JPH086297A - Toner for developing electrostatic charge image and electrophotographic developer using the same - Google Patents

Abstract

PURPOSE:To obtain a toner having stable triboelectric chargeability, ensuring easy control of the extent of triboelectric charge and excellent in environmental stability by incorporating a specified iron-contg. azo dyestuff as an electric charge controlling agent in a toner based on a resin binder, a colorant and the electric charge controlling agent. CONSTITUTION:This toner is based on a resin binder, a colorant and an electric charge controlling agent and contains an iron-contg. azo dyestuff represented by the formula as the electric charge controlling agent. The resin binder is polyester resin, epoxy resin or polyol resin obtd. by modifying epoxy resin. The iron-contg. azo dyestuff is highly hydrophobic, has satisfactory triboelectric charge controlling property and ensures a very slight change of the extent of triboelectric charge due to environment. The azo dyestuff is a sec. to quat. ammonium salt. Polystyrene, poly-p-chlorostyrene or a mixture of them may be used as the resin binder. Carbon black, lamp black or a mixture of them may be used as the colorant.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrostatic charge image developing toner used in electrophotography, electrostatic printing, and the like, and a two-component electrophotographic developer using the toner, and more particularly to negative charging. The present invention relates to a toner developer for sexual development.

[0002]

2. Description of the Related Art Conventionally, as disclosed in Japanese Patent Application Laid-Open No. 61-147261, methods for developing an electrostatic charge image by using toner are roughly classified into so-called two methods in which toner and carrier are mixed. There are a method of using a component type developer and a method of using a one component type developer which is used alone as a toner without being mixed with a carrier. In the former two-component developing method, the toner and the carrier are stirred and rubbed to charge each of them to different polarities, and an electrostatic charge image having an opposite polarity is visualized by the charged toner.
Depending on the types of toner and carrier, there are a magnet brush method using an iron powder carrier, a cascade method using a bead carrier, a fur brush method, and the like. The latter one-component developing method includes a powder cloud method in which toner particles are sprayed and used, a contact developing method in which toner particles are directly brought into contact with an electrostatic latent image surface to develop (also referred to as touchdown development), There is an induction developing method in which a magnetic conductive toner is brought into contact with the electrostatic latent image surface.

As the toner applied to these various developing methods, fine powder in which a colorant such as carbon black is dispersed in a binder resin made of natural resin or synthetic resin is used. For example, particles in which a colorant is dispersed in a binder resin such as polystyrene and finely pulverized to about 1 to 30 μm are used as toners. Further, a magnetic toner such as those containing a magnetic material such as magnetite is used as a magnetic toner.

As described above, the toner used in various developing methods has a positive or negative charge depending on the polarity of the electrostatic charge image to be developed. To make the toner have a charge, It is possible to utilize the triboelectric charging property of the resin which is a component of the toner, but since the toner has a low charging property in this method, the image obtained by development is apt to be fogged and unclear. Therefore, in order to impart a desired triboelectric chargeability to the toner, a dye, a pigment or a charge control agent which imparts the chargeability is added.

Conventionally, as negative charge control agents, metal complex salts of monoazo dyes, nitrohumic acid and its salts, salicylic acid, naphthoic acid, dicarboxylic acids such as Fe, Co and N.
There are metal complexes of i, Cr, Zn, etc., sulfonated copper phthalocyanine pigments, nitro groups, halogen-incorporated styrene oligomers, chlorinated paraffins, melamine resins, etc., but these dyes have complicated structures and constant properties. No, the stability is poor. Further, during thermal kneading, decomposition or mechanical shock, friction, changes in temperature and humidity conditions, and the like are likely to cause decomposition or deterioration, and a phenomenon in which charge controllability is deteriorated is likely to occur. Also, in many cases, the chargeability changes depending on the environment. Furthermore, when a conventional toner containing the charge control agent is used for a long time, filming may occur on the photoreceptor due to poor charging. Furthermore, these metal complexes include Co, Ni and C.
It contains heavy metals such as r, Zn, and Cu, which may cause environmental problems, and is not preferable for safety reasons. Also,
Japanese Unexamined Patent Publication (Kokai) No. 61-155464 proposes to use such an iron-containing azo dye containing no harmful metal as a charge control agent, but has a problem that the charge amount is lowered under high humidity. Have

Recently, a polyester resin or an epoxy resin has been often used as a binder resin because of its advantages such as vinyl chloride mat fusion resistance, storage stability and low temperature fixability. However, if a polyester resin or epoxy resin is used as a binder resin in a toner and is used in combination with a conventional charge control agent, the charge amount is low in either case, or even if it is high, the charge amount decreases with repeated use. However, there is a problem that it is difficult to use because of fog and toner scattering. It is considered that this is because functional groups such as —COOH group and —OH group remain in the polyester resin and the epoxy resin due to their chemical structures, which hinders maintaining stable chargeability.

