JPH02210459A - Toner - Google Patents

Abstract

PURPOSE:To improve electrostatic chargeability, environmental resistance (by which the amt. of electrostatic charges is made independent of environment), fog resistance and light resistance by blending a thermoplastic resin with a specified pigment. CONSTITUTION:A thermoplastic resin is blended with a pigment represented by formula I (where each of R1 and R2 is H, halogen, methyl, methoxy, nitro, amino, dimethylamino, hydroxy, acetyl or trihalogenomethyl). The pigment represented by the formula I is not known at all as a pigment for a color toner. The resulting toner has a stabilized amt. of electrostatic charges and hardly undergoes a change in electrostatic chargeability even at high temp. and humidity, an image is hardly fogged and the fading of the image is inhibited because of the superior light resistance of the toner.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a one-component or two-component developer for electrophotographic copying machines and printers.

Conventional Technology To obtain an image using an electrophotographic copying machine or printer, the surface of a photoreceptor, which is an image carrier, is first uniformly charged, and then this is exposed to light based on a pattern corresponding to the image on the original, or the output is The content of the image is drawn onto a photoreceptor with light to form an electrostatic latent image.

Next, the surface of the photoreceptor having this electrostatic latent image is developed (visualized) using a developing device, and the obtained toner image is transferred to a transfer material such as paper.

In such a developing device, a magnetic plano made of a magnetic carrier with toner attached to the surface is formed on the surface of the developing sleeve by magnetic force, and this is brought into sliding contact with the surface of the photoreceptor to develop an electrostatic latent image on the surface of the photoreceptor. make changes.

Conventionally, such a developer has an average particle size of 20 to 200 μm.
A mixture of a magnetic carrier having a particle size of about 1.0 m and a toner having an average particle size of about 5 to 20 m is used. Such toners typically contain a thermoplastic resin, a colorant, a charge control agent,
and a superplasticizer.

Problems to be Solved by the Invention Conventionally, as color toners in the auburn color toner, color toners containing quinacridone pigments or azo pigments as shown in the following formulas (■) (■) have been used. Are known. However, the chargeability of these color toners is subject to large fluctuations due to environmental changes such as temperature and humidity, and the prevention of fogging on images is still insufficient.

The object of the present invention is to develop a color toner that has extremely favorable physical properties as a color toner for developing electrostatic latent images by using a pigment with a completely different basic structure that has not been known as a pigment for color toners. It is something that was given.

Typical examples of such pigments include the following formulas (I) to (V
) are listed.

- to provide.

A unique means for solving the problems The present invention provides: (1) a thermoplastic resin and the following formula: The present invention provides a color toner for developing electrostatic latent images, which is characterized in that it contains a pigment represented by the following formula: acedel, meaning trihalogenomethyl.

The pigment represented by the above general formula used in the present invention has not been known at all as a pigment for color toners.

The color toner of the present invention is a pigment combination that exhibits excellent physical properties such as chargeability, environmental resistance (no change in charge amount due to environment), and fog resistance when actually used as a developer. The blending amount of thermoplastic resin 1.
The amount is 2 to 7 parts by weight per 00 parts. If the pigment content is less than 10% by weight, a sufficient color tone cannot be obtained as a toner, and if it exceeds 10% by weight, faithful gradation reproduction of the image becomes difficult and fixing performance deteriorates.

As other components such as binder resin used in the toner of the present invention, any of those conventionally used as components of known toners can be suitably used.

