JPS59195663A - Developer - Google Patents

Abstract

PURPOSE:To stabilize the extent of electrostatic charge caused on the surfaces of toner particles in a developer, to make the distribution of the extent of triboelectric charge sharp and uniform, and to control the extent of electrostatic charge to that suitable for a developing system used by adding phenothiazine or a phenothiazine deriv. to the developer as a positive charge controller. CONSTITUTION:Any compound represented by formula I can be used as a deriv. having phenothiazine as the skeleton. In the formula, each of R1, R2 and R3 is H, halogen, alkyl, alkenyl, alkynyl, alkoxy, ester, alkoxycarbonyl, phenyl, substituted phenyl, hydroxy, mercapto, alkylmercapto, amino, acyl, acylamino, nitro, imino, phenylimino, cyano, substituted azo, diazoamino, ureido, oxo or a heterocyclic ring contg. N, S or O. When phenothiazine or said phenothiazine deriv. is contained in a developer, the desired amount is 0.5-50pts.wt. per 100pts.wt. resin in the toner.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a developer used in electrophotography, electrostatic printing, etc., and particularly relates to a positively charged developer.
A number of methods are known, such as those described in No.

Further, a developing method for visualizing an electrical latent image using a developer (generally toner) is described, for example, in U.S. Patent No. 2.874.0.
No. 63, No. 2,618,552, No. 2,221,77
No. 6.

Various methods are known, as described in the specifications of No. 3,909,258.

As toners applied to these developing methods, fine powders in which dyes and pigments are dispersed in natural or synthetic resins have conventionally been used. For example, particles obtained by dispersing a colorant in a binder resin such as polystyrene and pulverizing the particles to about 1 to 30 microns are used as toner. As the magnetic toner, one containing magnetic particles such as magnetite is used. In the case of a system using a so-called two-component developer, the toner is usually mixed with carrier particles such as glass beads or iron powder. Examples of positive charge control agents used in such a dry developing toner include, for example. Generally amino compounds, quaternary ammonium compounds and organic dyes, especially basic dyes and their salts. Common positive charge control agents include benzyldimethyl-hexadecyl ammonium chloride, decyl-trimethylammonium chloride, difusine base, nigrosine hydrochloride, safranin r, and crystal violet.

In particular, nigelsine base and nigrosine hydrochloride are often used as positive charge control agents. These are usually added to a thermoplastic resin, heated and melted and dispersed, and then finely ground to adjust the particle size to an appropriate particle size as necessary before use.

However, these dyes used as charge control agents have complex structures, inconsistent properties, and poor stability. In addition, decomposition or deterioration occurs due to thermal crosstalk, mechanical shock, friction, changes in temperature and humidity conditions, etc., resulting in a phenomenon in which charge controllability is reduced.

Therefore, when a toner containing these dyes as a charge control agent is used for development in a copying machine, as the number of copies increases,
The dye decomposes or changes in quality, causing toner deterioration during durability.Many of the substances generally known to be positively chargeable are dark in color and cannot be incorporated into bright chromatic color developers. be.

Moreover, many of the positive charge controllable dyes are hydrophilic, and due to poor dispersion in these resins, the dyes are exposed on the toner surface when the toner is crushed after melt mixing. When these toners are used under high humidity conditions, they have the disadvantage that good quality images cannot be obtained because these dyes are hydrophilic.

In this way, when conventional dyes with positive charge control properties are used in the door, the toner particles are dispersed between the toner particles, between the toner and the carrier, or between the toner and the toner carrier such as a sleeve. The amount of charge generated on the particle surface becomes uneven, causing problems such as developer overflow, toner scattering, and carrier contamination.These phenomena become particularly noticeable when a large number of copies are made, and In fact, the results are not suitable for copying machines.Furthermore, under high humidity conditions, the transfer efficiency of the toner image decreases significantly, making the toner image unsuitable for use.

Furthermore, even at room temperature and humidity, when the toner is stored for a long period of time, K
, often causes toner aggregation and becomes unusable.

