JP4970733B2 - Toner for electrostatic image development - Google Patents

Description

  The present invention relates to a monoazo iron compound, a composition comprising a monoazo iron compound, or an electrostatic charge image developing toner containing them.

  In an electrophotographic image forming process, an electrostatic latent image is formed on a photoreceptor made of an inorganic or organic material, developed with toner, and transferred and fixed on paper, plastic film or the like to obtain a visible image. The photosensitive member has a negative charging property and a positive charging property depending on its structure. When the printed part is left as an electrostatic latent image by exposure, the photosensitive member is developed with a reverse sign charging toner. On the other hand, in the case of performing reverse development by removing the charge from the printing portion, development is performed with the same sign charging toner.

The toner is composed of a binder resin, a colorant, and other additives. A charge control agent is generally added to impart the desired charging characteristics. By adding the charge control agent, the toner characteristics are greatly improved.
Examples of conventionally proposed charge control agents having a negative charge imparting effect include 1: 2 type monoazo metal complex compounds and metal complexes such as aromatic oxycarboxylic acids.

However, most of the 1: 2 type monoazo metal complex compounds proposed as charge control agents generally have poor stability, such as mechanical friction and impact, changes in temperature and humidity conditions, electrical impact and light irradiation, etc. Therefore, the charge controllability is likely to be lost due to decomposition or alteration.
Patent Document 1 proposes a 1: 2 monoazo iron complex salt compound for the purpose of maintaining a high and stable triboelectric charge amount as a toner. According to this publication, the 1: 2 type monoazo iron complex salt compound has negative chargeability and exhibits extremely good resin compatibility, and it is a monoazo iron complex salt compound. It is disclosed that it is easy for it.
Further, Patent Document 2 discloses a 1: 2 type monoazo iron compound (iron atom 1: arrangement) described in Patent Document 1 for the purpose of improving environmental stability (stability of charge control with respect to changes in humidity and temperature) and the like. A composition comprising a ligand 2), a 2: 3 type monoazo iron compound, and a 4: 6 type monoazo iron compound is described.

  In recent years, printers and facsimiles that apply electrophotography have become widespread, and the speed of copying has been increasing year by year. Toners that maintain an appropriate charge instantaneously (good charge rise) are required compared to conventional copying machines. It is becoming. That is, it is required more than conventional toners to maintain appropriate charge instantaneously when entering the output state from the rest state, and the toner containing the monoazo iron (complex salt) compound described in Patent Document 1 and Patent Document 2 Is no exception.

JP 61-155464 A JP-A-9-169919

  The present invention aims to solve the problems as described in the prior art, has a remarkably good rise in charge that can be applied to speeding up printers in recent years, has little change in charge amount with changes in temperature and humidity, and is environmentally stable. It is an object of the present invention to provide a toner for developing an electrostatic image having good properties and a high triboelectric charge amount.

  As a result of earnest research to achieve the above object, the present invention has been completed. That is, the present invention provides the following general formula [1] that can be metallized.

(In the formula [1], A and B each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom, and X represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom. Y represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted aromatic ring group.) 3 monoazo compounds having two hydroxyl groups represented by The following general formula [2]

(In formula [2], D represents a ligand based on the monoazo compound of the general formula [1]).

  Further, the present invention provides the following general formula [3]

(In Formula [3], A and B each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom. X represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom. Y represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aromatic ring group), and a monoazo iron compound represented by the following general formula [4].

(In the formula [4], A and B each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom. X represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom. Y represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aromatic ring group, J represents a hydrogen ion, an alkali metal ion, an ammonium ion, or an alkylammonium ion. A composition comprising a monoazo iron compound, comprising one or more monoazo iron compounds selected from the monoazo iron compounds represented by the formula: It is.

  Furthermore, the present invention is metallizable and has the following general formula [5]

  (In the formula [5], X represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom. C and D are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or 1 to 1 carbon atoms. 8 represents an alkoxy group or a halogen atom.) 3 monoazo compounds having two hydroxyl groups represented by the following general formula [6]

(In formula [6], D represents a ligand based on the monoazo compound of general formula [5].)

