JPH05257322A - Electrophotographic green toner - Google Patents

Abstract

PURPOSE:To obtain a toner which stably gives clear picture images having little fog and excellent light resistance by using a dye stuff having a specified structure as a coloring agent. CONSTITUTION:This color toner contains at least a coloring agent in a binder resin and the coloring agent contains phthalocyanine dye expressed by formula I. In formula, R is expressed by formula II and the substituting position of R is 1- or 4-, 5- or 8-, 9- or 12-, 13- or 16-. R' is a substd. or unsubstd. alkyl group of 1-20 carbon number or hydrogen, X is independently -CH2CH2-, -CH2 CH2CH2-, -CH(CH3)CH2-, or isomers of these, n is an integer 0-10, Met is a metal. The unsubstd. alkyl group of 1-20 carbon number expressed by R' is methyl group, ethyl group, etc., and the substd. alkyl group of 1-20 carbon number is a hydroxymethyl group, and Met is Zn, or Mg, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color toner for electrophotography, and more particularly to a green toner for electrophotography containing a specific dye.

[0002]

2. Description of the Related Art In recent years, an electrostatic latent image of a document exposed by spectral light is formed and developed with color toner of each color to obtain a colored copy image, or the copy images of each color are superposed. A color copying method for obtaining a full-color copied image has been put into practical use, and as the color toner used for this method,
BACKGROUND ART Electrophotographic color toners (hereinafter, also simply referred to as color toners) in which colorants such as dyes and / or pigments of respective colors are dispersed in a binder resin are manufactured. However, conventional color toners have not always sufficiently satisfied various performances required for color toners. That is, the conventional color toner has the following problems. In case of multi-color overprinting due to insufficient light transmission, color reproduction becomes difficult and overhead projector (OHP)
A good transmission image cannot be obtained when the transparency for use is created. Poor spectral reflection characteristics, resulting in poor hue and hue. Light resistance and heat resistance are poor. Dye / pigment is transferred to the photoreceptor. Poor charging characteristics.

[0003]

SUMMARY OF THE INVENTION The object of the present invention is to solve the above-mentioned problems with conventional color toners, especially green color toners, and to stabilize clear, light-proof images free from fog. To provide a green toner for electrophotography.

[0004]

Means for Solving the Problems The inventors of the present invention have made extensive studies to achieve the above-mentioned object, and as a result, by using a dye having a specific structure as a coloring agent, the above problems have been solved. It has been known that an electrophotographic green toner can be obtained, and the present invention has been completed. That is, the present invention is
In the binder resin, in the electrophotographic color toner containing at least a colorant, as the colorant,
The present invention relates to an electrophotographic green toner containing a phthalocyanine dye represented by the following general formula (I) (Chemical Formula 3).

[0005]

[Chemical 3] (In the formula, R represents the following formula (Formula 4),

[0006]

[Chemical 4] The substitution position of the R group is 1 or 4 position, 5 or 8 position, 9 or 12 position, 13 or 16 position. Wherein each R 'is independently an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, or represents a hydrogen atom, -CH ₂ X are each independently
_{CH 2 -, - CH 2 CH} 2 CH 2 -, - CH (CH 3)
CH ₂ -, or an isomer thereof, n represents an integer of 0, Met represents a metal. ) What is used as a colorant in the present invention is a dye represented by the general formula (I), and as the unsubstituted alkyl group having 1 to 20 carbon atoms represented by R ′, a methyl group, an ethyl group, Propyl group, butyl group, hexyl group, i-propyl group, t-
Examples thereof include linear, branched or cyclic alkyl groups such as butyl group, 2-methylbutyl group, cyclopentyl group and cyclohexyl group. Further, as the substituted alkyl group having 1 to 20 carbon atoms, a hydroxymethyl group, a hydroxybutyl group,
Halogenation of hydroxyalkyl group such as hydroxyoctyl group, chloromethyl group, 2,2,2-trichloroethyl group, trifluoromethyl group, 1,1,1,3,3,3-hexafluoro-2-propyl group An alkyl group is mentioned.

Metals represented by Met include Zn and M
g, Si, Sn, Rh, Pt, Pd, Mo, Mn, P
b, Cu, Ni, Co, Fe, etc., as well as Al
Cl, InCl, FeCl, TiCl ₂ , SnCl ₂ ,
Also included are metal chlorides such as GeCl ₂ and metal oxides such as TiO, VO and MnO.

