JPS597385B2 - Toner for developing electrostatic images - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a toner used for developing electrostatic latent images in electrophotography, electrostatic recording, electrostatic printing, etc., and in particular to an improved metal for controlling the toner negatively. The present invention relates to a toner containing a complex compound.

Conventionally, various charge (tolipo) control agents have been used in toners for developing electrostatic latent images, but the ones currently in practical use in this technical field are those that impart positive charges to toners. In some cases, there are oil-soluble dyes such as nigrosine series shown in Japanese Patent Publication No. 41-2427, etc., and in the case of imparting a negative charge to the toner, there are generally metal-containing dyes. Examples of use in electrophotographic toners include Japanese Patent Publication No. 12915/1970, Japanese Patent Publication No. 17955/1973, Japanese Patent Publication No. 27596/1973, and Japanese Patent Publication No. 44-63/1989.
Publication No. 97, Japanese Patent Publication No. 45-26478, Japanese Patent Publication No. 1977
It is described in Japanese Patent No. 2-67331 and the like. These conventional metal-containing dyes have excellent properties in terms of the ability to impart a negative charge to toner particles; Additionally, when preparing toner using these dyes, when melting and kneading them thoroughly at high temperatures to obtain a homogeneous toner, the dyes may undergo thermal decomposition, resulting in changes in the chargeability of the toner or changes in color tone. is likely to change.

In addition, during the development process, it is constantly stirred and rubbed against carriers, etc., and is likely to be decomposed or altered by mechanical friction, impact, electrical impact, and irradiation with light, making the applied charge likely to be uneven. As a result, when such toner is used for development, the image density becomes non-uniform and fogging occurs, making it impossible to obtain clear copies. The inventors of the present invention have discovered that, without reducing the excellent negative chargeability of metal-containing dyes, the drawbacks of the conventional products described above can be removed, and uniform image density can be obtained, there is little fogging, and the life is long. As a result of extensive research into compounds that produce negative toner with stable chargeability, we found the following general formula [wherein A and A''(
Diazo component residues that may have a melon substituent, B and B'
are couple component residues that may have substituents, Yl, Y
2, Y3 and Y4 are H (but not /1'1H at the same time) or the general formula -SO2N3 (wherein R, and R
2 represents H, an alkyl group (C1-6), a cyclohexyl group, a phenyl group, or -C2H4OH.

), Z and Z' are present at the ortho position to the azo group, respectively -0- or -COO-,
M represents Cr, CO or Fe.

It was discovered that the metal complex compound represented by the following is superior, and the present invention was completed.

The present invention provides that the metal complex compound represented by the above general formula (1), which does not have a nitro group and has a sulfonamide group, has excellent heat resistance and light resistance, and has no risk of ignition when pulverized. In addition, those whose counter ions are hydrogen ions have excellent pulverization properties and strong chargeability compared to other cations.
Based on new knowledge that it has good miscibility and compatibility with toner resins, and when used in toners for charge control, homogeneous chargeable particles can be obtained and toners with excellent durability can be produced. Conventionally, it has never been thought of to use a metal complex compound having a sulfonamide group but not a nitro group as shown in the general formula (1) in a toner. Tokuko Sho 45-264
As described in Publication No. 78, it is said that the counter ion for a metal complex compound for toner containing a diazo group is preferably a sodium ion or a potassium ion, and the use of a hydrogen ion as a counter ion has never been seen in the past. However, in these respects, the structure of the present invention breaks the conventional common sense in the art.

The metal complex compound in the present invention is obtained by treating a metallizable azo compound with a metallizing agent by a known method, diluting it with acidic or mineral acid-containing water to precipitate it, and then taking it from the house. You can get it by twisting it.

Examples of amines used to obtain the metallizable azo compound in this case include 2-aminophenol,
4-tertiaryamyl-2-aminophenol, 4-methoxy-2-aminophenol, 4- or 5-chloro-
2-aminophenol, 4- or 5-sulfamoyl-2-aminophenol, 2-aminophenol-4- or 5-sulfonic acid cyclohexylamide, 2-aminophenol-4- or 5-sulfonic acid alkyl (C1
~6) Amide, 2-aminophenol-4 or 5-
Dialkyl sulfonate (Cl~6) amide, anthranilic acid, 4- or 5-sulfamoyl-anthranilic acid, 4- or 5-alkyl anthranilate-4- or 5-sulfonate (
Examples include Cl-6) amide, anthranilic acid-4 or 5-sulfonic acid mono- or di(2-hydroxyethyl)amide, and 2-aminophenol-4- or 5-sulfonic acid anilide. Next, examples of coupling components used to obtain metallizable azo compounds include 4-alkyl (C1-9)phenol, 2-naphthol, 6-sulfamomethyl-2-naphthol, 2-naphthol-6- Alkyl sulfonate (Cl,,6) amide, 4-sulfamoyl-1-naphthol, 1 naphthol-4-alkyl sulfonate (C1-6) amide, 1
-Phenyl-3-methyl-pyrazolone, 1-(3/-sulfamoyl)phenyl-3-methyl-pyrazolone, 1
-[3/-N-alkyl(C1,6)sulfamoyl]
Examples include phenyl-3-methylpyrazolone, acetoacetic acid anilide, and 3-sulfamoylacetoacetic acid anilide.