  Further, the present invention provides the following general formula [7]

(In the formula [7], X represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom. C and D each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and 1 to 1 carbon atoms. 8 mono-iron compound represented by the following general formula [8]:

(In Formula [8], X represents a hydrogen atom, a C1-C8 alkyl group, and a halogen atom, C and D are each independently a hydrogen atom, a C1-C8 alkyl group, and C1-C1. 8 represents an alkoxy group or a halogen atom of 8. J represents a hydrogen ion, an alkali metal ion, an ammonium ion, or an alkylammonium ion, and in J, two or more of these ions may be mixed.)
A composition comprising a monoazo iron compound, comprising one or more monoazo iron compounds selected from monoazo iron compounds represented by the formula:

  In the present invention, a toner having the following constitution can be obtained by using, as a charge control agent, a composition comprising the above monoazo iron compound or monoazo iron compound. An electrostatic image developing toner containing a binder resin, a colorant, and a charge control agent, wherein the charge control agent contains a monoazo iron compound represented by the general formula [2] as an active ingredient, or the general formula [3 A composition comprising a monoazo iron compound containing at least one monoazo iron compound selected from the monoazo iron compounds represented by the general formula [4] is effective. An electrostatic charge image developing toner, which is a charge control agent as a component.

  Similarly, a toner having the following constitution can be obtained by using the above-described composition comprising a monoazo iron compound or a monoazo iron compound as a charge control agent. An electrostatic charge image developing toner containing a binder resin, a colorant, and a charge control agent, wherein the charge control agent contains a monoazo iron compound represented by the general formula [6] as an active ingredient or the general formula [7 A composition comprising a monoazo iron compound containing at least one monoazo iron compound selected from the monoazo iron compounds represented by the general formula [8] An electrostatic charge image developing toner, which is a charge control agent as a component.

  The toner of the present invention has a remarkably good rise in charge, has a high charge amount, and can maintain a stable charge amount against changes in temperature and humidity.

  Of the compositions composed of the monoazo compound corresponding to the ligand D in each monoazo compound and the monoazo iron compound, preferred are the general formula [5], the general formula [7] and the general formula [8]. In the above, the substituent X is a methyl group, the substituents C and D are hydrogen atoms, the substituent X is a methyl group, the substituent is a hydrogen atom, and the substituent D is a 4-chloro group And the substituent X is a methyl group, the substituent is a 3-chloro group, and the substituent D is a 4-chloro group.

  Among the above-mentioned toners for developing an electrostatic image, a preferable one is that in the above general formula [5], general formula [7], and general formula [8], the substituent X is a methyl group, and the substituent C and D is a hydrogen atom, Substituent X is a methyl group, Substituent is a hydrogen atom, Substituent D is a 4-chloro group, Substituent X is a methyl group, Substituent is 3-chloro Group and substituent D may be a 4-chloro group.

  The monoazo iron compound or composition of the present invention can be obtained by diazotizing 4-chloro-2-aminophenol (diazo component) with sodium nitrite or the like to produce 3-methyl-1- (4-chlorophenyl) -5-pyrazolone or 3 Coupling with methyl-1-phenyl-5-pyrazolone (coupling component) or the like to obtain a metallizable monoazo compound represented by the formula [1], and further converting the monoazo compound into ferric chloride, sulfuric acid A monoazo iron compound (iron complex salt compound) can be obtained by reacting in water and / or an organic solvent with an iron complex chlorination agent such as ferrous sulfate and ferric sulfate and a complex chlorination aid such as salicylic acid. Usually, when obtaining a complex salt of iron: monoazo compound = 1: 2, it can be obtained by adding an iron complexing agent or a complexing aid to an organic solvent of monoazo compound or a solution of water. There. On the contrary, a product containing the monoazo iron compound (composition) of iron: monoazo compound = 2: 3 according to the present invention is obtained by adding a solution of the monoazo compound to a solution in which an iron complex chlorinating agent is dissolved. You can

  As an organic solvent used for such iron complex chlorination, alcohols such as water-soluble methanol, ethanol, butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, ethylene glycol, propylene glycol, Examples include ether-based and glycol-based organic solvents; aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and dimethyl sulfoxide. N, N-dimethylformamide is preferable.