That is, as the binder resin, for example, styrene resin, (meth)acrylic resin, olefin resin, which is obtained by polymerizing the following monomers,
Amide resins, carbonate resins, polyethers, polysulfones, etc. may be used alone or in combination of two or more. Specifically, monomers used in the production of such resins include those listed below. Examples of vinyl monomers include styrene, 0-methylstyrene, m-methylstyrene, p-methylstyrene, 2.
4-dimethylstyrene, p-n-butylstyrene, p-
tert-butylstyrene, p-n hexylstyrene,
l) n-occlestyrene, pn-nonylstyrene,
p-n-dodecylstyrene, p-methkinstyrene, p
- Styrene and derivatives thereof such as methkinstyrene, p-phenylstyrene, p-chlorostyrene, and 3,4-dichlorostyrene, among which styrene is most preferred. Examples of other vinyl monomers include ethylenically unsaturated monoolefins such as ethylene, propylene, butylene, and isobutylene, vinyl ethers such as vinyl chloride, vinylidene chloride, vinyl bromide, fluorinated hinal ether, and vinyl isobutyl ether, and vinyl methyl Ketones, vinyl ketones such as vinylhexylketone, medylisobropenylketone,
Examples include N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, and N-vinylpyrrolidone, and vinylnaphthalenes. These vinyl monomers may be a single polymer or a copolymer of a plurality of monomers.Also, as a monomer for obtaining an amide resin, caprolactam, and as a tribasic acid, Terephthalic acid, isophthalic acid, adipic acid, maleic acid, succinic acid, sebadic acid, thioglycolic acid, etc. can be mentioned, and diamines include ethylenediamine, diaminoethyl ether, 1.4-aminobenzene, l4 Examples include -aminobutane.

To the toner of the present invention, a charge control agent is added for the purpose of increasing the amount of charge and improving the stability of electrostatic charge. Vinyl esters such as vinyl butyrate, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-ocdyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, propyl methacrylate, n-octyl methacrylate, methacrylate acid dodenle,
α-methylene aliphatic monocarboxylic acid esters such as 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, dietylaminoethyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, etc. (Meth)acrylic acid derivatives, vinyl methyl ether, and vinyl ether may also be used. As the charge control agent, either a positive charge control agent or a negative charge control agent can be used.

Among the charge control agents, representative ones that impart positive chargeability to the toner include, for example, amino compounds, quaternary ammonium compounds, alkylamides, phosphorus, and tungsten compounds. Typical examples that impart negative chargeability include naphthenic acid metal salts, metal salts of fatty acids, reaction products of salicylic acid and its derivatives and metal salts, and hydroquinaphthoic acid and its derivatives and metal salts. Examples include reaction products, electron-accepting compounds, and metal salts of monoazo dyes. These charge control agents are usually thermoplastic resin 1
It is mixed and dispersed at a ratio of 1 to 20 parts by weight per 00 parts by weight. They can be used alone or in combination of two or more. The charge control agent may be colorless or colorless, and may have a color that does not interfere with the color reproducibility of the coloring material.

Furthermore, other additives, such as waxes, may be added to the toner of the present invention, if necessary.

As waxes, waxes made of low molecular weight olefin polymers can be used.

The low molecular weight olefin polymer is an olefin copolymer containing monomers and has a low molecular weight. Examples of low molecular weight olefin polymers include low molecular homopolymers, copolymers, or modified products thereof of the formula: For example, in addition to low molecular weight polyethylene, polypropylene, α- or β-polybutylene, ethylene-propylene copolymer, polyethylene wax, oxidized polyethylene, and chlorinated products, ethylene or propylene-based materials, vinyl acetate, maleic anhydride, acrylic acid, etc. or its ester, methacrylic acid or its ester, acrylamide,
Random copolymers modified with one or more other ethylenically unsaturated monomers such as methacrylamide, acrylonitrile, methacrylonitrile, etc.
CO to C72) saturated fatty acid amides, unsaturated fatty acid amides and hydroginate fatty acid amides, N-methylol fatty acid amides, N,N'-styrene fatty acid amides, N,N'-
IIJ fats such as amide waxes such as ethylene fatty acid amide, dialkyl ketones of higher fatty acids, waxy aliphatic amines, imides, glycerides (acylglycerin),
- Esters such as alcohol fatty acid ester, glycerin fatty acid ester, glycol fatty acid ester, solhitan fatty acid ester, voriquinedylene fatty acid ester, phthalic acid ester, calcium stearate,
Alkali metal salts of higher fatty acids such as aluminum stearate, magnesium stearate, and calcium palmitate, metal salts such as alkaline earth metal salts, zinc salts, and aluminum salts; hydrazides of higher fatty acids such as palmidic acid hydrazide and stearic acid hydrazide; Low molecular weight p-hydroxyanilide of higher fatty acids such as p-hydroxyanilide of myristylenic acid, p-hydroxyanilide of stearic acid, β-diethyaminoeloch copolymer or graft copolymer of lauric acid. are used.

