point of these binder resins is measured using a Koka type flow tester (manufactured by Shimadzu Corporation) and is usually within the range of 80 to 180°C. This value is determined from the viewpoints of toner crushability during production, blocking resistance during storage, fixability during image formation, etc. In the measurement of the softening point using the Koka type flow tester, a sample of 1 cm ³ (weight of true specific gravity x 1 cm 3 ) was put into a cylinder with a cross section of 1 cm ² and a depth of 5 cm, which had a nozzle of 1 mm length and 1 ^mm diameter on the bottom. and at 80℃
Preheat for 10 minutes, heat and melt under the pressure of a plunger with a load of 20 kg/cm ² while increasing the temperature at a rate of 6°C per minute. The softening point is defined as the temperature at 1/2 of the height h of the S-curve formed when this is measured on a graph. Specific examples of resins include polystyrene, chloropolystyrene, poly-α-methylstyrene, styrene-chlorostyrene copolymer, styrene-propylene copolymer, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, and styrene. −
Vinyl acetate copolymer, styrene-maleic acid copolymer, styrene-acrylic ester copolymer (styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, Styrene-octyl acrylate copolymer, styrene-phenyl acrylate copolymer, etc.), styrene-methacrylate copolymer, (styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene- butyl methacrylate copolymer, styrene-octyl methacrylate copolymer, styrene-phenyl methacrylate copolymer, etc.), styrene-α-methyl chloroacrylate copolymer, styrene-acrylonitrile-acrylic acid ester copolymer, etc. Polymers or copolymers of unsaturated compounds can be mentioned. In addition, the epoxy resin has an epoxy equivalent of 900 to 3500, and particularly preferable ones include Epicote 1004 and Epicote
1007, Epicote 1009 (manufactured by Ciel Chemical Co., Ltd.), Araldite GY6084, and Araldite GY6099 (manufactured by Ciba Geigy). Polyester resin is polycondensation consisting of polyhydric alcohol and polybasic acid, and preferred polyhydric alcohol components include ethylene glycol, glycerin, 1,2-propylene glycol, 1,3-propylene glycol, neopentyl glycol, and 1,4-butane. Diol, 1,
6-hexanediol, 1,4-cyclohexanedimethanol, trimethylolethane, trimethylolpropane, pentaerythritol, etc. are used, and the polybasic acid components include maleic acid, fumaric acid, isophthalic residue, terephthalic acid, adipic acid, and sebacin. Acid, trimellitic acid, pyromellitic acid, etc. can be used. In addition, the said resin can be used individually or in combination of 2 or more types. In the present invention, when a toner is produced by direct polymerization, suspension polymerization is the most suitable polymerization method. As the polymerizable monomer used for this, any polymerizable monomer can be used, and self-polymerizable vinyl monomers may be used. For example, monomers such as dibasic acids and glycols that can produce polyester resins can be used, but vinyl monomers are preferably used. The unsubstituted terphenyl compound of the present invention can be particularly effectively used in granulation polymerization such as suspension polymerization. Specific examples of polymerizable monomers preferably used in the present invention are listed below. These include, for example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene,
p-ethylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n-
Octylstyrene, p-n-nonylstyrene, p
- Styrene and styrene derivatives such as -n-decylstyrene, p-n-dodecylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, and 3,4-dichlorostyrene; styrene monomers is most preferred. Examples of other vinyl monomers include ethylenically unsaturated monoolefins such as ethylene, propylene, butylene, and isobutylene; and vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide, and vinyl fluoride. Furthermore, vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, acrylic Dodecyl acid, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-methacrylate Butyl, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, methacrylic acid 2
-ethylhexyl, stearyl methacrylate,
α-methylene aliphatic monocarboxylic acid esters such as phenyl methacrylate, dimethylaminoethyl methacrylate, and diethylaminoethyl methacrylate; nitriles such as acrylonitrile and methacrylonitrile; acrylic acid or methacrylic acid derivatives such as acrylamide; Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, and vinyl isobutyl ether; Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and methyl isopropenyl ketone;
N-vinylpyrrole, N-vinylcarbazole,
