JPH0318708B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to an electrostatic image developing toner having stable charge controllability and a method for producing the same. [Prior Art] Generally, in electrostatic recording, electrostatic printing, electrophotography, etc., visualization of an electrostatic charge image is performed using a toner, which is charged with a polarity opposite to the latent image charge of the electrostatic charge image due to triboelectric charging. This is accomplished by electrostatically attaching electrostatically colored particles to the electrostatic image. Such toner contains a colorant 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. Such charge control agents include, for example, oil black, lamp black, nigrosine, aniline blue, calco oil blue, chrome yellow,
Dyes and pigments such as ultramarine blue, methylene blue chloride, phthalocyanine blue, and rose bengal are known. In addition to being generally extremely expensive, these dyes and pigments are composed of complex organic compounds containing chromophores or auxochromes in their molecular structures, and are susceptible to decomposition or deterioration due to temperature, humidity, light, electric shock, mechanical shock, etc. Because of this tendency, when it is contained in a toner and used, the triboelectric charging properties of the toner change, resulting in a decrease in developability. On the other hand, the toner used in the dry development method is made by mixing a natural or synthetic resin with a coloring agent, melting and kneading the mixture at high temperatures, cooling the resulting mixture to room temperature, and further processing it into fine particles with the required particle size for the toner. In addition to the usual method of manufacturing by pulverizing and then subjecting it to a classification step, there is 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
As described in JP-A-53-17736 and JP-A-53-17737, a polymer composition containing a polymerizable monomer, a polymerization initiator, and a coloring agent is mixed with water. The toner is directly produced by suspending it in a dispersion medium and polymerizing it. 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 amount is limited, so it is difficult to produce a toner with satisfactory charge control properties. I can't. Furthermore, when charging is controlled by treatment with a surfactant as described in Japanese Patent Publication No. 36-10231, the temperature dependence of the surfactant directly affects the charging characteristics of the toner. This results in the drawback that the triboelectric charging properties of the toner are significantly unstable. Furthermore, as described in Japanese Patent Publication No. 14895/1983, when a toner binder resin is a polymer of monomers substituted or introduced with polar groups, and the charge is controlled by the polar groups, Since the toner binder resin is special, it is expensive and has the disadvantage of being restricted in controlling the softening point and glass transition point, which affect fixing properties and blocking. As a result of intensive research to solve this problem, the present inventor found an organic compound with a simple molecular structure that does not decompose or change in quality due to temperature, humidity, light, etc., and was able to complete the present invention. I've reached it. [Object of the Invention] A first object of the present invention is to provide a new toner for developing electrostatic images that eliminates the drawbacks of conventional toners. A second object of the present invention is to provide a toner for developing electrostatic images with excellent charging characteristics. A third object of the present invention is to provide a method for producing a toner for developing electrostatic images, which can achieve the above-mentioned objects. A fourth object of the present invention is to provide a method for producing a toner for developing electrostatic images that is inexpensive to produce. [Structure of the Invention] The toner for developing electrostatic images of the present invention contains a substance represented by the following general formula [] (hereinafter referred to as the substance of the present invention) as a charge control agent in the binder. It is characterized by General formula [] In the formula, X, Y and Z are hydrogen atom, halogen atom, _-NO2 group, N( _CH3 ) ₃₊ ^, -CN group, -COOH group,
It represents a _-SO3H group, a -CHO group, or a -COOR group (R represents an alkyl group, an alkenyl group, an allyl group, an aralkyl group, etc.), and each may be the same or different. M represents Bi, P or Sb, m and n are integers of 0 or 1,
p, q and r are integers from 0 to 3. Exemplary compounds of the substance of the present invention include the following. The method for producing the above compound is not particularly limited, but
For example, for triphenyl phosphate,
Cadogan, Molden J. Chem. Soc. 1961, p. 3079 and U.S. Pat.