In the present invention, the dye represented by the above general formula (I) is used as a colorant, but it is also possible to use a mixture of two or more kinds thereof, and to improve the color,
It can also be used as a mixture with other colorants. Further, the content of such a colorant is preferably 0.1 to 40 parts by weight with respect to 100 parts by weight of the binder resin. If the content is too small, the coloring effect as green becomes poor,
On the other hand, if the amount is too large, the fixing property becomes poor, which is not preferable.

As a method for synthesizing the dye represented by the general formula (I), the following general formula (II)

[0010]

[Chemical 5] (In the formula, R ′, X and n have the same meanings as in the general formula (I).) And the following general formula (III) Met-X ₂ (III) (in the formula, Met Represents the same meaning as Met in the general formula (I), and X represents 1 such as halogen atom, acetate anion or oxygen.
Represents a valent or divalent ligand. ) 0.1-1.
A method in which a metal compound is used in an amount of 0 mol times in a solvent such as alcohol, alkylamine urea, halogenated hydrocarbon, or quinoline at a temperature of 80 to 230 ° C. for about 2 to 20 hours is used.

The binder resin for toner can be widely used including known ones, but colorless and transparent ones are preferable, for example, polystyrene, chloropolystyrene, poly-α-methylstyrene, styrene-chlorostyrene copolymer. Coal, styrene-propylene copolymer, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, styrene-vinyl acetate copolymer, styrene-maleic acid copolymer, styrene-methyl acrylate copolymer,
Styrene-acrylic acid esters such as styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer and styrene-phenyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer Styrene-methacrylic acid ester copolymers such as polymer, styrene-butyl methacrylate copolymer, styrene-phenyl methacrylate copolymer, styrene-α-chloromethyl acrylate copolymer and styrene-
Acrylonitrile-styrene resin such as acrylic acid ester copolymer (a homopolymer or copolymer containing styrene and / or styrene substitution product), vinyl chloride resin, styrene-vinyl acetate copolymer, rosin-modified maleic acid resin,
Examples thereof include phenol resins, epoxy resins, polyester resins, low molecular weight polypropylene, ionomer resins, polyurethane resins, silicone resins, ketone resins, ethylene-ethyl acrylate copolymers, xylene resins and polyvinyl butyral resins. Particularly preferable resins for carrying out the present invention include styrene resins, polyester resins, silicone resins, and epoxy resins. Further, the above resins are not limited to be used alone, but two or more kinds may be used in combination.

The charge control of the toner may be carried out by the binder resin and the dye / pigment itself, but if necessary, a charge control agent which does not cause a problem in color reproduction may be used together. Use a quaternary ammonium salt, a basic / electron-donating organic substance as the positive charge control agent, and a metal chelate, a metal-containing dye, an acidic or electron-withdrawing organic substance, etc. as the negative charge control agent. You can In addition, inorganic particles such as metal oxides or inorganic substances surface-treated with the organic substance may be used. These charge control agents may be used by being mixed and added to the binder resin, or may be used by being attached to the surface of the toner particles. The addition amount of the charge control agent is determined in consideration of conditions such as the chargeability of the binder resin, the content of the colorant, the manufacturing method, and the chargeability of other additives. -10 parts by weight is suitable.

Further, a solid electrolyte, a polymer electrolyte, a charge transfer complex, a conductor such as a metal oxide such as tin oxide, a semiconductor and / or a ferroelectric substance, a magnetic substance and the like are added to control the electrical properties of the toner. I can do things. In addition, various plasticizers, releasing agents and other auxiliaries can be added to the toner for the purpose of adjusting thermal characteristics, physical characteristics and the like. Addition amount is 0.1
10 parts by weight is suitable. Further, by adding fine particles such as TiO ₂ , Al ₂ O ₃ and / or SiO ₂ to the toner particles and coating the surface of the toner particles, the fluidity and aggregation resistance of the toner can be improved. The addition amount is preferably 0.1 to 10 parts by weight.

The toner production method of the present invention may be applied to various toner production methods that have been conventionally used. For example, the following examples may be mentioned as general production methods. First,
A resin and a colorant (such as a charge control agent in some cases) are uniformly dispersed with a ball mill, a V-type mixer, a Herschel mixer, or the like. Next, the dispersion is melt-kneaded with a double-arm kneader, a pressure kneader, or the like. A hammer mill, jet mill,
It is crushed by a crusher such as a ball mill, and the obtained powder is classified by an air classifier or the like. The obtained color toner can be mixed with a carrier to form a developer for electrophotography, and can be used for copying by a conventionally practiced electrophotographic method. As the carrier, it is preferable to use 10 to 100 parts of a magnetic material such as a known iron powder-based or ferrite-based carrier or a material coated on the surface thereof with respect to 1 part of the toner.