Conventionally, as a mechanism of a two-component dry developer, fine toner particles are formed on the surface of relatively large particles.
It is held by the electric force generated by the friction of both particles, and when the electrostatic latent image is approached, the attraction force in the latent image direction to the toner particles by the electric field formed by the electrostatic latent image is generated between the toner particles and the carrier particles. It has been proposed that the toner particles are attracted and adhered onto the electrostatic latent image to make the electrostatic latent image visible by overcoming the binding force of. Since the developer is repeatedly used while replenishing the toner consumed by the development, the carrier must always frictionally charge the toner particles to a desired polarity and a sufficient charge amount during long-term use. . However, in the conventional developer, a toner film is formed on the carrier surface due to a collision between particles, a mechanical collision such as a collision between a particle and a developing machine, or heat generated by these effects, so-called spent formation occurs, and a carrier is generated. The charging characteristics of No. 1 deteriorate with the use time, and it becomes necessary to replace the entire developer.

In order to prevent such spent formation,
Conventionally, a method of coating various resins on the surface of a carrier has been proposed, but a satisfactory method has not been obtained yet. For example, a carrier coated with a resin such as a styrene-methacrylate copolymer or a styrene polymer has excellent charging characteristics, but has a relatively high critical surface tension on the surface, and therefore, after repeated copying, a spent state may occur. The life as a developer was not so long.

On the other hand, a carrier coated with a silicone resin having a low surface tension has been proposed. However, since the silicone resin has a weak mechanical strength, strong stirring such as in a high-speed copying machine or inside a developing portion is required. By stirring for a long time at
When the carrier particles collide with the inner wall of the developing unit or the surface of the photoconductor, or when the particles collide with each other, the silicone resin coating layer is worn or peeled off with time, and frictional electrification is caused by the electrification between the toner and the silicone resin. Since the charge between the carrier core particles changes, the charge amount of the developer cannot be kept constant, and there is a problem that the image quality deteriorates. Further, when the carrier particles are coated with a silicone resin, the silicone resin itself has a high electric resistance, so that when it is used as a developer, the image quality is deteriorated due to an edge phenomenon and a charge accumulation phenomenon.

The drawbacks of such a coated carrier can be ameliorated by dispersing a conductive substance in the coating layer. That is, when the carrier is given a certain degree of conductivity, the carrier acts as a developing electrode, and the development is carried out in a state where the developing electrode and the surface of the photoconductor to be developed are in close contact with each other. Even a large area of black area is faithfully reproduced as the original.

Conventionally, carbon, tin oxide, etc. have been used as such a conductive material, but when such a conductive material is dispersed in the coating layer of the carrier, the following drawbacks occur. Generally, the toner and the carrier are charged when they contact each other. In this case, when the electric resistance of the carrier becomes small, the charge generated in the toner is attenuated through the carrier, and the charge amount cannot be maintained. Further, there is a problem that the conductive material is separated from the coating layer due to use over time and the charge amount changes. In order to solve this problem, Japanese Patent Laid-Open No. 182759/1987 improves the treatment by treating carbon with aminosilane, amino-modified silicone oil or the like, but the cost increases due to an increase in treatment steps. Met.

[0012]

DISCLOSURE OF THE INVENTION The present invention has stable triboelectrification properties, particularly triboelectrification property of negative polarity, easy control of the amount of electrification, excellent environmental stability, and excellent initial stability even after continuous use. To provide an electrostatic charge image developing toner capable of obtaining an image similar to an image, and an electrophotographic developer using the toner, which is free from deterioration of image quality due to an edge phenomenon or a charge accumulation phenomenon and has excellent durability. With the goal.

[0013]

As a result of intensive studies, the inventors of the present invention have found that an electrostatic charge image in which the above-mentioned conventional drawbacks have been improved by using a specific charge control agent in the toner for developing an electrostatic charge image. The inventors have found that a developing toner can be obtained, and completed the present invention. According to the present invention,
An electrostatic charge comprising an iron-containing azo dye represented by the following general formula (I) as a charge control agent in a toner for developing an electrostatic charge image containing a binder resin, a colorant and a charge control agent as main components. An image developing toner is provided.

Embedded image In particular, there is provided the electrostatic image developing toner, wherein the binder resin is a polyester resin, an epoxy resin, or a polyol resin obtained by modifying an epoxy resin. Further, according to the present invention, in a two-component type electrophotographic developer comprising a carrier, the carrier has a silicone resin coating layer containing conductive fine powder and a silane coupling agent. An electrophotographic developer is provided.

In the iron-containing azo dye of the present invention, the charge control agent itself is very hydrophobic, the triboelectrification controllability is good, and the triboelectrification amount changes very little in the environment. The iron-containing azo dye of the present invention can be synthesized, for example, by subjecting the corresponding sodium salt to salt formation with a secondary amine or a tertiary amine, or by counterion exchange with a quaternary ammonium salt. As described above, the iron-containing azo dye of the present invention is characterized in that it is a secondary to quaternary ammonium salt, and in the case of a primary ammonium salt, the object of the present invention cannot be sufficiently exhibited. Typical examples of the compound represented by the general formula (I) of the present invention include the compounds shown in Table 1 below, but the invention is not limited thereto.