  The amount of the organic solvent used is not particularly limited, but can be 5 to 10 times the mass ratio of the monoazo compound (corresponding to D) used as the ligand in the monoazo iron compound.

  The amount of iron complex chlorinating agent such as ferric chloride is generally 0.5 to 1.0 atomic equivalent of metal (iron), preferably 0.5 to 1.0 equivalent to 1 equivalent of monoazo compound as a ligand. 0.6 atomic equivalent is used.

When synthesized by diazo coupling and iron complex chlorination by a known method as in Patent Document 1, a monoazo iron compound mainly comprising a 1: 2 type iron complex salt (formula [4]) is usually obtained. In addition, a solution in which a monoazo compound is separately dissolved in a solution of DMF or the like containing a complexing aid such as an iron complexing agent or salicylic acid is added and dispersed, as in a method of performing reaction, filtration and drying. Including the 2: 3 type monoazo iron compound represented by the formula [2] [D3 (Fe) 2] by reversing the one to be added and the one to be added, or changing the type of solvent, purification method, and reaction conditions A composition can be obtained.
The charge control agent according to the present invention need not be a single compound, and may be, for example, a composition of a 2: 3 type monoazo iron compound or a 1: 2 type monoazo iron compound. Each product can be confirmed by FD (Field Deposition) -MS analysis.

The 2: 3 type monoazo iron compound represented by the general formula [2] [D3 (Fe) 2] can be represented by a molecular model such as the following formula [9] or [10].

  Examples of the 2: 3 type monoazo iron compound represented by the general formula [2] [D3 (Fe) 2] include the following formula [11] and the following formula [12]. The molecular weight of the formula [11] is 1195, the molecular weight of the formula [12] is 1092, and the width in the molecular weight actually detected by the FD-MS method is based on the Cl isotope.

  The toner for developing an electrostatic charge image of the present invention contains at least a charge control agent, a binder resin, and a colorant containing the monoazo iron compound or the monoazo iron composition as active ingredients.

  The physical and chemical properties of the monoazo iron compound and the composition as the charge control agent in the present invention are not particularly limited, but the average particle size is 0.1 to 20 μm, preferably 0.5 to 10 μm, particularly Preferably it is 0.5-5 micrometers.

  In the electrostatic image developing toner of the present invention, 0.1 to 10 parts by mass of one or more of the above monoazo iron compounds as a charge control agent is added to 100 parts by mass of the binder resin. Is desirable. A more preferable blending amount is 0.2 to 5 parts by mass with respect to 100 parts by mass of the binder resin.

Next, specific constituent materials of the electrostatic image developing toner that can be used in the present invention will be shown. As the binder resin, any known resin can be used.
As the binder resin, styrene such as polystyrene, poly-p-chlorostyrene, polyvinyltoluene and the like, and polymers of the substitution products thereof; styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer Polymer, styrene-vinyl naphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methacrylic acid Methyl copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer , Styrene-butadiene copolymer, steel Styrene copolymers such as styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer; polymethyl methacrylate, polybutyl methacrylate, polychlorinated Vinyl, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, Aromatic petroleum resins, chlorinated paraffin, paraffin wax and the like can be mentioned, and these can be used alone or in combination.

  As the colorant, all known dyes and pigments can be used. However, the charge control agent used in the present invention is black or blue, and is preferably used for black toner or monocolor toner. For example, carbon black, nigrosine dye, iron black, iron oxide and compositions thereof can be used. The amount used is generally 0.1 to 50 parts by mass with respect to 100 parts by weight of the binder resin.

  The toner of the present invention may contain a charge control agent for reinforcement as required. All known charge control agents for reinforcement can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammoniums. Salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Nitronine dye Bontron 03, quaternary ammonium salt Bontron P-51, azochrome complex Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid zinc complex E-84, E-89 of a phenol-based condensate (above, manufactured by Orient Chemical Industries), TN-105 of a salicylic acid-based zirconium compound, T-77 of an azo iron complex, TP-302 of a quaternary ammonium salt molybdenum complex, TP-415 (Above, manufactured by Hodogaya Chemical Co., Ltd.), quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 (above, Hoechst LRA-901, a boron complex LR-1 7 (manufactured by Japan Carlit Co., Ltd.), copper phthalocyanine, perylene, quinacridone, azo pigments, sulfonate group, carboxyl group, and polymer compounds having a functional group such as a quaternary ammonium salt.

