JP2001060021A - New transition metallic complex of polyaniline derivative, electrostatic charge controlling agent comprising the same for developing electrostatic charge image, toner and electric charge imparting agent each using said electrostatic charge controlling agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrostatic charge controlling agent not containing a metal whose safety is not confirmed, e.g. chromium and to provide an electro static charge image developing toner, and an electric charge imparting material each using the electrostatic charge controlling agent. SOLUTION: The transition metallic complex of a polyaniline derivative is represented by the formula [where R1-R4 are each H, an alkyl, alkoxy, aryl, amino or carboxyl, X is an anionic group, M is a group IB to VIIB or VIII transition metal, (m) is an integer of 2-6, (n) is an integer of >=4 and p+q+r≠0]. The electrostatic charge controlling agent for developing an electrostatic charge image comprises the metallic complex.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel transition metal complex of a polyaniline derivative, a charge controlling agent for developing an electrostatic image used in an electrophotographic copying machine or a laser printer, and a toner and an electrostatic charge using the same. The present invention relates to a charge-imparting material that imparts electric charge to a toner used for developing an image.

[0002]

2. Description of the Related Art In a developing step, a developer used in an electrophotographic copying machine or the like is once adhered to an image carrier such as a photoreceptor on which an electrostatic image is formed. After being transferred from the photoreceptor to transfer paper, it is fixed on a copy paper surface in a fixing step. At that time, as a developer for developing an electrostatic image formed on the latent image holding surface, a two-component developer composed of a carrier and a toner and a one-component developer (magnetic toner, Non-magnetic toner) is known.

One of the important characteristics required for toner is chargeability. In particular, an appropriate positive or negative level of charge is generated by contact with a carrier or a vessel wall of a developing tank.
In addition, it is required that the charge level is substantially stable over time even during continuous use or in a severe environment. The chargeability of the toner can be provided by the resin or the colorant itself. However, it is difficult to obtain sufficient chargeability. It is known that a toner contains a nigrosine dye, a quaternary ammonium salt, a negatively charged metal-containing monoazo dye, a salicylic acid metal complex, a copper phthalocyanine pigment, or the like.

[0004]

However, these conventional charge control agents have several problems in terms of the effect of imparting charge and other characteristics required for the toner. One of them is the safety of the toner. Most of the conventional charge control agents, especially negative charge control agents, are metal-containing dye types containing heavy metals such as chromium, for example, because of the high charge level applied. It is preferable to avoid the use of a metal such as chromium, which has a questionable safety, as a component of a toner, a substance used in a place very close to the human body. Accordingly, it is an object of the present invention to provide a novel charge control agent containing no metal such as chromium, which is questionable in safety, a toner using the same, and a charge-imparting material.

[0005]

Means for Solving the Problems In order to overcome the above-mentioned drawbacks of the charge control agent, the present inventors have conducted intensive studies on compounds which are safer and have excellent charge providing performance. Finding that complex compounds are useful,
The present invention has been reached. That is, the gist of the present invention is a transition metal complex of a novel polyaniline derivative represented by the general formula,
And a charge controlling agent for developing an electrostatic charge image comprising the metal complex, and a toner and a charge providing material for developing an electrostatic charge image using the charge controlling agent.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The transition metal complex of the novel polyaniline derivative in the present invention (hereinafter, abbreviated as the present metal complex) is a compound represented by the following general formula.

Embedded image

(Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group which may have a carboxyl group, an alkoxy group, an aryl group, an amino group or a carboxyl group. X represents an anionic group, M represents a transition metal element shown in Groups 1B to 7B and 8 in the periodic table of elements, m represents an integer of 2 to 6, and n represents an integer of 4 or more. And p, q, and r are each independently 0, 1/7, 1/6, 1/5,
Represents a number selected from 1/4, 1/3, 1/2 and 1; p + q + r
≠ 0. )

In the above R _{1 to} R ₄ , the alkyl group which may have a carboxyl group includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group and the like.
And a lower alkoxy group such as a methoxy group and an ethoxy group, and an aryl group such as a phenyl group. X
Examples thereof include a carboxyl group; a halogen atom such as a chlorine atom and a bromo atom; a cyano group; a thiocyanate group; an acetyl group; and an anionic group such as a perchloric acid group. M is a transition metal element shown in Groups 1B to 7B and Group 8 in the periodic table of the elements, and examples thereof include V, Fe, Co, Ni, Cu, Zn, and Al. n is 4 or more, preferably 4 to 500.

The method for producing the metal complex of the present invention represented by the above general formula is not particularly limited, and a generally adopted electrode oxidation method can be used. After synthesizing the polyaniline derivative with an oxidizing agent such as ammonium persulfate under acidic conditions, the polyaniline derivative is easily dissolved in a polar organic solvent such as N, N-dimethylformamide at room temperature and reacted with a halide of a transition metal. You can get it.