[0015]

[Table 1]

In the present invention, the amount of the charge control agent used is determined by the type of binder resin, the presence or absence of additives used as necessary, and the toner production method including the dispersion method, and is uniquely limited. Although not included, it is used in an amount of 0.1 to 10 parts by weight, preferably 2 to 5 parts by weight, based on 100 parts by weight of the binder resin. When the amount is less than 0.1 parts by weight, the negative charging of the toner is insufficient, which is not practical. When the amount is more than 10 parts by weight, the chargeability of the toner is too large, and electrostatic attraction with the carrier is increased, so that development is performed. This leads to a decrease in fluidity of the agent and a decrease in image density. The charge control agent represented by the general formula (I) may be used in combination with another charge control agent, if necessary.

These compounds of the present invention may be polyester resins, epoxy resins or polyol resins obtained by modifying epoxy resins, which are binder resins having good vinyl chloride matting resistance, storage stability and low temperature fixability. It has excellent charging characteristics and is optimal as a negative charge control agent for low temperature fixing toner.

Examples of the binder resin used in the present invention include polymers of styrene such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene and their substitution products; styrene-p-chlorostyrene copolymer, styrene-propylene copolymer. Coalesce, styrene-vinyltoluene copolymer,
Styrene-vinyl naphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer Polymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene -Styrene-based copolymers such as butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer; polymethylmethacrylate, Polybutyl methacrylate Polyvinyl chloride, polyvinyl acetate,
Polyethylene, polypropylene, polyester, polyurethane, polyamide, epoxy resin, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, Paraffin wax and the like can be used, and they can be used alone or in combination.

In particular, the polyester resin used in the present invention is obtained by polycondensation of a polyhydric alcohol and a polycarboxylic acid. For example, the polyhydric alcohol may be polyethylene glycol, diethylene glycol or triethylene. Diols such as glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-propylene glycol, neopentyl glycol and 1,4-butenediol, 1,4-bis (hydroxymethyl)
Etherified bisphenols such as cyclohexane, bisphenol A, hydrogenated bisphenol A, polyoxyethylenated bisphenol A, polyoxypropyleneized bisphenol A, and the like, which are substituted with a saturated or unsaturated hydrocarbon group having 3 to 22 carbon atoms. Monohydric alcohol monomers, other dihydric alcohol monomers, sorbitol, 1,2,3,6-hexanetetrol, 1,4-salbitan, pentaesthritol, dipentaesthritol, tripenta Erythritol, sucrose, 1,2,4-butanetriol, 1,2,
5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-
Examples include trihydric or higher polyhydric alcohol monomers such as trihydroxymethylbenzene.

Examples of the polycarboxylic acid used to obtain the polyester resin include maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid,
Cyclohexanedicarboxylic acid, succinic acid, adipic acid,
Sebacic acid, malonic acid, divalent carboxylic acid monomers in which they are substituted with saturated or unsaturated hydrocarbon groups having 3 to 22 carbon atoms, anhydrides of these acids, lower alkyl esters, and dimer of linoleic acid Body, other divalent carboxylic acid monomers, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 2,5,7-naphthalene Tricarboxylic acid, 1,2,4-naphthalene tricarboxylic acid, 1,2,4-butane tricarboxylic acid, 1,2,
5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, tetra (methylenecarboxylic) methane, 1,2,7,8-octanetetracarboxylic acid, embol trimer acid, these Examples thereof include trivalent or higher polyvalent carboxylic acid monomers such as acid anhydrides. Further, a monovalent carboxylic acid such as palmitic acid, stearic acid and oleic acid may be used in combination.

Further, the epoxy resin used in the present invention is a polycondensation product of bisphenol A and epichlorohydrin, for example, Epomic R362, R3.
64, R365, R366, R367, R369, (Mitsui Petrochemical Industry Co., Ltd.
Made), Epotote YD-011, YD-012, YD-014, YD-904, YD-01
Commercially available products such as 7, (manufactured by Toto Kasei Co., Ltd.) and Epicoat 1002, 1004, 1007 (manufactured by Shell Chemical Co., Ltd.) can be mentioned.

Further, as the polyol resin obtained by modifying the epoxy resin used in the present invention, a compound having one active hydrogen such as monovalent phenol or secondary amine at the terminal glycidyl group of these epoxy resins is used. It was made to react. By reacting the terminal glycidyl group in advance, it is possible to prevent the reaction between other materials and the terminal glycidyl group during kneading, and to avoid biochemical problems such as sensitization.