Other examples include naturally occurring waxes such as vegetable waxes, animal waxes, solid fats, and mineral waxes, waxes made of higher fatty acids or their derivatives, candelilla wax, carnauba wax, rice wax, and wood waxes. Plant-based waxes such as wax, palm wax, auriculie wax, sugarcane wax, esparto wax, and park wax; animal-based waxes such as beeswax, lanolin, and squeeze wax; mineral waxes such as montan wax, oshikerite, and selenone; and paraffin wax. , microcrystalline wax, petroleum wax such as petrolactam, synthetic hydrocarbons such as Fisonyer-Tropsch wax (Zazol wax), modified waxes such as Monkun wax derivatives, paraffin wax derivatives, microcrystalline wax derivatives, hardened Himashiura, Hydrogenated waxes such as hydrogenated castor oil derivatives, 12-hydroxystearic acid, its amides, esters, delester hydrochloride such as metal soaps, and β-node of higher fatty acids such as stearic acid β-diethyaminoethyl ester hydrochloride. Ethylaminoethyl ester hydrochloride; higher fatty acid amide-polmaldehyde condensates such as stearic acid amide-polmaldehyde condensates and palmidic acid amide-polmaldehyde condensates; petroleum residues such as asphalt and giltstone;
Rubbers such as nitrile rubber and chlorinated rubber, synthetic hydrocarbons such as Fischer Tropune wax and derivatives, halogenated hydrocarbons such as chlorinated paraffin and chlorinated propylene, hardened caster curves, hardened curves such as hardened tallow oil, etc. These can be used alone, in combination, or in combination with the low molecular weight olefin polymer.

A fluidizing agent may be further added to the toner of the present invention.

As the fluidizing agent, silica/aluminum oxide, titanium oxide, warp/aluminum oxide mixture, silica/titanium oxide mixture, etc. are used. The fluidizing agent may be subjected to hydrophobization treatment using a coupling agent or a surfactant.

Such coupling agents include coupling agents such as so-called silane coupling agents, titanium coupling agents, aluminum coupling agents, zircoaluminum coupling agents, or noricorn oil alone or in combination of two or more. It can be used as

In addition, as surfactants, aliphatic amine salts, quaternary ammonium salts, alkylpyridinium salts, benzyl halide type cationic surfactants, fatty acid salts, sulfated oils, sulfated esters 411, sulfated amide oils, and olefins. sulfate ester salts, fatty alcohol sulfate ester salts,
Alkyl sulfate salts, fatty acids, ethyl sulfonates, alkyl sulfonates, alkylnaphthalene sulfonates, alkylbenzene sulfonates, mixtures of naphthalene sulfonates and formalin, succinate sulfonates, phosphate ester salts, etc. Anionic surfactants, polyogine ethylene alkyl ethers,
Polyquine ethylene alkylphenol ethers, polyoxyethylene alFe-Zn ferrite fine particles
500MFP-2 (manufactured by TDK Corporation) Carbon black (manufactured by Mitsubishi Chemical Industries, Ltd., AM#8) 2
The two materials were thoroughly mixed using a Hennoermi grinder and ground. Next, the cylinder part was heated to 180°C, and the cylinder head part 17
0°C (: Melt,
Kneaded. The kneaded product was left to cool, then coarsely ground using a feather mill, further finely ground using a jet mill, and then classified using a classifier to obtain a carrier having an average particle size of 60 μm.

[Evaluation Method] The properties of the toners obtained in Examples and Comparative Examples were evaluated by the following method. The toner used in the evaluation was one in which 100 parts by weight of the toner was post-treated with 041 parts by weight of Colloidal Lenorica R-972 (manufactured by Nippon Aeronol Co., Ltd.).

Kill esters, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters, ethylene oxide of fatty alcohols, nonionic surfactants such as polyethylene glycol, imidacillin derivatives, higher alkylaminos, sulfate esters, phosphate esters Ampholytic surfactants such as surfactants, sulfonic acid surfactants, and oil-soluble surfactants can be used alone or in combination of two or more.

Other mold release agents such as polypropylene and polyethylene, etc.
Known additives may also be blended.