Forward et.al. J. Chem. Soc 1949, p. Antimony is
It can be produced by the method described in Beilstein Vol. 16, 891, and other compounds can be produced in the same manner as above. The content of the substance of the present invention in the binder resin is
0.1 to 15% by weight, preferably 1 to 5% by weight
It is. When the content is less than 0.1% by weight, there is no effect on charging, and when it exceeds 15% by weight, the amount of charging becomes saturated, and a large amount of the substance of the present invention adversely affects other electrophotographic properties. As a method for producing the toner in the present invention, a kneading method is usually adopted, but a commonly used polymerization method can also be used as another method. As the binder resin used in the present invention,
Conventionally known resins include polystyrene resin, acrylic resin, epoxy resin, and polyester resin. The softening point of these binder resins is
It 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 addition, when measuring the softening point using the above-mentioned Koka type flow tester, a 1 cm 2 sample was placed in a cylinder with a cross section of 1 cm ² and a depth of 5 cm, which had a nozzle with a length of 1 cm and a diameter of ^{1 cm} on the bottom. ) and heat to 80℃.
The temperature is heated at a rate of 6°C per minute under the pressure of a plunger with a load of 20 kg/ ^cm2 , and heated and melted. The softening point is defined as the temperature at 1/2 of the height h of the S-shaped curve that is created when this is measured on a graph. Specific examples of the binder resin include polystyrene, chloropolystyrene, poly-α-methylstyrene, styrene-chlorostyrene copolymer,
Styrene-propylene copolymer, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, 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-butyl methacrylate copolymer, styrene-octyl methacrylate copolymer, etc.) copolymers, styrene-phenyl methacrylate copolymers, etc.), styrene-α-methyl chloroacrylate copolymers, styrene-acrylonitrile-acrylic acid ester copolymers, etc. can be mentioned. The epoxy resin has an epoxy equivalent of 900 to 3,500, and particularly preferred is Epicoat 100.
4. Epicote 1007, Epicote 1009
(manufactured by Ciel Chemical Co., Ltd.), Araldite GY6084,
Araldite GY6099 (manufactured by Ciba Geigy)
The polyester resin is a polycondensate consisting of a polyhydric alcohol and a polybasic acid, and preferred polyhydric alcohol components include ethylene glycol, glycerin, 1,2-propylene glycol, and 1,3-propylene glycol. , neopentyl glycol, 1,4-butanediol, 1,
6-hexanediol, 1,4-cyclohexanedimethanol, trimethylolethane, trimethylolpropane, pentaerythritol, etc. are used, and the polybasic acid components include maleic acid, fumaric acid, isophthalic acid, terephthalic acid, adipic acid, Sebacic acid, trimellitic acid, pyromellitic acid, etc. are used. The above resins can be used alone or in combination of two or more. To the toner of the present invention, optional colorants such as pigments and dyes can be added as necessary during polymerization of monomers or after obtaining the polymer. Known coloring agents are used, such as carbon black, nigrosine dye, aniline blue, calco oil blue, chrome yellow, ultramarine blue, Dupont oil red, quinoline yellow, methylene brake chloride, phthalocyanine blue, and malacide. Green oxalate, lamp black, oil black, azo oil black, rose bengal and mixtures thereof are used. Additionally, the toner may be made from a black dye, such as a black dye such as carbon black or an amablast black dye, where conventional xerographic reproduction of printed documents is desired. Although the amount of the colorant used in the toner of the present invention may vary widely, it is usually
The amount is 1 to 20 parts by weight per 100 parts by weight. 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, heptene-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-n
- Vinyl ethers such as 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, acrylics such as methyl acrylate, ethyl acrylate, n-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, stearyl methacrylate, N,N-dimethylaminoethyl methacrylate, and t-butylaminoethyl methacrylate. Acid esters or methacrylic ester acids; 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 a monomer component, such as an ethylene-propylene copolymer,
Ethylene-butene copolymer, ethylene-pentene copolymer, propylene-butene copolymer, propylene-pentene copolymer, ethylene-3-methyl-1-butene copolymer, ethylene-propylene-
Butene copolymers or the like, or olefin copolymers containing as monomer components at least one of the above-mentioned olefins and at least one of the above-mentioned monomers other than olefins, such as ethylene-vinyl acetate copolymers. , 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-vinylmethyl methacrylate copolymer, pentene-vinyl acetate copolymer, hexene-vinyl butyrate copolymer,
These include 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.
