JPS61236556A - Electrostatic charge image developing toner - Google Patents

Abstract

PURPOSE:To obtain stable triboelectrification quantity and to keep its distribu tion sharp and uniform by incorporating triarylstibine oxide as a tribo electrification controller. CONSTITUTION:Triarylstibine oxide (TASO) is incorporated as a tribo electrification controller, it is stale thermally and for a long period, low in hygroscopicity and it has high triboelectrification control performance and accordingly the addition of it to a toner permits triboelectrification quantity between particles to be uniformed, triboelectrification to be easily controlled and scattering and deterioration of triboelectrification quantity due to the degra dation of it during its use to be prevented, the toner to be maintained stable, the toner to be prevented from operation trouble, such as development fog, scattering of powder and staining of equipment and from storage trouble such as toner flocculation, blocking, lowering of fluidizing temp., accordingly, the toner to be stored for a long period and the obtained toner image to be im proved in abrasion resistance, fixability and adhesion of the image. Further, since occurrence of less color tone trouble due to its addition permits a superior color image to be formed.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a new toner for developing electrostatic images in electrophotography, electrostatic recording, electrostatic printing, and the like.

[Conventional technology]

Conventionally, as an electrophotographic method, U.S. Patent No. 2,217゜68
1, Special Publication No. 42-23910, and Special Publication No. 43
Various methods are described in Japanese Patent No. 24748, etc., but in short, these methods apply a uniform electrostatic charge on a photoconductive insulating layer and irradiate the insulating layer with a light image to generate static electricity. An electrostatic latent image is formed, and then this latent image is developed and visualized using a fine powder called toner using the technology, and after transferring a starch image to paper or the like as necessary, it is fixed by heating, pressure, or solvent vapor. This is what we do.

The developing methods applied to these electrophotographic methods include:
Broadly speaking, there are dry development methods and wet development methods. The former method is further divided into a method using a two-component developer and a method using a -component developer. Two-component developing methods include:
Magnetic brush method using iron powder carrier, beads and
There are a cascade method using a carrier, a fur brush method using fur, etc.

In addition, those belonging to the -component type development method include a powder cloud method in which toner particles are sprayed, and a contact development method (contact development, or (also referred to as toner development), jumping development method in which toner particles are not brought into direct contact with the electrostatic latent image surface, but are charged and flown toward the latent image surface by the electric field of the electrostatic latent image; and magnetic conductive method. There is the MagneDry method, which develops by bringing a toner into contact with the electrostatic latent image surface.

Conventionally, toners used in these development methods are fine powders in which dyes and pigments are dispersed in natural or synthetic resins. Particles obtained by pulverizing the particles to about 1 to 30 particles 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 and iron powder. Further, the toner is made to have a positive or negative charge depending on the polarity of the electrostatic latent image to be developed.

In order to make the toner hold an electric charge, it is also possible to use the triboelectricity of the resin that is a component of the toner, but since the toner's chargeability is small with this method, the image obtained by development is prone to fogging and is unclear. Become something. Therefore, in order to impart desired triboelectrification properties to toners, dyes and pigments that impart electrostatic properties, as well as charge control agents, are added.

Charge control agents known in the art today include the following:

(1) The following substances can be used to control the toner to be positively charged.

Nicrosine, azine dyes containing carbon a2-1B alkyl groups (Japanese Patent Publication No. 42-1827), basic dyes (e.g. C,I-Ba5ic Yellow 2 (C,
1,4100G), C, 1, Ba5ic Yellow
3, C,1,Ba5ic Red l (C,1
゜45180), C,1,Ba5ic Red 9 (
C,1,42500), C,I.

Ba5ic Violet I (G, 1.42535
), C,1,l1iasicViolet 3
(C,1,42555), C,1,Ba5i
c Violet.

1G (C, 1, 45170), C, 1, Ba5ic V
iolet 14 (C, I.

42510), C, r, Ba5ic Blue 1
(C,1,42G25),C,I.

Ba5ic Blue 3 (C, 1, 51005)
, C,1,Ba5ic Blue5 (C,!, 4
214G), C,1,Ba5ic Blue 7 (
(Nee I.

42595), C,1,Ba5ic Blue 9 (
C, 1, 52015), c, r.