Examples include N-vinyl compounds such as N-vinylindole and N-vinylpyrrolidone; vinylnaphthalenes and the like. These vinyl monomers may be used alone or in combination. As polymerizable monomers other than vinyl monomers, the following can be used. First, as monomers for obtaining polyester resin, examples of dibasic acids include terephthalic acid, isophthalic acid, adipic acid,
Maleic acid, succinic acid, sebacic acid, thioglycolic acid, diglycolic acid, etc. can be mentioned, and glycols include ethylene glycol, diethylene glycol, 1,4-bis(2-
Examples include hydroxyethyl)benzene, 1,4-cyclohexanedimethanol, propylene glycol, and the like. Monomers for obtaining polyamide resin include caprolactam, dibasic acids include terephthalic acid, isophthalic acid, adipic acid, maleic acid, succinic acid, sebacic acid, thioglycolic acid, and diamines. is ethylenediamine, diaminoethyl ether, 1,4-diaminobenzene, 1,4-
Examples include diaminobutane. As monomers for obtaining polyurethane resin, examples of diisocyanates include p-phenylene diisocyanate, p-xylene diisocyanate, and 1,4-tetramethylene diisocyanate, and examples of glycols include ethylene glycol, diethylene glycol, and propylene. Glycol, polyethylene glycol, etc. can be mentioned. As monomers for obtaining polyuric resin, diisocyanates include p-phenylene diisocyanate, p-xylylene diisocyanate, 1,4-tetramethylene diisocyanate, etc., and diamines include ethylene diamine, diamino diisocyanate, etc. ethyl ether, 1,
Examples include 4-diaminobenzene and 1,4-diaminobutane. As monomers for obtaining epoxy resin, amines include ethylamine, butylamine, ethylenediamine, 1,4-
Examples of diepoxies include diaminobenzene, 1,4-diaminobutane, and monoethanolamine. Examples of diepoxies include diglycidyl ether, ethylene glycol diglycidyl ether, bisphenol-A-diglycidyl ether, and hydroquinone diglycidyl ether. can be mentioned. In addition, the said monomer can be used individually or in combination of 2 or more types. For 100 parts by weight of the above monomer, a polymerization initiator,
If necessary, 5 to 95 parts by weight of prepolymer and 1 to 20 parts by weight of colorant are added. For example, gelatin,
Suspended at 60°C to 120°C in a nitrogen stream in the presence of a dispersant such as starch, polyvinyl alcohol, barium sulfate, calcium sulfate, barium carbonate, magnesium carbonate, calcium phosphate, talc, clay, diatomaceous earth or metal oxide powder. Either by turbid polymerization or by using a water-soluble polymerization initiator in the presence of a surfactant such as sodium dodecylbenzenesulfonate, an alkyl sulfate type anionic emulsifier, or sodium dodecylsulfonate, under a nitrogen stream at a temperature of 40 to 90°C. Emulsion polymerization is performed to obtain a polymer. It is desirable to carry out the polymerization so that the average molecular weight of the obtained polymer is 50,000 to 200,000. When the polymer according to the present invention is a condensation polymer or an addition polymer, a general dibasic acid and a glycol are mixed with a strong acid (for example, sulfuric acid, p-toluenesulfonic acid, etc.).
A polyester resin can be produced by a method of synthesis by heating reaction at 100° C. to 180° C. or under reduced pressure. Ordinary polyamide resins can also be produced by reacting a dibasic acid and a diamine salt in a molten state by heating at 140° to 200°C. In addition, phenol-formalin resin can be obtained by the usual method of heating formalin, phenols, and a strong acid or base catalyst to 100° to 150°C. Polyurethane resins can also be produced by the usual method of heating reaction at 50° to 150°C in the presence of glycol and diisocyanate. Polyurea resins can also be produced by the usual method of reacting diamines and diisocyanates at 20° to 100°C. When the polymer according to the present invention is a ring-opening polymer, an epoxy resin can be prepared by the usual method of reacting a diamine and a diepoxy compound at 50° to 120°C. The monomers used in the present invention may be used alone, but self-polymerizable monomers and other monomers may be used in various combinations. All of the obtained polymers according to the present invention had a softening point measured by a Koka type flow tester (manufactured by Shimadzu Corporation).
A temperature of 100° to 170°C is particularly effective as a resin for toner, and a glass transition point of about 40° to 110°C is effective. That is, if the softening point is below 100°C, excessive pulverization or toner filming phenomenon may occur, which tends to contaminate the photoconductive plate.