If it exceeds 20 parts by weight, gelation may occur in the weight, 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 monomer polymerization,
A magnetic material having a pH of 6 or more, preferably 6 to 10 is preferable. The magnetic substance used in the present invention is a substance that is strongly magnetized in the direction of a magnetic field, is preferably black in color, is well dispersed in the resin, is chemically stable, and has a particle size of 1μ
It is desirable that the following fine particles can be easily obtained, and magnetite (triiron tetroxide) is the most preferred. Typical magnetic or magnetizable materials include metals such as cobalt, iron, nickel; aluminum, cobalt, copper, iron, lead, magnesium, nickel, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, Alloys of metals and mixtures thereof such as manganese, selenium, titanium, tungsten, panadium; metal compounds including metal oxides such as aluminum oxide, iron oxide, copper oxide, nickel oxide, zinc oxide, titanium oxide and magnesium oxide; Refractory nitrides such as vanadium nitride and chromium nitride; carbides such as tungsten carbide and silica carbide; ferrites and mixtures thereof, and the like may be used. These ferromagnetic materials have an average particle size of 0.1~
The amount of the resin component is preferably about 1 μm, and the amount contained in the toner is preferably about 30 to 300 parts by weight per 100 parts by weight of the resin component.
The amount is 50 to 200 parts by weight per 100 parts by weight. In the toner of the present invention, a polymer resin is obtained by polymerizing monomers constituting the binder resin by emulsion polymerization, suspension polymerization, solution polymerization, etc., and a colorant (usually, Carbon black) is mixed with 3 to 20% by weight, heated and melted, kneaded, cooled, crushed and classified to obtain a particle size of 1 to 50μ, preferably 5 to 30μ.
toner. If the particle size is less than 1μ, it will cause fogging, and if it exceeds 50μ, it will cause uneven image quality. In addition, the monomer of the binder resin is combined with a polymerization initiator (lauroyl peroxide, benzoyl peroxide, 2,2'-azobisisobutyronitrile, etc.),
A toner composed of colored polymer particles may be formed by dispersion and suspension polymerization in an aqueous medium with the addition of a coloring agent, and the toner may be further crushed and classified to obtain a toner having a desired particle size. In the present invention, when a toner is produced by direct polymerization, the most suitable polymerization method is a suspension polymerization method. Any polymerizable monomer can be used as long as it is a polymerizable monomer, 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 it is preferable to use vinyl monomers. Specific examples of polymerizable monomers preferably used in the present invention are listed below. Examples include styrene, α-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, and 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 butyrate; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate,
Propyl acrylate, 2-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, α-
Methyl chloroacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, methacrylate
α-methylene aliphatic monocarboxylic acid esters such as 2-ethylhexyl, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; Nitriles such as acrylonitrile and methacrylonitrile; acrylamide, etc. Acrylic acid or methacrylic acid derivatives; Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone; N-vinylpyrrole, N-vinyl Examples include N-vinyl compounds such as carbazole, 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 a monomer for obtaining polyester resin, as a dibasic acid,
Examples of glycols include terephthalic acid, isophthalic acid, adipic acid, maleic acid, succinic acid, sebacic acid, thioglycolic acid, and diglycolic acid. Examples of glycols include ethylene glycol, diethylene glycol, and 1,4-bis(2- Examples include hydroxyethyl)benzene, 1,4-cyclohexanedimethanol, propylene glycol, and the like. As a monomer for obtaining polyamide resin, caprolactam is used, and as dibasic acids, terephthalic acid, isophthalic acid, adipic acid,
Examples of the diamine include maleic acid, succinic acid, sebacic acid, and thioglycolic acid. Examples of the diamine include ethylenediamine, diaminoethyl ether, 1,4-diaminobenzene, and 1,4-diaminobutane. As a monomer for obtaining a polyurethane resin, examples of diisocyanates include p-phenylene diisocyanate and p-phenylene diisocyanate.
-xylylene diisocyanate, 1,4-tetramethylene diisocyanate, etc., and examples of the glycols include ethylene glycol, diethylene glycol, propylene glycol, polyethylene glycol, and the like. As monomers for obtaining polyurea resin, diisocyanates include p-phenylene diisocyanate, p-xylylene diisocyanate,
Examples of diamines include 1,4-tetramethylene diisocyanate, ethylenediamine, diaminoethyl ether, and 1,4-tetramethylene diisocyanate.