That is, an object of the present invention is to maintain a stable amount of frictional bands between toner particles, between toner and carrier, or between toner and a toner carrier such as a sleeve in the case of component development, and to reduce the amount of frictional charge. The object of the present invention is to provide a developer which has a sharp and uniform distribution and can be controlled to a charge amount suitable for the developing system used.

Still another objective is to develop faithfully to the latent image and to prevent toner from adhering to the background area during development, i.e., toner scattering around capri and etch areas of the latent image. The object of the present invention is to provide a developer which can obtain high image density and have good halftone reproducibility.

Still another object is to provide a developer that maintains its initial characteristics even when the developer is used continuously over a long period of time, and that causes no toner aggregation or change in charging characteristics.

Another objective is to develop a developer that reproduces stable images that are not affected by changes in temperature and humidity, especially a developer that has high transfer efficiency and does not cause scattering or transfer dropouts during transfer at high or low humidity. On offer.

Still another object is to provide a developer with excellent storage stability that maintains its initial characteristics even during long-term storage.

Still another object is to provide a bright chromatic developer.

The present inventors have solved the various problems associated with the conventional positively charged toner as described above, and have developed an electrophotographic method that is uniformly and strongly positively charged, visualizes a negative electrostatic charge image, and produces a high-quality image. As a result of intensive research aimed at providing a developer for use in electrophotography, it was discovered that by incorporating phenothiazine or a phenothiazine derivative into the developer as a positive charge control agent, an electrophotographic developer exhibiting various excellent properties was obtained. Found 0
Add Mori to the developer toner, binder resin, colorant, if necessary.
Figure 1 is an explanatory diagram showing an example of a combination of toner components using additives etc. Of course, the above positive charge control agent phenothiazine itself is also effective, but when handling and handling and charging stability are taken into consideration. , derivatives thereof are preferred.

As the derivative having a phenothiazine skeleton, all derivatives represented by the following general formula can be used.

(Here, RI HR2+ R3 is hydrogen,) ・Rogen,
Alkyl group, alkenyl group, alkynyl group, alkoxy group, ester group, alkoxycarbonyl group, phenyl group, phenyl group, hydroxy group, methane group,
Alkyl mercapto group, amino group, acyl group, acylamino group, nitro group, imino group, phenylimino group, cyano x, substituted aso group, cyaso amino group, ureido group, oxo group or any heterocycle containing nitrogen, sulfur or oxygen represents a substituent. ) The charge control effect of these substituents on the phenothiazine derivatives basically depends on the phenothiazine skeleton, and the color can be changed by selecting various substituents.

They have different melting points and can be selected according to needs.

Methods for incorporating at least one of these phenothiazine or phenothiazine derivatives into the developer include a method of adding it inside the toner particles (internal addition) and a method of adding it to the outside (external addition).

When internally added, the content is 100% of the binder resin of the toner.
It is desirable to use 0.5 to 50 parts by weight.

In addition, when externally added, 0.0 parts by weight per 100 parts by weight of resin.
1 to 40 parts by weight is desirable.

As the binder resin of the toner, monopolymers of styrene and its substituted products such as polystyrene, poly-P-chlorostyrene, and polyvinyltoluene; styrene-P-chlorostyrene copolymer, styrene-propylene copolymer, nuterene-vinyl Toluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer,
f-rene-ethyl acrylate copolymer, styrene-methyl acrylate copolymer, styrene-octyl acrylate co-i11[, styrene-methacrylic dispersion methyl copolymer,
Styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-alpha chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene/:/-hinyl methyl ether copolymer , styrene-vinylethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-
Styrenic copolymers such as maleic y-co-x combinations, styrene-maleic acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride,
polyvinyl acetate, polyethylene, polypropylene, polyester, polycrethane,
Polyamide, epoxy resin, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax nat, alone or Can be used in combination.

Any suitable pigment or dye can be used as a colorant in the toner of the present invention. For example, carbon black,
There are known dyes and pigments such as iron black, phthalocyanine blue, ultramarine blue, quinacridone, and benzidine yellow.