Ba5ic Blue 24 (C, 1, 52030)
,C,1,Ba5ic Blue25 CC,1,52
025), C,1,Ba5ic Blue 2B
(C-I.

44045), C,1,Ba5ic Green 1
(C,1,4204G), C,1,Ba5ic Gr
een 4 (G, 1.42 (100), etc.), lake pigments of these basic dyes (as lake agents,
phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.),
C:, I, 5olvent Black 3 (C.

1, 213150), Hansa Yellow G (C, 1, 1
1880), C.

1, Mordant Black 11,
C, 1, Pigment Black 1, Gilt Night, Asphalt, etc.

Quaternary ammonium salts, such as benzyl-dimethyl-hexadecyl ammonium chloride, decyl-trimethyl ammonium chloride, organotin compounds such as dibutyltin oxide, metal salts of higher fatty acids, glass, mica,
Inorganic fine powder such as zinc oxide, metal complexes such as EDTA and acetylacetone, vinyl polymers containing amide 7 groups,
Polyamine resins such as condensation polymers containing amide 7 groups.

(2) The following substances can be used to control the negative chargeability of toner.

Metal complex salts of monoazo dyes described in Japanese Patent Publications Nos. 41-20153, 43-27598, 44-8397, and 45-28478.

Dyes and pigments such as nitrofumic acid and its salts or C,1,14845 described in JP-A No. 50-133338, JP-B No. 55-42752, JP-B No. 58-4150
No. 8, Special Publication No. 59-7384, Special Publication No. 513-738
Metal complexes such as C01Cr and Fe of salicylic acid, naphthoic acid, and guicarboxylic acid described in No. 5, etc., sulfonated copper phthalocyanine pigments, nitro groups, styrene oligomers into which halogens have been introduced, chlorinated paraffins, melamine resins, etc.

Many of these charge control agents are derived from dyes and pigments.
Generally, they have a complex structure, and many of them have strong coloring properties.

Recently, there are some newly proposed products that are different from these, but none have superior overall performance to dyes and pigments, and examples of dyes and pigments still being used are still unsatisfactory. Most of them are.

These are usually added to a thermoplastic resin, thermally melted and dispersed, finely pulverized, and adjusted to an appropriate particle size as required before use.

However, these dyes used as charge control agents have a complex structure, inconsistent properties, and poor stability, and are susceptible to decomposition during thermal kneading and mechanical impact.

It is easily decomposed or deteriorated due to friction, changes in temperature and humidity conditions, etc., and tends to cause a phenomenon in which charge controllability is deteriorated.

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 charge control agent decomposes or changes in quality, which may cause deterioration of the toner during durability.

Furthermore, since it is extremely difficult to uniformly disperse these charge control agents in thermoplastic resins, they have the fatal drawback of causing a difference in the amount of frictional charge between toner particles obtained by pulverization. are doing. For this reason, various methods have been used in the past to achieve more uniform dispersion. However, unreacted fatty acids or salt dispersion products are often
It is exposed on the surface of the toner and contaminates the carrier or toner carrier, causing low fluidity of the toner, fogging, and a decrease in image density. Alternatively, in order to improve the dispersion of these charge control agents into the resin, a method has also been adopted in which charge control agent powder and resin powder are mechanically pulverized and mixed in advance and then hot melt-kneaded. but,
The inherent poor dispersion cannot be avoided, and the current situation is that sufficient charge uniformity has not yet been obtained for practical use.

Further, most of the substances generally known as charge control agents have a dark color and cannot be incorporated into a bright chromatic developer.

In addition, many charge control agents are hydrophilic, and due to poor dispersion in these resins, the dye is exposed on the toner surface when it is crushed after melting and mixing, and when the toner is used under high temperature conditions. However, since these charge control agents are wood-philic, they have the disadvantage that good quality images cannot be obtained.

In this way, when conventional charge control agents are used in toner,
Between toner particles, between toner and carrier, between toner and toner carrier such as a sleeve,
This causes variations in the amount of charge generated on the surface of toner particles, which tends to cause problems such as development fog, toner scattering, and carrier contamination, and these problems become noticeable when copying is repeated many times. The result is practically unsuitable for copying machines.