As the compound having one active hydrogen for producing the polyol resin, there are monovalent phenol and secondary amine, and as the monovalent phenol, phenol, cresol, isopropylphenol, aminophenol, nonylphenol, p- Examples include cumylphenol, and secondary amines include diethylamine, dibutylamine, ethyleneimine, piperidine, piperazine and the like. Since the present invention aims to supply a negatively chargeable toner, a monohydric phenol is preferable.

As the binder resin suitable for pressure fixing, the following resins may be used alone or in combination. Polyolefin (low molecular weight polyethylene, low molecular weight polypropylene, polyethylene oxide, polytetrafluoroethylene, etc.), epoxy resin, polyester resin, styrene-butadiene copolymer (monomer ratio 5 to 30:95 to 7)
0), olefin copolymer (ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-vinyl chloride copolymer, Ethylene-vinyl acetate copolymer, ionomer resin), polyvinylpyrrolidone resin and the like.

Examples of the colorant used in the present invention include carbon black, lamp black, iron black, ultramarine blue, nigrosine dye, aniline blue, phthalocyanine blue, phthalocyanine green, hansa yellow G and rhodamine 6.
G, lake, chalco oil blue, chrome yellow, quinacridone, benzidine yellow, rose bengal, triallylmethane dyes, monoazo dyes, disazo dyes, dyes and pigments can be used alone or in combination. obtain.

Further, the toner of the present invention can be used as a magnetic toner by further containing a magnetic material. As the magnetic material contained in the magnetic toner of the present invention, magnetite,
Iron oxides such as hematite and ferrite, metals such as iron, cobalt and nickel or aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium and titanium of these metals. , Alloys of metals such as tungsten, vanadium, and mixtures thereof. These ferromagnetic materials have an average particle size of 0.1 to 2 μm.
It is desirable that the amount is about 20 to 200 parts by weight based on 100 parts by weight of the resin component.
Particularly preferably, it is 40 to 15 with respect to 100 parts by weight of the resin component.
0 parts by weight.

Further, the toner of the present invention may be mixed with additives as required. Examples of the additives include lubricants such as Teflon and zinc stearate, abrasives such as cerium oxide and silicon carbide, fluidity imparting agents such as colloidal silica and aluminum oxide, anti-caking agents, or carbon black, tin oxide. And the like, or a fixing aid such as a low molecular weight polyolefin.

When the toner of the present invention is used as a two-component developer, it is used as a mixture with carrier powder. As the carrier that can be used in the present invention, all known carriers can be used, for example, iron powder, ferrite powder, magnetic powder such as nickel powder, glass beads, etc., and their surfaces treated with a resin or the like. The thing etc. are mentioned.

In the present invention, by coating the surface of the core particles with the silicone resin containing the conductive fine powder and the silane coupling agent, the advantages of the conventional silicone resin-coated carrier are maintained, By imparting conductivity to the carrier, the phenomenon of charge accumulation in the carrier, the peeling of the coating layer, and the detachment of the conductive fine powder can be effectively suppressed. Particularly, an aminosilane coupling agent having a primary and / or secondary amino group is preferable from the viewpoint of negative charge controllability of the toner.

The carrier core particles coated with a silicone resin in the present invention may be conventionally known ones, for example, ferromagnetic metals such as iron, cobalt and nickel; alloys and compounds such as magnetite, hematite and ferrite;
Examples thereof include glass beads. The average particle diameter of these core particles is usually 10 to 1000 μm, preferably 30 to 500.
μm. The amount of silicone resin used is
Usually, it is 1 to 10% by weight based on the carrier core particles.

The silicone resin used in the present invention may be any conventionally known silicone resin, for example, commercially available KR261, KR271, KR272, KR275, manufactured by Shin-Etsu Silicone Co., Ltd.
KR280, KR282, KR285, KR251, K
R155, KR220, KR201, KR204, KR
205, KR206, SA-4, ES1001, ES1
001N, ES1002T, KR3093 or Toray Dow Corning Silicone SR2100, SR210
1, SR2107, SR2110, SR2108, SR
2109, SR2115, SR2400, SR241
0, SR2411, SH805, SH806A, SH8
40 or the like is used.

The conductive fine powder dispersed in the coating layer may be conventionally known carbon black, such as conductive black, furnace black and thermal black. The conductive fine powder is 0.01 to 5.0 μm.
A silicone resin having a particle size of about m is preferable.
It is preferably added in an amount of 0.01 to 30 parts by weight, more preferably 0.1 to 20 parts by weight, based on parts by weight.

Examples of the silane coupling agent include ""
X—Si (OR) 3 ″ is a compound represented by the formula:
Here, X is a functional group that reacts with an organic substance, and R is a hydrolyzable group. In the present invention, in order to impart a stable negative charge to the toner, an aminosilane coupling agent having an amino group is desirable, and examples of the aminosilane coupling agent include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl)
Aminopropylmethyldimethoxysilane, γ-anilinopropyltrimethoxysilane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride and the like can be mentioned. The silane coupling agent is
0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight is added to 100 parts by weight of the silicone resin.