Furthermore, if the softening point exceeds 170°C, the toner will be hard and difficult to crush, and moreover, a large amount of heat will be required during fixing, resulting in poor fixing efficiency. On the other hand, if the glass transition point is below 40°C, agglomeration is likely to occur due to the cold flow phenomenon since toner storage conditions are usually below 40°C, and if the glass transition point exceeds 110°C, In the case of the roller fixing method, even if the fixing roller material is metal, for example, if the fixing roller is made of Teflon (manufactured by Dupont), the roller may wear out if the temperature of the fixing roller exceeds 250°C.
In addition, there is a restriction that the temperature cannot be raised too high due to the heat resistance limit of the roller material, such as decomposition, so that sufficient fixing cannot be achieved, especially when fixing is performed at a high speed. The polymer according to the present invention obtained as described above is
In the case where the toner is in the form of fine particles that can be put to practical use as it is, in the case where the toner is produced by crushing this polymer using a pulverizer and classifying it using a zigzag classifier, and in the case where the toner is produced by mixing this polymer with a coloring agent, etc.
The toner may be produced by grinding, cooling and crushing in a grinder. In either case, the average particle size of the toner of the present invention is the same as that of commonly used toners, preferably in the range of 7 to 30 μm. If large particles of 50 μm or more are included, the image quality will be significantly degraded, and if fine powder particles of 1 μm or less are included, the fine powder particles may contaminate the surface of the photoreceptor, reduce the sensitivity of the photoreceptor, degrade the image, etc. This is not preferable because it causes a phenomenon. The polymer according to the invention may be a crosslinked polymer. This crosslinked polymer may be one that undergoes self-crosslinking polymerization, such as a prepolymer (in this case, the monomer that undergoes self-crosslinking polymerization may be used in combination with other monomers), or A crosslinking agent may be present during polymerization. Any known crosslinking agent can be used as long as it crosslinks and polymerizes the monomer according to the present invention. This crosslinking agent is preferably a compound having at least two polymerizable vinyl groups.
Specifically, aromatic divinyl compounds such as divinylbenzene, divinylnaphthalene, and derivatives thereof; ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane triacrylate, allyl methacrylate, t-butylaminoethyl methacrylate,
Tetraethylene glycol dimethacrylate,
Diethylenically unsaturated carboxylic acid esters such as 1,3-butanediol dimethacrylate, N,
All divinyl compounds such as N-divinylaniline, divinyl ether, divinyl sulfide, and divinyl sulfone, and compounds having three or more vinyl groups can be used alone or in combination of two or more. Furthermore, ethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4
-butanediol, neopentyl glycol,
1,4-butenediol, 1,4-bis(hydroxymethyl)cyclohexane, bisphenol
A, dihydric alcohols such as hydrogenated bisphenol-A, polyoxyethylenated bisphenol-A, polyoxypropylenated bisphenol-A; maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, glutacone acids, dibasic acids such as phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, succinic acid, adipic acid, sebacic acid, malonic acid, their anhydrides or their esters with lower alcohols; and their derivatives; glycerin, Trivalent or higher valent alcohols such as trimethylolpropane and pentaerythritol and trivalent or higher valent carboxylic acids such as trimellitic acid and pyromellitic acid are used as crosslinking agents in the present invention. The amount of such crosslinking agent added to the monomer is 0.005 to 20% by weight, preferably 0.1 to 5% by weight.
A weight percent range is selected. If the amount added is too large, the toner becomes insoluble and infusible, and the fixing properties for toners tend to be poor. If the amount added is too small, it becomes difficult to impart the characteristics of toner such as durability, storage stability, and abrasion resistance. . In the present invention, a polymer is obtained by polymerizing a polymerizable monomer in the presence of the terphenyl of the present invention, and a polymerization initiator may be used during the polymerization. Examples of the polymerization initiator include lauroyl peroxide, benzoyl peroxide, 2,2'-azobisisobutyronitrile, 2,2'-azobis-(2,4-dimethylvaleronitrile), orthochlorobenzoyl peroxide, Orthomethoxybenzoyl peroxide is mentioned. In the present invention, the polymer obtained by the above-described method is used as a toner, and at that time, optional coloring agents such as pigments and stains are added as necessary to improve the properties as a toner. be able to. These coloring agents are known ones, such as carbon black, nigrosine dye, aniline blue, calco oil blue, chrome yellow,
Ultramarine blue, Dupont oil red,
These are quinoline yellow, methylene blue chloride, phthalocyan blue, malachide green oxalate, lamp black, oil black, azo oil black, rose bengal and mixtures thereof. Also, where conventional xerographic reproduction of printed documents is desired, the toner is
For example, it may be made from a black dye such as carbon black or a black dye such as amablast black dye. The amount of the colorant used in the toner of the present invention may vary widely, but is usually 1 to 20 parts by weight per 100 parts by weight of the monomer. When adding a coloring agent after obtaining the polymer, it may be added in the same manner as described above. When the toner of the present invention is used in a roller fixing method (particularly a hot roller fixing method), a release agent may be added to prevent offset. Various types of release agents are known, and the most preferred is an olefin polymer. This olefin polymer is an olefin polymer containing only olefin as a monomer component or an olefin copolymer containing a monomer other than olefin as a monomer component, and has a low softening point. Examples of olefins as monomer components include ethylene, propylene, butene-1, pentene-1, and hexene-1.