  In the present invention, the amount of the charge control agent used for reinforcement is determined by the toner production method including the amount of the charge control agent according to the present invention, the type of binder resin, the presence or absence of additives used as necessary, and the dispersion method. Although it is not limited uniquely, Preferably it is used in 0.2-10 mass parts with respect to 100 weight part of binder resin. Preferably, the range of 0.2-5 mass parts is good.

  In order to give the toner releasability, it is possible to include a wax in the manufactured toner. The wax for this purpose has a melting point of 40 to 120 ° C., particularly preferably 50 to 110 ° C. When the melting point of the wax is excessive, the fixing property at a low temperature may be insufficient. On the other hand, when the melting point is excessively low, the offset resistance and durability may be decreased. The melting point of the wax can be obtained by differential scanning calorimetry (DSC). That is, the melting peak value when a sample of several mg is heated at a constant temperature increase rate, for example, (10 ° C./min) is defined as the melting point.

  Examples of the wax that can be used in the present invention include solid paraffin wax, micro wax, rice wax, fatty acid amide wax, fatty acid wax, aliphatic monoketone, fatty acid metal salt wax, fatty acid ester wax, and partial kenne. And fatty acid ester wax, silicone varnish, higher alcohol, carnauba wax and the like. Also, polyolefins such as low molecular weight polyethylene and polypropylene can be used. Particularly, a polyolefin having a softening point of 70 to 150 ° C. by the ring and ball method is preferable, and a polyolefin having a softening point of 120 to 150 ° C. is more preferable.

As the external additive, inorganic fine particles can be preferably used. The average primary particle diameter of the inorganic fine particles is preferably 0.005 to 2 μm, and particularly preferably 0.005 to 0.5 μm.
Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The use ratio of the inorganic fine particles is preferably 0.01 to 5% by mass of the toner, and particularly preferably 0.01 to 2% by mass. Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. In addition, polymer fine particles, such as polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization, methacrylate esters, acrylate copolymers, polycondensation systems such as silicone, benzoguanamine, and nylon, thermosetting Examples thereof include polymer particles made of a resin.

  Such a fluidizing agent can be surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, a silane coupling agent, a silylating agent, a silane coupling agent having a fluorinated alkyl group, an organic titanate coupling agent, an aluminum coupling agent and the like are preferable surface treatment agents.

  Examples of the cleaning property improver for removing the developer after transfer remaining on the photoreceptor or the primary transfer medium include, for example, zinc stearate, calcium stearate, fatty acid metal salts such as stearic acid, such as polymethyl methacrylate fine particles, polystyrene fine particles, etc. And polymer fine particles produced by soap-free emulsion polymerization. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.

The electrostatic image developing toner of the present invention is produced, for example, as follows.
That is, a binder resin as described above, a colorant (preferably carbon black), a charge control agent comprising a monoazo iron compound of formula (2) as an active ingredient, and a magnetic material (for example, iron or cobalt as required) Ferromagnetic metal fine powder, ferrite, etc.), fluidity modifiers (eg, silica, aluminum oxide, titanium oxide), offsett inhibitors (eg, wax, low molecular weight olefin wax) etc. After mixing, melt kneading using a heat kneader such as a heating roll, kneader, extruder, etc., and cooling and solidifying the kneaded product, and then pulverizing and classifying the solidified product, the volume average particle size 3 A 10 μm toner can be obtained.

  The production method by the pulverization method will be described in more detail. First, a binder resin, a colorant, a charge control agent, waxes, and other necessary additives are uniformly mixed. For mixing, a known stirrer such as a Henschel mixer, a super mixer, or a ball mill can be used. The obtained mixture is hot-melt kneaded using a closed kneader or a single-screw or twin-screw extruder. After cooling, the kneaded product is coarsely pulverized using a crusher or a hammer mill, and further finely pulverized by a pulverizer such as a jet mill or a high-speed rotor rotary mill. Further, classification is performed to a predetermined particle size using an air classifier, for example, an inertia class elbow jet utilizing the Coanda effect, a cyclone (centrifugal) class microplex, a DS separator, and the like. Furthermore, when processing the external additive on the toner surface, the toner and the external additive are stirred and mixed with a high-speed stirrer such as a Henschel mixer or a super mixer.