The coating layer-forming silicone resin composition is prepared by adding conductive fine powder and a silane coupling agent to a silicone resin solution and dispersing them with an appropriate mixer.
As a method for forming the silicone resin layer, the silicone resin composition may be applied to the surface of the carrier core particles by a method such as a spraying method or a dipping method as in the conventional method.

A developing method using the developer of the present invention will be described with reference to FIG. In the developing device shown in FIG. 1, the toner 6 contained in the toner tank 7 is forced to the sponge roller 4 by the stirring blade 5, and the toner is supplied to the sponge roller 4. And sponge roller 4
When the sponge roller rotates in the direction of the arrow, the toner taken in by the toner is conveyed to the toner conveying member 2 and is rubbed and electrostatically or physically adsorbed to the toner conveying member 2.
Rotates strongly in the direction of the arrow, a uniform thin toner layer is formed by the elastic blade 3, and the toner is triboelectrically charged. After that, the toner is conveyed to the surface of the electrostatic latent image carrier 1 which is in contact with or in the vicinity of the toner conveying member 2, and the latent image is developed.

[0036]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited thereto. All parts are parts by weight.

Example of Synthesis of Charge Control Agent By subjecting the compound (II) represented by the following structural formula to a salt formation treatment with diethylamine, the exemplified compound (1) in Table 1 was obtained. In addition, an exemplary compound (7) in Table 1 was obtained by performing a counterion exchange reaction using tetramethylammonium chloride and compound (II).

Embedded image

Production Example of Carrier The production example of a carrier having a silicone resin in the coating layer is shown below. These can be performed by known means. Carrier Production Example 1 <Composition of coating layer forming liquid> Silicone resin (KR206 Shin-Etsu Silicone) 100 parts by weight Carbon black (# 44 Mitsubishi Kasei Co., Ltd.) 3 parts by weight A mixture of the above composition is dispersed for 30 minutes with a homomixer to form a coating layer. A liquid was prepared. This coating layer forming liquid has an average particle size of 1
A coating layer was formed on the surface of 1000 parts by weight of spherical ferrite having a diameter of 00 μm by using a fluidized bed type coating device to obtain a carrier A.

Carrier Production Examples 2 to 5 The following components were mixed with 100 parts of toluene and dispersed for 30 minutes with a homomixer to prepare a coating layer forming liquid. Carrier Production Example 2 Silicone Resin (SR2400 Toray Dow Corning Silicone) 100 parts Tin Oxide (S-1 Mitsubishi Metals) 2 parts Carrier Production Example 3 Silicone Resin (SR2400 Toray Dow Corning Silicone) 100 parts Carbon Black (Ketjen Black Lion Lion Akzo) 1.5 parts γ-anilinopropyltrimethoxysilane 0.3 parts (SZ6083 Toray Dow Corning Silicone) Carrier Production Example 4 Silicone resin (KR206 Shin-Etsu Silicone) 100 parts Carbon Black (# 3600 Mitsubishi Kasei) 1 part γ- ( 2-Aminoethyl) aminopropyltrimethoxysilane 0.1 part (SH6020 Toray Dow Corning Silicone) Carrier Production Example 5 Silicone resin (KR206 Shin-Etsu Silicone) 100 parts Carbon black (# 44 Mitsubishi Kasei Co., Ltd.) 1.5 parts γ- (2-aminoethyl) aminopropylmethyldimethoxysilane (SH6020 Toray Dow Corning Silicone) 0.4 parts This coating layer forming liquid is used to form spherical ferrite having an average particle diameter of 70 μm and 1000 parts by weight. Carriers B, C, D, and E having a coating layer formed on the surface of each part using a fluidized bed coating apparatus were obtained.

Production Example of Binder Resin The production example of the binder resin will be described below. Polyol resin synthesis example 1 Bisphenol A type epoxy resin (Mn; about 3500) 94 parts p-cresol 6 parts Xylene 20 parts The above raw materials were put in a separable flask and heated to 90 ° C. Furthermore, 0.015 parts of lithium chloride was added to give 170
The reaction was carried out for 10 hours while distilling off xylene at ℃. The obtained solid was dissolved in MEK, reprecipitated in hexane and purified to obtain a polyol resin A.

Polyol resin synthesis example 2 Bisphenol A type epoxy resin (Mn; about 3200) 88 parts p-cumylphenol 12 parts xylene 20 parts The above raw materials were placed in a separable flask and heated to 90 ° C. Furthermore, 0.015 parts of lithium chloride was added to give 170
The reaction was carried out for 10 hours while distilling off xylene at ℃. The obtained solid was dissolved in MEK, reprecipitated in hexane and purified to obtain a polyol resin B.