When the toner is a magnetic toner, conventional materials such as ferromagnetic elements and alloys and compounds containing them such as iron, cobalt, nickel, and manganese such as magnetite, hematite, and ferrite, and other ferromagnetic alloys are used. It may also contain magnetic powder known as a magnetic material.

Additives may be mixed with the toner as necessary. Such additives include, for example, lubricants such as d-teflon, zinc stearate, fixing aids (such as low molecular weight polyethylene), flow agents, anti-caking agents (such as colloidal silica), and conductive agents. Metal oxides such as tin oxide can be used as the properties imparting agent.

It is also possible to have the above toner structure supported on the wall material, the core material, or both of them in the microcapsule toner.

The toner may be mixed with a carrier particle such as iron powder, glass beads, nickel powder, or ferrite powder, if necessary, and used as a developer for an electrical latent image.

Toner is produced by thoroughly kneading the constituent materials using a thermal kneader such as a hot roll, niegu, or extruder, and then mechanically crushing and classifying the materials, or by dispersing the materials in a binder resin solution. A toner manufacturing method, etc., in which a toner is obtained by spray-drying, or a toner is obtained by mixing a predetermined material with a monomer to constitute a binder resin, and then polymerizing the emulsified suspension. Each method can be applied. The developer of the present invention can be applied to various developing methods. For example, a magnetic brush development method, a cascade development method, a method using an electrocardiographic magnetic toner described in U.S. Pat. Method using JP-A-1987
-42141 publication, 55-18656 publication, 55-18656 publication
4-43027, etc., the fur brush development method, the powder cloud method, the impression development method, etc.0 Also, when holding the developer in a developer carrier such as a sleeve, magnetic force is used. , Coulomb force, electrostatic force, image force, mechanical force, etc.0 Examples will be described below, but the present invention is not limited thereto in any way. Parts by weight.

[Example 1] 1000 parts of an iron powder carrier was mixed with 100 parts of a toner having an average particle size of 8 μ and made of 2 parts of phenothiazine, and a developer was prepared. And so.

When this developer was used to print an image on a Canon NP-8500 copying machine, a good image with a bright blue color and no fog was obtained, and the image did not change even after printing 100,000 copies. There wasn't.

In addition, under a high humidity environment of 65℃, 901 (H), and 15℃
Even under low humidity conditions such as , 1Q% RH, images with almost no difference from normal humidity were obtained.

[Example 2] When images were produced using a Canon NP-200 copying machine modified to form a negative charge latent image using toner consisting of Even after image printing, the condition continued to be good.

Also, under high humidity conditions of 65°C and 90% RH, and at 15°C.

Even under the low humidity of 10% RH, there is almost no difference from normal humidity.
i! An iI image was obtained.

[Example 6] An experiment was conducted in the same manner as in Example 1, except that 10-phenodeazinylglobylamine was used in place of the phenothiazine used in Example 1, and good results were obtained.

[Example 4] Good results were obtained in the same manner as in Example 1 except that β-('1O-(3-chlorophenothiazinyl)globimenimidoyl]-dimethylamine hydrochloride was used. It was done.

[Example 5] N-(3-(2'-methoxy-phenothiazine-101)
-yl)-2-methyl-propyl)-N-methyl-〇-
Example 2 was carried out in the same manner as in Example 2, except that 15 parts of penzoyl hydroxylamine was used, and similarly good results were obtained.

[Comparative Example 1] An experiment was conducted in the same manner as in Example 1 except that the phenothiazine derivative in Example 1 was not used.
[Comparative Example 2] An experiment was conducted in the same manner as in Example 2, except that the phenothiazine derivative in Example 2 was not used, and an image with a large amount of capri was obtained. After obtaining 500 consecutive images,
I could only get very faint images.

[Brief explanation of the drawing]

FIG. 1 is an explanatory diagram showing an example of a combination of toner components.

Claims (1)

[Claims] A developer containing a phenothiazine or a phenothiazine derivative.