Organic or inorganic chromium salts, salts and iron salts can be used as metallizing agents for treating the metallizable azo compounds.

Cobalt Examples of the metal complex compound represented by the general formula (1) of the present invention are as follows.

As mentioned above, the metal complex compound used in the present invention has excellent heat resistance, light resistance, and fine pulverization properties, has no risk of ignition during pulverization, and has extremely good dissolution and dispersibility in toner resins. However, as shown by the above-mentioned exemplified compounds, the color tone ranges from black-purple to reddish-purple to yellow, and colorants for color copying toners, such as copper phthalocyanine, quinacridone,
Even when used in combination with benzidine yellow, it has the excellent property of being able to obtain images with high clarity without deteriorating the color tone.

Incidentally, the amount of the metal complex salt compound of general formula (1) added to the toner component is generally 0.1 to 10 parts by weight based on 100 parts by weight of the resin, but preferably 0.5 parts by weight.
~5 parts by weight.

The toner of the present invention contains a known toner resin and colorant in addition to the metal complex compound. Examples of the added resin include polystyrene, poly-p-chlorostyrene,
Monopolymers of styrene and its substituted products such as polyvinyltoluene, styrene-p-chlorostyrene copolymers, styrene-propylene copolymers, styrene-vinyltoluene copolymers, styrene-vinylnaphthalene copolymers, styrene-acrylics acid methyl copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer Polymer, styrene-butyl methacrylate copolymer, styrene chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinylethyl ether copolymer, styrene - Styrenic copolymers such as vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene , silicone resins, polyesters, polyurethanes, polyamides, epoxy resins, polyvinyl butyral, Kuchichi, modified Kuchichi, terpene resins, phenolic resins, xylene resins, aliphatic and alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated Examples include paraffin and paraffin wax, which may be used alone or in combination.

Further, as the coloring agent, many known dyes and pigments can be used. The toner of the present invention is mixed with a carrier to form a developer. As the carrier, any known carrier can be used, such as magnetic powder such as iron powder, glass beads, and the like. There are also those whose surfaces are treated with resin. EXAMPLES Specific examples of the present invention will be described below in Examples.

In addition, in Examples, parts by weight are abbreviated as parts.
Example 1 A toner was prepared as follows.

Styrene-acrylic copolymer ・・・・・・・・・10
0 parts (Permer-SMB6OO manufactured by Sanyo Chemical Co., Ltd.) are uniformly premixed in a ball mill to prepare a premix.

Next, it is melt-kneaded using hot rolls, and after cooling, it is coarsely ground,
A toner having a particle size range of 5 to 15 μm was prepared by pulverization and classification. 5 parts of this toner and 9 parts of iron powder carrier
A developer was prepared by mixing 5 parts. The initial tripocharge amount of the toner was -14 μc/9.

Furthermore, when a toner image was formed on a commercially available selenium drum by magnetic brush development, no deterioration in copy quality was observed even after 50,000 copies were made continuously.

Note that a comparison with reference examples and the like is shown in Table 1 below. Example 2 A toner was prepared in the same manner as in Example 1 except that the complex compound of structural formula (4) was used in place of the complex compound of structural formula (1), and the copying quality and initial tripocharge were measured.

The results are shown in Table 1 below. Example 3 A toner was prepared by processing in the same manner as in Example 1, and the copying quality and initial tripo charge were measured.

The results are shown in Table 1 below. Example 4 A toner was prepared by processing in the same manner as in Example 1, and the copying quality and initial tripo charge were measured.

The results are shown in Table 1 below. Reference Example 1 A developer was prepared using a toner containing no complex compound of structural formula (1) in Example 1, and the same test was conducted.

Claims (1)

[Claims] 1 General formula ▲ Numerical formulas, chemical formulas, tables, etc. Couple component residues, Y_1, Y_2, Y_3 and Y_4, which may be
H (but not H at the same time) or general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 and R_2 are H, alkyl group (C_1_
~_6), cyclohexyl group, phenyl group or -C_
Indicates 2H_4OH. ), Z and Z' are present at the ortho position to the azo group, respectively -O- or -COO-,
M represents Cr, Co or Fe. ] A toner for developing an electrostatic image, characterized by containing a metal complex compound represented by the following. 2 The amount of metal complex compound is 0 with respect to 100 parts by weight of resin.
．． The toner for developing an electrostatic image according to claim 1, wherein the amount is 5 to 5 parts by weight.