Example 1 Styrene-2-ethylhexyl acrylate copolymer 100 parts Carbon black 8 parts Exemplified compound (1) 3.5 parts The mixture having the above composition was sufficiently stirred and mixed in a Henschel mixer, and then 130 to 140 with a roll mill. About 3 at a temperature of ℃
After heating and melting for 0 minutes and cooling to room temperature, the obtained kneaded product was pulverized and classified to obtain a toner having a particle diameter of 5 to 20 μm. 2.5 parts of this toner was mixed with 97.5 parts of 100-250 mesh iron powder carrier in a ball mill to obtain a developer. Next, the above developer was set in FT7570 manufactured by our company, and development was performed. As a result, a good image was obtained, and the image did not change even after printing 80,000 sheets. When the toner charge amount was measured by the blow-off method, the initial charge amount was -19.2 μC / g, and the toner charge amount after running 80,000 sheets was -16.7 μC / g, which is almost the initial value. There was no difference. Moreover, even in a low humidity environment of 10 ° C. and 15% RH and in a high humidity environment of 35 ° C. and 90% RH,
An image equivalent to normal humidity was obtained. 10 ℃ at the beginning, 1
The charge amount at 5% RH is -20.1 μC / g,
The charge amount at 90 ° C. and 90% RH is -17.8 μC / g,
There was almost no difference. There was also no toner filming on the photoconductor.

Example 2 A toner was prepared in the same manner as in Example 1 except that the carrier A was used.
When a developer was prepared and the same image output test was carried out, a good image was obtained, and the image did not change after 100,000 images were output. When the charge amount of the toner was measured by the blow-off method, the initial charge amount was -20.1 μC /
The charge amount of the toner after running 100,000 sheets was -18.9 μC / g, which was almost the same as the initial value. Also, in a low humidity environment of 10 ° C. and 15% RH, and 3
Even under a high humidity environment of 5 ° C. and 90% RH, an image equivalent to normal humidity was obtained. The charge amount at 10 ° C. and 15% RH in the initial stage is −21.3 μC / g, and 35 ° C. and 90% RH
The amount of charge was -17.8 μC / g, and there was almost no difference. There was also no toner filming on the photoconductor.

Example 3 Epoxy resin (R365 manufactured by Mitsui Petrochemical Co., Ltd.) 80 parts Epoxy resin (YD-017 manufactured by Toto Kasei Co., Ltd.) 20 parts Carbon black 8 parts Exemplified compound (2) 2 parts A raw material mixture having the above composition was used as an example. Melt kneading, as in 1.
After cooling, crushing and classification, a toner having a particle size of 5 to 25 μm was obtained. 2.5 parts of this toner was mixed with 97.5 parts of carrier B coated with a silicone resin in a ball mill,
A developer is obtained. Next, this developer was set in the copier FT7570 manufactured by our company in the same manner as in Example 1, and an image test was carried out. As with Example 1, a good image with high sharpness was obtained. It didn't change even after displaying 10,000 images. When the toner charge amount was measured by the blow-off method, the initial charge amount was −26.0 μC / g, and the toner charge amount after running 120,000 sheets was −23.7 μC.
There was almost no difference between C / g and the initial value. Also 10 ℃, 1
Images equivalent to normal humidity were obtained even in a low humidity environment of 5% RH and a high humidity environment of 35 ° C. and 90% RH. The charge amount at 10 ° C. and 15% RH in the initial stage is −27.3 μ.
C / g, and the charge amount at 35 ° C. and 90% RH is -24.
It was 9 μC / g, and there was almost no difference. There was also no toner filming on the photoconductor.

Example 4 Polyol resin A 100 parts Carbon black 8 parts Exemplified compound (3) 2 parts A raw material mixture having the above composition was melt-kneaded in the same manner as in Example 1,
After cooling, crushing and classification, a toner having a particle size of 5 to 25 μm was obtained. 2.5 parts of this toner was mixed with 97.5 parts of a carrier C coated with a silicone resin in a ball mill,
A developer is obtained. Next, this developer was set in a copier FT7570 manufactured by our company in the same manner as in Example 1, and an image test was carried out. As with Example 1, a good image with high sharpness was obtained. It didn't change even after displaying 10,000 images. When the charge amount of the toner was measured by the blow-off method, the initial charge amount was -21.3 µC / g, and the toner charge amount after running 150,000 sheets was -19.1 µC.
There was almost no difference between C / g and the initial value. Also 10 ℃, 1
Images equivalent to normal humidity were obtained even in a low humidity environment of 5% RH and a high humidity environment of 35 ° C. and 90% RH. The charge amount at 10 ° C. and 15% RH in the initial stage is −22.0 μ
C / g, and the charge amount at 35 ° C. and 90% RH is -19.
It was 0 μC / g, and there was almost no difference. There was also no toner filming on the photoconductor.