1, hebutene-1, octene-1, nonene-1,
Decene-1 or its homologues with different positions of the unsaturated bond or e.g. 3-methyl-1-
All kinds of olefins such as butene, 3-methyl-2-pentene, 3-propyl-5-methyl-2-hexene, etc. into which an alkyl group is introduced as a branched chain are included. In addition, monomers other than olefin that form a copolymer with olefin include, for example, vinyl methyl ether, vinyl-
Vinyl ethers such as n-butyl ether and vinyl phenyl ether; vinyl esters such as vinyl acetate and vinyl butyrate; haloolefins such as vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, vinyl chloride, vinylidene chloride, and tetrachloroethylene; For example, methyl acrylate, ethyl acrylate, n-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, stearyl methacrylate, N,N-dimethylaminoethyl methacrylate, t-butylaminoethyl methacrylate, etc. acrylic esters or methacrylic esters; for example, organic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, and itaconic acid; various examples include diethyl fumarate and β-pinene. The olefin polymer used in the present invention is an olefin polymer consisting only of olefins containing at least two or more of the above-mentioned olefins as monomer components, such as ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-butene copolymer, At least one of the above-mentioned olefins, such as pentene copolymer, propylene-butene copolymer, propylene-pentene copolymer, ethylene-3-methyl-1-butene copolymer, ethylene-propylene-butene copolymer, etc. An olefin copolymer containing at least one monomer other than olefin as a monomer component, such as ethylene-
Vinyl acetate copolymer, ethylene-vinyl methyl ether copolymer, ethylene-vinyl chloride copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-acrylic acid copolymer, propylene- vinyl acetate copolymer, propylene-vinylethyl ether copolymer, propylene-ethyl acrylate copolymer, propylene-methacrylic acid copolymer, butene-vinyl methyl methacrylate copolymer, pentene-vinyl acetate copolymer, These include hexene-vinyl butyrate copolymer, ethylene-propylene-vinyl acetate copolymer, ethylene-vinyl acetate-vinyl methyl ether copolymer, and the like. Among the olefin polymers used in the present invention, in those containing monomers other than olefin as monomer components, it is desirable that the olefin component contained in the copolymer be as large as possible. This is because, in general, as the content of the olefin component decreases, the mold releasability decreases, and characteristics such as toner fluidity and image quality tend to deteriorate. Therefore, it is desirable that the content of the olefin component in the copolymer be as high as possible, and in particular, copolymers containing about 50 mol% or more of the olefin component are effectively used in the present invention. The olefin polymer preferably has a softening point of 100° to 180°C, particularly 130° to 160°C. The amount of the olefin polymer used is 1 to 20 parts by weight, preferably 3 to 15 parts by weight, per 100 parts by weight of the resin component of the toner, and if it is less than 1 part by weight, it may not have a sufficient offset prevention effect.