A charge controlling agent for developing an electrostatic image (hereinafter, sometimes referred to as a charge controlling agent) comprising the metal complex of the present invention having excellent charging performance is useful for a toner. A case where the toner is used as a toner for developing a charge image will be described. The toner for developing an electrostatic image of the present invention contains at least the charge control agent, the resin and the colorant.

As the resin component used in the toner, various known resins that are generally used can be used. Specific resins include, for example, styrene resins such as polystyrene, polychlorostyrene, and styrene-butadiene copolymer; styrene acrylic copolymer resins such as styrene-acrylate copolymer and styrene-methacrylate copolymer Polyester resin; epoxy resin;
And a mixed resin thereof.

The colorant used in the toner is appropriately selected from known organic pigments, inorganic pigments and dyes. For example, C.I. I. Pigment Red 48: 1, C.I.
I. Pigment Red 57: 1, C.I. I. Pigment Red 122, C.I. I. Pigment Yellow 17, C.I.
I. Pigment Yellow 97, C.I. I. Pigment Yellow 12, C.I. I. Pigment Blue 15: 1, C.I.
I. Pigment Blue 15: 3, carbon black, nigrosine dye, metal complex dye, derivative of metal complex dye,
And mixtures thereof.

The content of the metal complex of the present invention in the toner is preferably from 0.1 to 20 parts by weight, more preferably from 0.1 to 10 parts by weight, based on 100 parts by weight of the resin. When the metal complex of the present invention represented by the above general formula is contained in a toner, these complexes may be used alone or in combination of two or more.

In the toner of the present invention, other than the above-mentioned metal complex component of the present invention, if necessary, other charge control agents, further, waxes, various additives and the like may be added. Known compounds are used as other charge control agents, for example,
Examples include metal complexes of hydroxycarboxylic acids, metal complexes of azo compounds, naphthol compounds, metal compounds of naphthol compounds, nigrosine dyes, quaternary ammonium salts, and mixtures thereof.

As the wax, any wax can be used as long as it has a releasing property. Specifically, carnauba wax, vegetable wax such as rice wax,
Solid silicone wax such as alkyl denatured silicone, amide wax such as stearic acid amide, higher aliphatic alcohol wax, higher fatty acid ester wax,
Synthetic hydrocarbon waxes such as polyethylene and polypropylene and mixtures thereof.

A known external additive may be added to the toner for developing an electrostatic image of the present invention in order to control fluidity and developability. As an external additive, various inorganic oxide particles such as silica, alumina, titania, etc. (hydrophobizing treatment if necessary)
Vinyl polymer particles and the like can be used. The amount of the external additive is preferably in the range of 0.05 to 5 parts by weight based on the toner particles.

The electrostatic image developing toner of the present invention can be developed by a known developing method. For example, it can be used in any of a two-component developing method such as a cascade method, a magnetic brush method, and a microtoning method, a conductive and insulating one-component developing method, and a non-magnetic one-component developing method.

Next, the case where the metal complex of the present invention is used as a charge imparting material will be described. The charge imparting material has the metal complex of the present invention on at least a part of the surface of the base material. here,
The charge imparting material is a carrier, a developing sleeve, a layer forming blade or the like, which comes into contact with the toner prior to the development process or development, and imparts a charge necessary for development to the toner,
Alternatively, it is a general term for a material or a member to which an electric charge can be supplemented, and the base material means the material or the member.

The coating solution obtained by dissolving or dispersing the metal complex of the present invention in a solvent or a dispersion medium together with a binder resin, if necessary, is applied to the base material of the charge-imparting material by dipping, spraying, brushing, or the like. Or, if the base material is in the form of carrier particles, by a method of immersing and mixing this in the coating solution and then drying, or by a method of coating a direct mixture with the base material using a fluidized bed,
The charge-imparting material of the present invention can be obtained by forming a coating layer containing the metal complex of the present invention on the base material. Alternatively, the charge-imparting material may be obtained by directly melting and kneading the binder resin and the metal complex and extruding and laminating the mixture on a base material. Further, the metal complex may be contained in a moldable resin, and this may be formed into a shape of a carrier particle, a developing sleeve or a layer forming blade to serve as a charge imparting material.

The binder resin or the molding resin can be appropriately selected from those usually used.
For example, rubber-based resins such as polystyrene, polyacrylate, polymethacrylate, isoprene or butadiene, polyester, polyurethane, polyamide, epoxy resin and the like can be mentioned.

The transition metal complex of the polyaniline derivative of the present invention, by utilizing its excellent charging characteristics, imparts a charge to the above-mentioned charge control agent for electrostatic image development, and a toner using the same and a toner for electrostatic image development. It is used for the purpose of charge-imparting material,
It is also useful as an electrode material of an optical element, an electrode material of various primary batteries and secondary batteries, a conductivity adjusting material of an electrophotographic photosensitive member, and the like.