  The toner of the present invention can also be produced by a suspension polymerization method. In the suspension polymerization method, a monomer composition is prepared by uniformly dissolving or dispersing a polymerizable monomer, a colorant and a polymerization initiator, a charge control agent, and, if necessary, a crosslinking agent and other additives. Then, the monomer composition is mixed into a continuous phase containing a dispersion stabilizer, for example, an aqueous stirrer and a disperser, such as a homomixer, a homogenizer, an atomizer, a microfluidizer, a one-fluid fluid nozzle, a gas-liquid. Toner particles having a desired particle diameter can be obtained by dispersing using a fluid nozzle, an electric emulsifier, and the like, and simultaneously performing a polymerization reaction. The method described above can be used for the external addition treatment after the preparation of the particles.

When the toner of the present invention is used as a two-component developer, the toner of the present invention can be mixed with carrier powder and developed by a magnetic brush developing method or the like.
Any known carrier can be used. For example, iron powder, nickel powder, ferrite powder, glass beads and the like having a particle size of about 50 to 200 μm, and their surfaces are made of an acrylate copolymer, styrene-acrylate copolymer, styrene-methacrylic acid. Examples include those coated with an ester copolymer, a silicone resin, a polyamide resin, an ethylene fluoride resin, and the like.

  When the toner of the present invention is used as a one-component developer, an appropriate amount of fine powder made of a ferromagnetic material such as iron powder, nickel powder or ferrite powder is added and dispersed when the toner is manufactured as described above. Can be used. Examples of the developing method in this case include a contact developing method and a jumping developing method.

  In addition, the monoazo iron compound or monoazo iron composition of the formula [11] or the formula [12] can be used as a charge enhancer of a powder coating for electrostatic coating, and is excellent when used as a charge enhancer. A powder coating with good charging characteristics, environmental stability and coating efficiency can be obtained.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, these do not limit this invention at all. In the following description, “part by mass” is abbreviated as “part”.

(Production Example 1)
4 parts of 7.3 parts of monoazo compound (formula 13) synthesized by general diazotization coupling reaction using 4-chloro-2-aminophenol and 3-methyl-1- (4-chlorophenyl) -5-pyrazolone A solution dispersed in 50 parts of a sodium hydroxide aqueous solution was dissolved in 3.3 parts of salicylic acid, 20 parts of a 16% sodium hydroxide solution, and 18.8 parts of a 38% aqueous ferric chloride solution in 100 parts of DMF and stirred at 60 ° C. The resulting solution was added and reacted at 100 ° C. for 3 hours. Further, 2.6 parts of 38% ferric chloride aqueous solution was added and reacted for 2 hours.
This reaction solution was dispersed in 100 parts of 1.5% aqueous hydrochloric acid and stirred at 60 ° C. for 30 minutes. The resulting precipitate was collected by filtration, washed with water, and dried to obtain 9.2 parts of black powder.

When the molecular weight of this powder was measured by the FD-MS method, the mass spectrum shown in FIG. 1 was obtained. (The horizontal axis indicates M / Z [mass / charge], and the vertical axis indicates relative abundance [abundance ratio]. The same applies to [FIG. 2].)
From the mass spectrum of [FIG. 1], the main product, 2: 3 type monoazo iron compound [formula 11, M / Z = 1195 (M +)] and 1: 2 type monoazo iron compound (formula 13 below) [M / Z = 779 (M +)] was confirmed.

In addition, the measurement of the molecular weight by FD-MS method was performed as follows. It measured similarly about the manufacture example 2 and the comparative manufacture example.
The sample was dissolved or dispersed in toluene and measured with a mass spectrometer (trade name: MS700, manufactured by JEOL Ltd.), and a mass spectrum diagram showing the molecular weight of the sample was represented.
Conditions of FD-MS method (electrolytic desorption ionization method) Accelerating voltage using carbon emitter: 8 kV
Cathode voltage: 2 kV
Emitter current: 2-50mA, 2mA / min program

(Production Example 2)
A black powder was obtained in the same manner as in Production Example 1 using 4-chloro-2-aminophenol and 3-methyl-1-phenyl-5-pyrazolone.