Examples include diaminobenzene and 1,4-diaminobutane. As monomers for obtaining epoxy resin, examples of amines include ethylamine, butylamine, ethylenediamine, 1,4-diaminobenzene, 1,4-diaminobutane, monoethanolamine, etc., and examples of diepoxies include Examples include glycidyl ether, ethylene glycol diglycidyl ether, bisphenol-A-diglycidyl ether, and hydroquinone diglycidyl ether. 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 60-120°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. Polymerization is carried out using a water-soluble polymerization initiator in the presence of a surfactant such as sodium dodecylbenzene sulfonate, an alkyl sulfate type anion emulsifier, or sodium dodecyl sulfonate, at a normal temperature of 40 to 90°C under a nitrogen stream. A polymer is obtained by emulsion polymerization using a method. In the above polymerization method, it is desirable to polymerize the polymerizable monomers so that the weight average molecular weight is 50,000 to 200,000. When the polymer in the present invention is a condensation polymer or an addition polymer, a general dibasic acid and a glycol are heated to 100 to 180°C in the presence of a strong acid (e.g. sulfuric acid, p-toluenesulfonic acid, etc.) or Polyester resin can be made by a method of synthesis by heating reaction 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. Furthermore, a 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 and reacting 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 used in the present invention is a ring-opening polymer, an epoxy resin can be produced 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 are particularly effective as toner resins because they have a softening point of 100 to 170°C using a Koka flow tester (manufactured by Shimadzu Corporation), and a glass transition point of approximately 40 to 110°C. things are valid. In other words, if the softening point is less than 100°C, over-fractionation or toner filming phenomenon may occur, which may easily cause contamination of the photoconductive photosensitive plate.
If the temperature exceeds 170°C, the toner will be hard and difficult to crush, and a large amount of heat will be required during fixing, resulting in poor fixing efficiency. On the other hand, the glass transition point is 40
If the temperature is below ℃, the storage condition for toner is usually 40℃.
If the glass transition temperature exceeds 110℃, it is likely that lumps will occur due to the cold flow phenomenon, and in the case of a roller fixing method, even if the material of the fixing roller is metal, for example, Teflon. (manufactured by Dupont), etc., the roller tends to wear out and start to decompose when the temperature of the fixing roller exceeds 250℃, and there is a restriction that the temperature cannot be raised too much due to the limit of heat resistance based on the roller material, so especially at high speed fixing When doing so, sufficient fixing is not achieved. The polymer obtained as described above can be used as a fine particulate toner that can be put to practical use as it is, or it can be crushed using a crusher and then classified using a zigzag classifier to produce toner. The toner may be produced by mixing the polymer with a coloring agent, etc., grinding the mixture using a grinder, cooling it, and pulverizing it. The polymer 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),
A crosslinking agent may be present during polymerization of the monomers.
Any known crosslinking agent can be used as long as it crosslinks and polymerizes the monomers 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-butylamino ethyl 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, polyoxypropylenated 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, tilephthalic 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 is too small, it is difficult to impart toner properties such as durability, storage stability, and abrasion resistance. Become. In the present invention, a polymer is obtained by polymerizing a polymerizable monomer in the presence of the substance 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), orthochlorobendoyl peroxide,
Orthomethoxybenzoyl peroxide is mentioned. In the present invention, the polymer obtained by the above-described method is used as a toner. At that time, in order to improve the properties as a toner, the above-described colorant, release agent, fluidizing agent, magnetic material, Other binder resins and the like may be added as toner property improvers.
Furthermore, 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. When the toner of the present invention is used as a two-component developer, a carrier is mixed with a toner obtained by a method similar to the above method without adding a magnetic material. As the carrier, a conductive carrier such as iron powder or an insulating carrier in which core particles made of a ferromagnetic material such as iron, nickel, or ferrite are coated with a resin is used. 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;
Also used is a photoreceptor in which a photosensitive layer containing an organic photoconductive material such as anthracene, polyvinylcarbazole, bisazo, trisazo, hydrazone, etc. 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, for example, by a cascade method or a magnetic brush method, with a developer consisting of a mixture of the toner of the present invention and a carrier such as glass beads or iron powder 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. In the transfer, it is also possible to employ a pressure transfer method using an intermediate transfer body. [Example] The present invention will be illustrated below with reference to Examples. 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), Viscol 550P (low molecular weight polypropylene: Sanyo Chemical Industries) ) and 3 parts of triphenyl bismuth were thoroughly melted and kneaded in a kneader, cooled, coarsely pulverized in a hammer mill, finely pulverized in a jet mill, and classified with an average particle size of 15 μm in a classifier to obtain toner. I got it. Using a developer consisting of 2 parts of this toner and 100 parts of iron powder carrier, an image was formed using Ubix 3000 (manufactured by Konishiroku Photo Industries). Example 2 A developer was prepared and an image was formed in the same manner as in Example-1 except that the amount of triphenyl bismuth as a charge control agent was changed to 5 parts. Example 3 A developer was prepared in the same manner as in Example 1, except that triphenyl phosphate was used instead of the charge control agent triphenyl bismuth in Example 1, and image formation was performed. . Example 4 A developer was prepared in the same manner as in Example-1, except that triphenylphosphine oxide was used instead of the charge control agent triphenyl bismuth in Example-1, and image formation was performed. . Example 5 85 parts of styrene, 15 parts of n-butyl acrylate,
0.4 parts of ethylene glycol dimethacrylate, 10 parts of Mitsubishi Carbon Black #30 (manufactured by Mitsubishi Chemical Industries),
A polymer composition was prepared by mixing and dispersing 4 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 triphenyl bismuth. Place this in a stainless steel beaker with a capacity of 3
In addition to a colloidal solution of wt% calcium phosphate and 0.04 wt% sodium dodecylbenzenesulfonate, a TK homogiator (manufactured by Tokushu Kika Kogyo) was added.