Example 5 Polyol resin B 100 parts Carbon black 8 parts Exemplified compound (4) 2 parts The mixture having the above composition was thoroughly stirred and mixed in a Henschel mixer in the same manner as in Example 1, and then 130 to 1 by a roll mill.
After heating and melting at a temperature of 40 ° C. for about 30 minutes and cooling to room temperature, the obtained kneaded product was pulverized and classified to obtain a black toner having a particle size of 5 to 20 μm. To 100 parts of this toner, 3 parts of silicon carbide (particle size: 2 μm) and 0.1 part of hydrophobic colloidal silica were sufficiently stirred and mixed with a speed kneader to obtain a toner. When this toner was loaded into a developing device as shown in FIG. 1, continuous copying was carried out, and an image test was conducted, a good image was obtained. The image did not change after 40,000 images were printed. The electrostatic latent image was formed by exposing the organic photoconductor to a negative DC charge of 800 V and then exposing it to form a latent image, which was then subjected to reversal development. Further, the specific charge amount of the toner on the toner conveying member:
In order to measure Q / M, the toner on the toner conveying member is sucked through a Faraday cage equipped with a filter layer on the outlet side, and the specific charge of the toner trapped in the Faraday cage is measured. With the quantity measuring device,
When Q / M was measured, it was confirmed that sufficient charge of -15.1 μC / g was made. In addition, the amount of charge during running of 40,000 sheets was -12.1 μC / g, which was almost the same as the initial value. Further, even under low and high humidity, image quality equivalent to normal humidity was obtained. Initially 10 ℃, 15% R
The charge amount at H is -16.3 μC / g, at 35 ° C, 90 ° C.
The charge amount at% RH was -14.8 μC / g, which was almost the same. There was also no toner filming on the photoconductor.

Example 6 Polyester resin 100 parts (Luna Pale 1447 manufactured by Arakawa Chemical Co., Ltd.) Polypropylene 5 parts Carbon black 8 parts Exemplified compound (5) 2 parts The raw material mixture having the above composition was melt-kneaded in the same manner as in Example 1.
After cooling, crushing and classification, a black toner having a particle size of 5 to 25 μm was obtained. 2.5 parts of this toner was mixed with 97.5 parts of carrier D coated with a silicone resin in a ball mill to obtain a developer. Next, this developer was set in a copier FT7570 manufactured by our company in the same manner as in Example 1, and an image test was performed. As with Example 1, a good image with high fidelity was obtained, and the image was 15 It didn't change even after displaying 10,000 images. Moreover, when the charge amount of the toner was measured by the blow-off method, the initial charge amount was −22.4 μC / g.
The toner charge amount after running 50,000 sheets was -20.
There was almost no difference from the initial value of 3 μC / g. Again 10
℃, low humidity environment of 15% RH, and 35 ℃, 90%
Even under a high humidity environment of RH, an image equivalent to normal humidity was obtained. The charge amount at 10 ° C and 15% RH in the initial stage is -2
The amount of charge was 3.0 μC / g, and the charge amount at 35 ° C. and 90% RH was −20.5 μC / g, showing almost no difference. There was also no toner filming on the photoconductor.

Example 7 Polyester resin 100 parts (Luna Pale 1447 manufactured by Arakawa Chemical Co., Ltd.) Candelilla wax 102 (manufactured by Noda Wax Co.) 5 parts Carbon black 8 parts FCA-1001N manufactured by Fujikura Kasei 2 parts Exemplified compound (6) 2 parts The raw material mixture having the composition was melt-kneaded in the same manner as in Example 1,
After cooling, crushing and classification, a black toner having a particle size of 5 to 25 μm was obtained. 2.5 parts of this toner was mixed with 97.5 parts of carrier E coated with a silicone resin in a ball mill to obtain a developer. Next, this developer was set in a copier FT7570 manufactured by the same company as in Example 1, and an image test was conducted. As with Example 1, a good image with high fidelity was obtained. It didn't change even after displaying 10,000 images. Moreover, when the charge amount of the toner was measured by the blow-off method, the initial charge amount was -24.3 μC / g.
The toner charge amount after running 70,000 sheets was -22.
There was almost no difference from the initial value of 0 μC / g. Again 10
℃, low humidity environment of 15% RH, and 35 ℃, 90%
Even under a high humidity environment of RH, an image equivalent to normal humidity was obtained. The charge amount at 10 ° C and 15% RH in the initial stage is -2
The amount of charge was 4.4 μC / g, and the amount of charge at 35 ° C. and 90% RH was −1.9 μC / g, showing almost no difference. Also, there was no toner filming on the photoconductor.