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples and Examples.
It is not limited to the following embodiments. In the following examples, “parts” simply means “parts by weight”. Synthesis Example 8.56 g of ortho-toluidine was added to 1N hydrochloric acid aqueous solution 1
It was added to a solution consisting of L (liter) and 400 ml of ethanol, and the resulting solution was cooled to -5 ° C. 1.8 g of ammonium persulfate was added to this solution. After continuing the reaction at -5 ° C for 5 hours, the temperature was returned to room temperature, and the precipitate from the reaction solution was filtered to obtain a compound having ortho-toluidine as a repeating unit. After washing the compound with water, it is treated with 400 ml of a 1N aqueous solution of sodium hydroxide for 2 hours, and thereafter,
After filtration and washing with water, 6.5 g of a reaction product was obtained.

6.5 g of the above reaction product and 4.7 g of vanadium (III) chloride were added to 500 ml of dimethylformamide to form a complex at room temperature. Filtering the reaction product,
Upon drying, 5.9 g of polyortho-toluidine vanadium chloride complex could be obtained. The results of infrared absorption spectrum measurement (IR) and elemental analysis of the complex thus obtained are shown below. IR (KBr, cm ^-1 ): 3785, 3693, 3374, 1570, 1483, 137
9, 1257, 1211, 1152, 1104, 999, 941, 805 Elemental analysis Found: H: 5.67, C: 59.04, N: 10.11, Cl: 1
3.71%

Example 1 100 parts by weight of a styrene acrylic copolymer resin having an average particle size of 10 μm (manufactured by Nippon Carbide Co., Ltd .; product number G-10) and 1 part by weight of the complex synthesized according to the above synthesis example were put into a coffee mill. And stirred for 1 minute. One part by weight of the sample thus prepared was mixed with 99 parts by weight of an iron powder carrier, and the charge amount with respect to the mixing time was measured by a suction blow method.
Further, the same measurement was performed for a styrene-acrylic copolymer resin alone to which no complex was added. The results are shown in Table 1 below.
Shown in

[0025]

[Table 1]

As a result, it can be seen that, while the charge amount of the resin alone increases greatly with the mixing time, the increase in the complex-added sample is very small, and the chargeability is sufficiently controlled.

Example-2 100 parts of a polyester resin (FC-023 manufactured by Mitsubishi Rayon Co., Ltd.) 4 parts Carbon black (MA-100 manufactured by Mitsubishi Chemical Corporation) 4 parts Complex of the synthesis example 2 parts The above materials were mixed and kneaded and crushed and classified. Average particle size
A 5 micron black toner was obtained. 5 parts of this toner and a ferrite carrier having an average particle diameter of about 90 microns (acrylic coat)
95 parts were mixed and stirred to prepare a developer. Then, when this developer was actually photographed by a copying machine using a negatively chargeable OPC (laminated system) as a photosensitive member, a clear copy was obtained.

Example 3 Instead of the polyester resin, a styrene (St) / butyl acrylate (BA) copolymer resin (St / BA = 7/3, Sp
= About 140 ° C), and a developer was prepared and photographed in the same manner as in Example 2. As a result, a good copy was obtained as in Example 2.

[0029]

The toner for developing an electrostatic image and the charge-imparting material using the charge controlling agent for developing an electrostatic image comprising the novel metal complex of the present invention are excellent in safety, good in chargeability and high in quality. And a charge imparting material.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) G03G 15/08 504 G03G 9/10 341 362 (72) Inventor Osamu Ando 1000 Kamoshidacho, Aoba-ku, Yokohama-shi, Kanagawa Prefecture Address Mitsubishi Chemical Corporation Yokohama Research Laboratory F-term (reference) 2H005 AA06 AA08 BA05 BA07 CA25 DA02 2H077 AE03 AE04 AE05 AE06 EA02 EA03 EA12 EA13 EA14 FA25 4H050 AA01 AB91 WB14 WB17

Claims (4)

[Claims] 1. A novel transition metal complex of a polyaniline derivative represented by the following general formula. Embedded image (Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom,
X represents an alkyl group, an alkoxy group, an aryl group, an amino group or a carboxyl group which may have a carboxyl group, X represents an anionic group, and M represents 1B in the periodic table of elements.
To 7B and 8 represent transition metal elements, and m is 2
Represents an integer of 6 to 6, and n represents an integer of 4 or more. Also p,
q and r are each independently 0, 1/7, 1/6, 1/5, 1/4, 1/3, 1 /
Represents a number selected from 2 and 1, and p + q + r ≠ 0. ) 2. A charge controlling agent for developing an electrostatic image, comprising the metal complex according to claim 1. 3. A toner for developing an electrostatic image, comprising a resin, a colorant and the charge controlling agent for developing an electrostatic image according to claim 2. 4. A charge providing material for developing an electrostatic image, comprising the charge control agent for developing an electrostatic image according to claim 2 on at least a part of the surface of the base material.