To produce the toner of the present invention, the above-mentioned components are mixed,
Dispose of using conventional methods.

Next, the present invention will be explained in more detail with reference to examples and proportions.

Reference Example (Manufacture of Carrier) Sphere: Part by Weight Polyester Resin 100 (Softening Point 123°C, Glass Transition Point 65°C, AV23.0HV40) Charge Amount (Q/M) 2g of surface-treated toner and 28g of the carrier 5
Place it in a 0cc plastic bottle and place it on a rotating stand and rotate it at 120 rpm.
The initial charge amount after stirring for IO minutes was measured.

Environmental resistance: ◎, 10-15% for those with a difference of 0-10% between the charge amount under high temperature and high m (30℃, 85%) and the charge amount under normal temperature and normal humidity.
Those with 15% to 20% were evaluated as △, and those with 20% or more were evaluated as ×. Δ or more is practical.

A two-component developer was prepared by mixing the toner obtained in the Kafuri Example or Comparative Example and the carrier produced in the Reference Example at a ratio of toner/carrier of 7/93. Using this developer, EP-570Z was used for Example 1.3 and Comparative Example 1.
(manufactured by Minolta Camera Co., Ltd.), and for Example 2.4 and Comparative Example 2, an initial image output evaluation was performed using EP-470Z (manufactured by Minolta Camera Co., Ltd.).

Regarding fog in "Image" 2, toner fog on a white background image was evaluated and ranked. A rank of △ or lower is "2" and is usable for practical use, but a rating of 0 or higher is desirable.

Example 1 Polyester resin 100 parts by weight Mn=5
300, Mw/Mn=25, AV25.0HV38, softening point 120°C, glass transition point 65°C 3 parts by weight of the above compound (I) The above raw materials were thoroughly mixed in a Hennermigizer and kneaded in a twin-screw extruder. After that, it was cooled. Coarsely crush the mixed material, then crush it with a shot crusher, and then classify it with a wind classifier to give a size of 5 to 25μ.
A magenta toner of m (average particle size: 13.5 μm) was obtained.

The evaluation results of the toner are shown in Table 1.

Example 2 Styrene-acrylic copolymer 100 parts by weight fln=
12000, Kl w / Mn = 20 Softening point 13
2°C1 Glass transition point 60°C The above compound (■)
3 parts by weight Hontron P-514 parts by weight (manufactured by Orient Chemical Co., Ltd.) The above raw materials were treated in the same manner as in Example I to obtain a red toner. The results are shown in Table 1.

Comparative Example 1 A magenta toner was obtained in the same manner as in Example 1 except that compound (V) was used instead of compound (1) as the pigment.

The results are shown in Table 1.

Comparative Example 2 Compound (Vl) instead of compound (1'I) as pigment
A violet toner was obtained in the same manner as in Example 1 except that . The results are shown in Table 1.

The above compound (■): 3 parts by weight Bontron P-512 parts by weight (manufactured by Orient Chemical Co., Ltd.) The above raw materials were treated in the same manner as in Example 1 to obtain a violet toner. The results are shown in Table 1.

Example 3 Styrene-acrylic copolymer 100 parts by weight Mn=7
800, FJAw/Mn=2.5 Softening point 105°C, Glass transition point 65°C The above compound (■) 3 parts by weight Bontron E-812 parts by weight (manufactured by Orient Chemical) The above raw materials were treated in the same manner as in Example 1. , got the red toner. The results are shown in Table 1.

Example 4 Polyester tree MW 100 parts by weight Mn
=3000, Mw/Mn=2.8, A, V9.0HV3
7. Softening point: 92° C. Glass transition point: 60° C. Effects of the Invention The color toner of the present invention has a stable charge amount and shows little change in chargeability even under high temperature and high humidity conditions. Furthermore, since the image has less fog and is excellent in light resistance, the image is less likely to fade.

Patent applicant: Minolta Camera Co., Ltd.

Claims (1)

[Claims] (1) Thermoplastic resin and the formula below: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 and R_2 each independently represent hydrogen, halogen,
Methyl, methoxy, nitro, amino, dimethylamino,
A color toner for developing electrostatic latent images, characterized in that it contains a pigment represented by: hydroxy, acetyl, trihalogenomethyl.