Example 8 Polyester resin 100 parts (Luna Pale 1447 manufactured by Arakawa Chemical Co., Ltd.) Candelilla wax 102 (manufactured by Noda Wax Co., Ltd.) 5 parts Carbon black 8 parts Exemplified compound (7) 2 parts A raw material mixture having the above composition was used in Example 1 Similarly, melt kneading,
After cooling, crushing and classification, a black toner having a particle size of 5 to 25 μm was obtained. 2.5 parts of this toner was mixed with 97.5 parts of carrier E coated with a silicone resin in a ball mill to obtain a developer. Next, this developer was set in a copier FT7570 manufactured by the same company as in Example 1, and an image test was conducted. As with Example 1, a good image with high fidelity was obtained. It didn't change even after displaying 10,000 images. Further, when the charge amount of the toner was measured by the blow-off method, the initial charge amount was −24.4 μC / g.
The toner charge amount after running 70,000 sheets was -22.
There was almost no difference from the initial value of 1 μC / g. Again 10
℃, low humidity environment of 15% RH, and 35 ℃, 90%
Even under a high humidity environment of RH, an image equivalent to normal humidity was obtained. The charge amount at 10 ° C and 15% RH in the initial stage is -2
It was 4.5 μC / g, and the charge amount at 35 ° C. and 90% RH was −23.0 μC / g, which was almost the same. Also, there was no toner filming on the photoconductor.

Comparative Example 1 Instead of the exemplified compound (1) of Example 1, a compound in which the counter ion of the compound was changed to NH ₃ (C ₂ H ₅ ) + was used, and toner was prepared in the same manner as in Example 1. To prepare a developer. Further, when an image test was conducted by the same procedure, thin background stain was observed especially under high temperature and high humidity. When the charge amount was measured in the same manner as in Example 1, it was 10 ° C. and 15% R at the initial stage.
The charge amount at H is -19.1 μC / g, at 35 ° C, 90
The charge amount at% RH was -14.1 μC / g, and the charge amount was significantly reduced under high temperature and high humidity.

Comparative Example 2 Developer in the same manner as in Example 3 except that instead of the exemplified compound (2) in Example 3, a compound in which the counter ion of the compound was changed to NH ₃ (C ₄ H ₉ ) + was used. And an image test was performed. The charge amount at 10 ° C. and 15% RH in the initial stage is −
The charge amount was 21.3 μC / g, the charge amount at 35 ° C. and 90% RH was −10.2 μC / g, and the charge amount was low under high temperature and high humidity.

Comparative Example 3 A developer was obtained in the same manner as in Example 7 except that a compound in which the counter ion of the compound was changed to NH ₃ (CH ₃ ) + was used instead of the exemplified compound (6) in Example 7. , An image test was conducted. The charge amount at 10 ° C. and 15% RH in the initial stage is −
The charge amount was 20.3 μC / g, the charge amount at 35 ° C. and 90% RH was −14.0 μC / g, and the charge amount was low under high temperature and high humidity.

[0053]

The toner for developing an electrostatic charge image of the present invention contains a specific iron-containing azo dye as a charge control agent.
Friction electrification between toner particles or between toner and carrier, toner in case of one-component developer and electrifying member such as developing sleeve or blade, especially stable triboelectrification of negative polarity and triboelectrification The quantity distribution is sharp and uniform, the charge rising property and environmental stability are good, the charge amount can be controlled to be suitable for the developing system to be used, and an image similar to the initial image can be obtained even during continuous use. In addition, the charge control agent is particularly hydrophobic, and the change in the toner charge amount due to the environment is extremely small. Further, even if a polyester resin or an epoxy resin having excellent vinyl chloride mat fusion resistance, storage stability and low-temperature fixability is used as a binder resin, environmental stability is good, and the charge amount can be controlled to be suitable for the developing system used. . Further, by using the toner and providing a carrier with a silicone resin coating layer containing conductive fine powder and a silane coupling agent, there is no background stain or toner scattering, and the image quality is improved by the edge phenomenon and the charge accumulation phenomenon. Of two-component electrophotography that does not deteriorate, and that the carrier coating layer does not peel off or the conductive fine powder does not separate even during continuous use, so triboelectric charging is stable and an image with high fidelity equivalent to the initial image can be obtained. It can be used as a developer.

[Brief description of drawings]

FIG. 1 is a schematic view of an electrostatic image developing device.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Electrostatic latent image carrier 2 ... Toner conveying part agent 3 ... Elastic blade 4 ... Sponge roller 5 ... Stirring blade 6 ... Toner 7 ... Toner tank

Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical indication location G03G 9/08 333 9/10 352 361 (72) Inventor Kunihiko Tomita 1-3-6 Nakamagome, Ota-ku, Tokyo No. Within Ricoh Co., Ltd. (72) Inventor Hitoshi Ueda 1-3-6 Nakamagome, Ota-ku, Tokyo Within Ricoh Co., Ltd.

Claims (3)

[Claims] 1. A toner for developing an electrostatic charge image containing a binder resin, a colorant and a charge control agent as main components, wherein an iron-containing azo dye represented by the following general formula (I) is contained as a charge control agent. And a toner for developing an electrostatic image. Embedded image 2. The electrostatic image developing toner according to claim 1, wherein the binder resin is a polyester resin, an epoxy resin, or a polyol resin obtained by modifying an epoxy resin. 3. A two-component electrophotographic developer comprising the electrostatic charge image developing toner according to claim 1 and a carrier, wherein the carrier is a conductive fine powder and a silane coupling agent. A developer for electrophotography, which has a silicone resin coating layer containing.