  When the molecular weight of this powder was measured by the FD-MS method, as in Production Example 1, the main product was a 2: 3-type monoazo iron compound [formula 12, M / Z = 1092 (M +)]. , 1: 2 type monoazo iron compound [the following formula (14), M / Z = 710 (M +)] was confirmed.

(Production Example 3)
A black powder was obtained in the same manner as in Production Example 1 using 4-chloro-2-aminophenol and 3-methyl-1- (3,4-dichlorophenyl) -5-pyrazolone.

  When the molecular weight of this powder was measured by the FD-MS method, it was 1: 2 together with the 2: 3 type monoazo iron compound [M / Z = 1299 (M +)] as the main product, as in Production Example 1. Type monoazo iron compound [the following formula (15), M / Z = 848 (M +)] was confirmed.

(Production comparison example)
Compound of the following structural formula [16] (included in Patent Document 2) by the method described in Patent Document 2 using 4-chloro-2-aminophenol and naphthol AS (3-hydroxy-2-naphthanilide) Was synthesized, filtered, washed with water, and dried. When the molecular weight of this powder was measured by the FD-MS method, the mass spectrum shown in FIG. 2 was obtained.
From the mass spectrum diagram of [FIG. 2], the 2: 3 type monoazo iron compound [M / Z = 1359 (M +)] as the main product, the 2: 3 type monoazo iron compound [M / Z Z = 886 (M + of negative ions)] was confirmed.

Example 1
The product obtained in Production Example 1 whose main component is a monoazo iron compound (and a monoazo iron composition) was used as a charge control agent, and each was blended in the following proportions.

91 parts of styrene-acrylic copolymer resin (Mitsui Chemicals, trade name CPR-300)
Composition obtained in Production Example 1 1 part Carbon black (trade name MA-100, manufactured by Mitsubishi Chemical Corporation) 5 parts Low molecular weight polypropylene (trade name, Viscol 550P, manufactured by Sanyo Chemical Co., Ltd.) 3 parts

  The above blend was melted and mixed with a heating and mixing apparatus (biaxial extrusion kneader) at 130 ° C., and the cooled mixture was coarsely pulverized with a hammer mill. Further, it was finely pulverized by a jet mill and classified to obtain a nonmagnetic toner having a volume average particle size of 9 ± 0.5 μm. A developer was prepared by mixing 4 parts of the obtained toner with 100 parts of a silicon-coated carrier (trade name: F96-100, manufactured by Powdertech Co., Ltd.). The obtained developer was thoroughly stirred, and the charge amount was measured with a blow-off charge amount measuring machine. The results are shown in Table 1.

In addition, a time constant (τ), which is an index of charge rising property, was also calculated. For the time constant (τ), the amount of charge until saturation charge is reached is measured with a blow-off charge amount measuring device at regular intervals, and described in (Electrophotographic Society of Japan, P307, Vol. 27, No. 3 (1988)). Then, ln (qmax-q) was calculated according to the following equation, and the relationship between time t and ln (qmax-q) was plotted on a graph to obtain the time constant τ. The results are shown in Table 1.
(Qmax−q) / (qmax−q0) = exp (−t / τ)
Here, qmax is the saturation charge amount, q0 is the initial charge amount (here, the value when the charge time is 30 seconds), t is each measurement time, and the charge amount at that time is q.
Those with good rise in charge have a smaller time constant. The unit of time constant is seconds.

In addition, the environmental stability evaluation method for evaluating the environmental stability of charging is not only the measurement under the normal 25 ° C.-50% RH (relative humidity) environment but also the high humidity environment (35 ° C.- It was determined by measuring the charge amount at 85% RH).
In the measurement of the charge amount, the developer exposed to each environment for 24 hours was sufficiently charged in the environment, and the saturation charge amount was measured with a blow-off charge amount measuring machine.
In two environments, the variation in charge amount was less than 15% was evaluated as good (◯), 15 to 20% was evaluated as slightly defective (Δ), and the value exceeding 20% was determined as defective (x). The results are shown in Table 1.