Moreover, if it exceeds 20 parts by weight, gelation may occur during polymerization, which is not preferable. When the toner of the present invention is used as a one-component developer, any magnetic material can be added. Any acidic, neutral, or basic magnetic material can be used as this magnetic material, but when it is present during polymerization,
A magnetic material with a pH of 6 or more, preferably 6 to 10 is preferable. The magnetic material used in the present invention includes:
It is a substance that is strongly magnetized by a magnetic field, is preferably black in color, is well dispersed in resin, is chemically stable, and can be easily obtained in the form of fine particles with a particle size of 1μ or less. Magnetite (triiron tetroxide) is the most preferable. Typical magnetic or magnetizable materials include metals such as cobalt, iron, and nickel; aluminum cobalt, copper, iron, lead, magnesium,
Alloys and mixtures of metals such as nickel, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, panadium; aluminum oxide, iron oxide, copper oxide, nickel oxide, zinc oxide, Metal compounds including metal oxides such as titanium oxide and magnesium oxide; refractory titanides such as vanadium titanide and chromium titanide; carbides such as tungsten carbide and silica carbide;
Ferrites, mixtures thereof, etc. can be used. These ferromagnetic materials preferably have an average particle size of about 0.1 to 1 μm, and the amount contained in the toner is preferably about 30 to 300 parts by weight based on 100 parts by weight of the resin component, and it is particularly preferable that The amount is 50 to 200 parts by weight per 100 parts by weight. The toner of the present invention can be obtained as described above,
During the polymerization of the monomers or when producing the toner after obtaining the polymer, a binder resin known for use in toners may be further combined. To form an image using the toner of the present invention, for example, by electrophotography, a selenium photoreceptor or an inorganic photoconductive material such as zinc oxide, cadmium sulfide, cadmium selenide, cadmium selenide sulfide, lead oxide, mercury sulfide, etc. A photoreceptor in which a photosensitive layer containing a conductive material dispersed in a binder resin is provided on a conductive support;
Alternatively, a photoreceptor may be used in which a photosensitive layer containing an organic photoconductive material such as anthracene or polyvinylcarbazole in a binder resin is provided on a conductive support, if necessary. The surface of the photosensitive layer of such a photoreceptor is entirely charged by corona discharge using, for example, a corotron or scorotron charger, and then imagewise exposed to light or the like to form an electrostatic charge image. Next, this electrostatic charge image is developed by, for example, a cascade method or a magnetic brush method, with a developer comprising, for example, a mixture of the toner of the present invention and a glass beads or iron powder carrier to form a toner image. This toner image is transferred onto the transfer paper by being pressed against the transfer paper under, for example, corona discharge.
The toner image transferred onto the transfer paper is heat-fixed by a heat roll fixing device coated with, for example, a fluorine-based resin or silicone rubber having mold-releasing properties. EXAMPLES Hereinafter, the present invention will be illustrated by Examples, but the embodiments of the present invention are not limited thereby. In addition, "parts" shown in the following examples indicate "parts by weight" unless otherwise specified. Example 1 100 parts of styrene/butyl acrylate copolymer (composition ratio: 85:15) (softening point: 125°C), 10 parts of Mitsubishi Carbon Black #30 (manufactured by Mitsubishi Chemical Industries, Ltd.), Piskol 550P (low molecular weight) Polypropylene (manufactured by Sanyo Chemical Industries, Ltd.) (6 parts) and paraterphenyl (3 parts) were thoroughly melted and kneaded in a kneader, cooled, coarsely crushed in a hammer mill, further finely crushed in a jet mill, and then finely crushed in a classifier to an average particle size of 15 μm. The material was classified and made into toner.
Using a developer consisting of 2 parts of this toner and 100 parts of iron powder carrier, Ubitx V (Konishi Roku Photo Industry Co., Ltd.
A 10,000-time image test was carried out by the company (manufactured by Co., Ltd.). The obtained toner image was clear with no fog, had a high degree of blackening, and had good fixing properties such as prevention of offset. Example 2 A developer was prepared in the same manner as in Example 1, except that 100 parts of styrene/butyl acrylate copolymer (composition ratio: 85:15) (softening point: 125°C) and 3 parts of m-terphenyl were used. Example 3 Example-1 except that 3 parts of o-terphenyl was used
A developer was prepared in the same manner. Comparative Example 1 A developer was prepared in the same manner as in Example 1 except that terphenyl was not used as the charge control agent. Comparative Example 2 Using 100 parts of styrene/butyl acrylate (85/15) copolymer, 2 parts of Barrier First Black-3804 (manufactured by Orient Chemical Co., Ltd.), 10 parts of Mitsubishi Carbon Black #300, and 6 parts of Viscoel 550P, the others were A developer was prepared in the same manner as in Example-1. When copying tests were conducted in the same manner as in Example 1 using each of the developers of Comparative Examples 1 and 2, the triboelectric charging properties of the toners decreased from around the initial 1000 copies, resulting in a decrease in copy density. , and fog started to appear. Above Examples-1 to Example-3 and Comparative Example-1
~Comparative Example-2 Each of the developers was idly stirred 100 times in the developing device of a Ubix V copying machine to triboelectrically charge the toner in each developer, and the amount of charge of this toner was measured by the blow-off method. The results are shown in the table below.