[0015]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to the examples. In the examples, "part" means "part by weight". Example 1 100 parts of unsaturated polyester, 3 parts of copper tetra-([alpha] -hydroxyethoxy) phthalocyanine and 1 part of zinc salicylate complex compound were melt-kneaded with a hot roll mill, cooled and coarsely crushed with a hammer mill, and then air jetted. Finely pulverized with a fine pulverizer according to the method. The obtained fine powder was classified, and a particle size of 5 to 25 μm was selected to obtain a toner. 4 parts of this toner was added to 100 parts of iron powder and mixed by a V-type mixer to obtain a developer. When this developer was used to make a copy on a dry plain paper electrophotographic copying machine, there was no fog,
A clear image was obtained with excellent spectral reflection characteristics. In addition, 20000 sheets were continuously copied using this developer, but the quality of the copied image did not deteriorate. The image densities after the initial copy and 20000 copies are 1.47 and
1.44, and the toner charge amount is 200
After 00 copies, -15.8μc / g and -16.9μ respectively
It was c / g, and the charge amount was stable. The light resistance of the obtained image was 6 to 7 grade. [Synthesis of copper tetra- (α-hydroxyethoxy) phthalocyanine] 3-hydroxyethoxyphthalonitrile 17
5 parts, 45 parts of copper acetate, 10 parts of diazabicycloundecene and 1000 parts of N, N-dimethylaminoethanol were reacted under reflux, and the obtained crystals were purified by a column to obtain 100 parts of the target compound.

Example 2 A styrene-n-butyl acrylate copolymer was used in place of the unsaturated polyester resin, and copper tetra- was used as a colorant.
The same procedure as in Example 1 was carried out except that (α-methoxy) phthalocyanine was used. As a result, a clear image having good spectral reflection characteristics without fog was obtained. The light resistance of the obtained image was 6 to 7 grade. [Synthesis of Copper Tetra- (α-methoxy) phthalocyanine]
3-Methoxyphthalonitrile 177 parts, copper chloride 33.6
Parts were reacted in 1000 parts of chlornaphthalene at 200 ° C. for 3 hours. The reaction solution was discharged into 10,000 parts of methanol to obtain 100 parts of the target compound.

Example 3 Using iron tetra- (α-methoxyethoxy) phthalocyanine as a colorant, a developer was prepared in the same manner as in Example 1,
When copying was performed on a transparency for OHP with a dry electrophotographic copying machine, a clear image having excellent transmittance characteristics without fog was obtained. The light resistance of the obtained image is 6 to 7.
It was class. Example 4 The procedure of Example 1 was repeated except that iron tetra- (α-n-octyloxy) phthalocyanine was used as the colorant. As a result, clear images with good fog and spectral reflectance characteristics were obtained. It was The light resistance of the obtained image was 6 to 7 grade.

Examples 5 to 22 Met, R'and n in the general formula (I) are used as colorants.
Used a phthalocyanine dye as shown in Table 1 (Table 1). When Examples 5 to 19 were carried out in the same manner as Example 1, clear images were obtained with good spectral reflection characteristics.
When Examples 20 to 22 were carried out in the same manner as Example 3, clear images were obtained with excellent transmittance characteristics.

[0019]

[Table 1]

[0020]

The green toner for electrophotography using the phthalocyanine dye of the present invention as a coloring agent has excellent compatibility between the dye and the resin, and a copy made using this toner has no fog. Further, it is possible to stably provide a clear image having excellent transmittance characteristics and excellent light resistance.

Claims (1)

[Claims] 1. A color toner for electrophotography, which comprises a binder resin and at least a colorant, and a phthalocyanine dye represented by the following general formula (I) (Chemical Formula 1) as the colorant. Characteristic green toner for electrophotography. [Chemical 1] (In the formula, R represents the following formula (Formula 2), and The substitution position of the R group is 1 or 4 position, 5 or 8 position, 9 or 12 position, 13 or 16 position. Wherein each R 'is independently an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, or represents a hydrogen atom, -CH ₂ X are each independently
_{CH 2 -, - CH 2 CH} 2 CH 2 -, - CH (CH 3)
CH ₂ -, or an isomer thereof, n represents an integer of 0, Met represents a metal. )