The mixture was stirred at a stirring speed of 9000 rpm. The particle size range of the dispersed particles after stirring for 30 minutes was 10-15μ. 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 completion of polymerization, treat with dilute hydrochloric acid, separate the solids, wash with water and dry to obtain an average particle size of 12 μm.
A toner of the present invention was obtained. Two parts of this toner were mixed with 100 parts of iron powder carrier to form a two-component developer.
Using this two-component developer, an image was formed in the same manner as in Example-1. In the present invention, when a toner is produced by direct polymerization, a charge control agent having a substituent that adversely affects the polymerization process is not preferred. For example, carboxylic acid groups, sulfonic acid groups, trimethylamine cation groups, etc. are not preferred for toner production by suspension polymerization. Example 6 A developer was prepared in the same manner as in Example 5, except that tris(p-chlorophenyl) bismuth was used instead of the charge control agent triphenyl bismuth in Example 5, and image formation was performed. I did it. Example 7 Image formation was carried out in the same manner as in Example 5, except that tris(p-bromphenyl)phosphine oxide was used instead of the charge control agent triphenyl bismuth. Comparative Example-1 Example-1 except that triphenyl bismuth, which is a charge control agent, is not added.
A developer was prepared in the same manner as above, and an image was formed. Comparative Example 2 Styrene-butyl acrylate (composition ratio 85:
15, softening point 125℃) copolymer 100 parts, Varifast Black-3804 (manufactured by Orient Chemical Co., Ltd.) 2 parts, Mitsubishi Carbon Black #30/10 parts, Viscoel
A developer was prepared in the same manner as in Example 1 except that 6 parts of 550P was used, and an image was formed. The images obtained in the above examples and comparative examples were free from fog in Examples 1 to 7, were clear, had a high degree of blackening, and had good fixing properties such as prevention of offset. On the other hand, in Comparative Examples-1 and 2, the initial
Around the 1000th copy, the triboelectricity of the toner decreased, and a decrease in copy density and fogging began to occur. Next, Examples-1 to Example-7 and Comparative Example-1,
The toner in each developer was triboelectrically charged by stirring each of the two developers 100 times in the developing device of a Ubix 3000 copying machine, and the amount of charge on this toner was measured by the blow-off method. Table 1 shows the results of a comparison of the amount of charge and image quality.

〔Effect of the invention〕

As is clear from the above embodiments, according to the present invention, the first to fourth objects of the present invention can be achieved.

Claims (1)

[Scope of Claims] 1. A toner for developing electrostatic images, characterized in that a binder resin contains a substance represented by the following general formula [] as a charge control agent. General formula [] [Wherein, X, Y and Z are hydrogen atoms, _halogen atoms, -NO2 group, N( _CH3 ) ₃₊ ^, -CN group, -COOH group,
It represents a _-SO3H group, a -CHO group, or a -COOR group (R represents an alkyl group, an alkenyl group, an allyl group, an aralkyl group, etc.), and each may be the same or different. M represents Bi, P or Sb, m and n are integers of 1, and p, q and r are integers of 0 to 3. ] 2. A method for producing a toner for developing an electrostatic image, comprising the step of polymerizing a polymerizable monomer in the presence of a substance represented by the general formula [].