(Example 2 and comparative example)
Instead of “Composition obtained in Production Example 1”, “Composition obtained in Production Example 2” and “Composition obtained in Production Comparative Example” were used, respectively, and also included the blending amount. A toner was prepared in the same manner as in Example 1, and the charge amount, time constant, and environmental stability were evaluated using a blow-off charge amount measuring device. The results are shown in Table 1 as Example 2 and Comparative Example, respectively.
In Table 1, the unit of charge amount is (μC / g), and the unit of time constant τ is (seconds).

  As is apparent from [Table 1], the toners of Example 1 and Example 2 have a smaller time constant τ than the toner of the comparative example, which is a conventional toner, and show a quick rise in charging. Further, the toner exhibits a sufficiently high charge amount as a toner and has good environmental stability.

  The toner of the present invention has a remarkably good rise in charge, has a high charge amount, and is useful for applications that need to maintain a stable charge amount against changes in temperature and humidity.

2 is an FD-MS spectrum diagram of the composition obtained in Production Example 1. FIG. It is a FD-MS spectrum figure of the composition obtained by manufacture comparative example.

Claims (7)

The following general formula [3]

(In Formula [3], A and B each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom. X represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom. Y represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aromatic ring group), and a monoazo iron compound represented by the following general formula [4].

(In the formula [4], A and B each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom. X represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom. Y represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aromatic ring group, J represents a hydrogen ion, an alkali metal ion, an ammonium ion, or an alkylammonium ion. A composition comprising a monoazo iron compound, comprising one or more monoazo iron compounds selected from the monoazo iron compounds represented by the formula: . The following general formula [7]

(In the formula [7], X represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom. C and D each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and 1 to 1 carbon atoms. 8 mono-iron compound represented by the following general formula [8]:

(In Formula [8], X represents a hydrogen atom, a C1-C8 alkyl group, and a halogen atom, C and D are each independently a hydrogen atom, a C1-C8 alkyl group, and C1-C1. 8 represents an alkoxy group or a halogen atom, and J represents a hydrogen ion, an alkali metal ion, an ammonium ion, or an alkylammonium ion, and two or more of these ions may be mixed in J). A composition comprising a monoazo iron compound, comprising at least one monoazo iron compound selected from the group of monoazo iron compounds. The composition which consists of a monoazo iron compound of the said General formula [7] and General formula [8] whose substituent X is a methyl group and whose substituents C and D are a hydrogen atom.   The monoazo iron compound according to claim 2, wherein, in the general formula [7] and the general formula [8], the substituent X is a methyl group, the substituent C is a hydrogen atom, and the substituent D is a 4-chloro group. A composition comprising:   The monoazo according to claim 2, wherein, in the general formula [7] and the general formula [8], the substituent X is a methyl group, the substituent C is a 3-chloro group, and the substituent D is a 4-chloro group. A composition comprising an iron compound. The following general formula [3]

(In Formula [3], A and B each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom. X represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom. Y represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aromatic ring group), and a monoazo iron compound represented by the following general formula [4].

(In the formula [4], A and B each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom. X represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom. Y represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aromatic ring group, J represents a hydrogen ion, an alkali metal ion, an ammonium ion, or an alkylammonium ion. A composition comprising a monoazo iron compound, comprising one or more monoazo iron compounds selected from the monoazo iron compounds represented by the formula: Charge control agent containing as an active ingredient. The following general formula [7]

(In the formula [7], X represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a halogen atom. C and D each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and 1 to 1 carbon atoms. 8 mono-iron compound represented by the following general formula [8]:

(In Formula [8], X represents a hydrogen atom, a C1-C8 alkyl group, and a halogen atom, C and D are each independently a hydrogen atom, a C1-C8 alkyl group, and C1-C1. 8 represents an alkoxy group or a halogen atom, and J represents a hydrogen ion, an alkali metal ion, an ammonium ion, or an alkylammonium ion, and two or more of these ions may be mixed in J). A charge control agent comprising a composition comprising a monoazo iron compound as an active ingredient, wherein the charge control agent comprises one or more monoazo iron compounds selected from the above-mentioned monoazo iron compounds.

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