[Table] Example 4 85 parts of styrene, 15 parts of n-butyl acrylate,
0.4 parts of ethylene glycol dimethacrylate,
Mitsubishi Carbon Black #30 (manufactured by Mitsubishi Chemical Industries, Ltd.)
10 parts of 2,2'-azobis(2,4-dimethylvaleronitrile), 6 parts of Viscol 550P (low molecular weight polypropylene: manufactured by Sanyo Chemical Industries, Ltd.), and 3 parts of o-terphenyl were mixed and dispersed and polymerized. Prepare a composition, add this to a colloidal solution of 3% by weight calcium phosphate and 0.04% by weight sodium dodecylbenzenesulfonate in a stainless steel beaker with a solubility of 1, and add it to a colloidal solution of 3% by weight calcium phosphate and 0.04% by weight sodium dodecylbenzene sulfonate in a TK homogeter (manufactured by Tokushu Kika Kogyo Co., Ltd.).
The mixture was stirred at a stirring speed of 9000 r.pm. The particle size range of the dispersed particles after stirring for 30 minutes was 10-15 microns. Thereafter, the temperature was raised to 60° C., and the polymerization reaction was allowed to proceed for 7 hours while stirring at a stirring speed of 100 rpm using an ordinary stirrer to complete the polymerization. After the polymerization was completed, the solid matter was separated and dried to obtain the toner of the present invention having an average particle size of 12 microns. Two parts of this toner were mixed with 100 parts of iron powder carrier to form a two-component developer. An image was formed using this two-component developer in Ubix-V (manufactured by Konishiroku Photo Industry Co., Ltd.). The obtained toner image had no fog, was clear, had a high degree of blackening, and had good fixing properties such as prevention of offset. Example 5 A developer was prepared in the same manner as in Example 4 except that m-terphenyl was used in an amount of 3 parts. Comparative Example 3 A developer was prepared in the same manner as in Example 4 except that terphenyl was not used. The developer prepared in Examples 4 to 5 and Comparative Example 3 above was processed using Ubitx V (manufactured by Konishiroku Photo Industry Co., Ltd.) in the same manner as in Examples 1 to 3 and Comparative Examples 1 to 2. After performing an image test 10,000 times,
The toner was triboelectrically charged by idling and stirring 100 times, and the amount of charge on the toner was measured by a blow-off method.

[Table] From the above results, it was found that by using terphenyl as a charge control agent as in the present invention, very good charge control properties with high charge stability can be obtained. Example 6 67 parts of Mabiko Black BL-500 (triiron tetraoxide powder: manufactured by Titan Kogyo Co., Ltd.), 1 part of benzoyl peroxide, 85 parts of styrene, 15 parts of n-butyl methacrylate, 0.5 part of triethylene glycol methacrylate, and 3 parts of terphenyl. A polymeric composition was prepared by mixing the two parts. This was added to a 2-capacity separable flask containing distilled water containing 1.0% by weight of tricalcium phosphate, and thereafter a toner was produced in the same manner as in Example-4. This toner was used as a component-based developer, and an electrostatic latent image formed on a selenium photoreceptor was developed with the developer. The resulting images were clear with no fog, had a high degree of blackening, and had good fixing properties such as anti-offset properties.

Claims (1)

[Claims] 1. A toner for developing electrostatic images, characterized by containing one or more compounds selected from the following general formulas [], [], and []. l represents an integer from 0 to 3, m represents an integer from 0 to 2, and n represents an integer from 0 to 3. In the formula, X, Y and Z may be the same or different and each represents a halogen atom, a nitro group, a cyano group, an aldehyde group or an alkoxycarbonyl group. However, in the formula, when l is 2 or more, X may be a different group. When m is 2 or more, Y may be a different group. When n is 2 or more, Z may be a different group. 2. The toner for developing electrostatic images according to claim 1), wherein the compound is contained in the binder resin in an amount of 0.1 to 15% by weight. 3. The toner for developing an electrostatic image as set forth in claim 1) or 2), wherein the compound is contained in a vinyl binder resin. 4. A method for producing a toner for developing an electrostatic image, comprising a step of polymerizing a polymerizable monomer in the presence of the compound. 5. The method for producing a toner for developing an electrostatic image according to claim 4), wherein the polymerization is carried out by a suspension polymerization method. 6. The method for producing a toner for developing an electrostatic image according to claim 4) or 5), wherein the compound is added in an amount of 0.1 to 15% by weight.