Furthermore, under high humidity conditions, the transfer efficiency of toner images decreases significantly, making many toner images unusable.Even at room temperature, when the toner is stored for a long time, the charge used Due to the instability of the control agent, it often undergoes deterioration and becomes unusable due to poor charging properties.

Furthermore, when conventional charge control agents are used in toners, long-term use can cause the charge control agents to adhere to the surface of the photoreceptor or promote toner adhesion, which may adversely affect Nl image formation (filming phenomenon). ), those that cause scratches on the surface of the photoreceptor or cleaning members such as cleaning blades, or those that accelerate wear of these members, etc., have a negative effect on the cleaning process of copying machines.

Furthermore, when conventional charge control agents are used in toner, many of them have a large effect on the thermal melting properties of the toner and reduce fixing performance.In particular, they worsen offset resistance at high temperatures, and when heat roll fixing There are some cases where the transfer material increases the clinging property of the roller to the roller and reduces the durability life of the roller.

As described above, conventional charge control agents have many drawbacks.
There is a strong demand in the technical field to improve these.
Although many improved techniques have been proposed so far, the reality is that no one has yet been found that is comprehensively satisfactory for practical use.

[Problem that the invention seeks to solve]

The object of the present invention is to provide a new technique for toner charge control that overcomes these drawbacks.

An object of the present invention is to stabilize the triboelectric charge between toner particles, between a toner and a carrier, or between a toner and a toner carrier such as a sleeve in the case of -component development, and to have a sharp triboelectric charge distribution. The purpose of the present invention is to provide a developer that has a uniform charge and can be controlled to have a charge amount suitable for the developing system used.

Still another object is to develop a developer that is faithful to the latent image and to perform the transfer, that is, without toner adhesion in the background area during development, without fogging or toner scattering around the edges of the latent image. High image density can be obtained,
To provide a developer with 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 unaffected by changes in temperature and humidity, especially a developer with high transfer efficiency that prevents scattering and transfer failure during transfer at high humidity and low humidity. On offer.

Still another object is to provide a bright chromatic developer.

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 developer that does not stain, abrade, or scratch the electrostatic latent image surface and is easy to clean.

Still another object is to provide a developer that has good fixing properties, particularly a developer that does not have problems such as high-temperature offset.

[Means for solving problems]

That is, the present invention is characterized by a developer containing triarylstibine oxide.

The present inventors have discovered that triarylstibine oxide is thermally stable for one hour, has low hygroscopicity, and is a high-quality charge control agent that provides a developer with excellent electrophotographic properties when included in a developer. I discovered that.

The aryl group constituting the compound of the present invention is preferably a phenyl group or a naphthyl group that may have a substituent, and typical examples of the triaryl oxide compound of the present invention include: There are the following:

H3 H3 These compounds are synthesized by known methods.

That is, it can be obtained by suspending the corresponding doaryrylstivine in a potassium hydroxide solution and oxidizing it with hydrogen peroxide while cooling.

For example, compound example (1) is synthesized as follows.

P-chlorotoluene is reacted with metallic magnesium in ether, Grignard reagent is gradually added, and after a sufficient reaction, it is filtered to obtain tritolylantimony. Compound Example (1) is obtained by suspending this in a potassium hydroxide solution and oxidizing it with hydrogen peroxide while cooling.

Generally, the above compound has an average particle size of lθ to 0. O1μ.

In particular, it is preferable to use the particle size in the range of 5 to 0.1 JL for toner adjustment.

1: Methods for incorporating the combination compound into the developer include a method of adding it inside the developer and a method of adding it externally. When internally added, the amount of these compounds used depends on the type of stone resin,
It is determined by the toner production method including the presence or absence of additives used as necessary and the dispersion method, and is not uniquely limited, but preferably the binder resin 100
0.1 to 20 parts by weight (more preferably 0 parts by weight)
．． It is used in a range of 5 to 10 parts, II [parts].

In addition, when externally added, 0.0 parts by weight per 100 parts by weight of resin.
1 to 10 parts by weight is preferred.

Furthermore, conventionally known charge control agents can be used in combination with the charge control agent of the present invention.

Coloring agents used in the present invention include carbon black, lamp black, iron black, ultramarine blue, nigrosine dye, aniline blue, phthalocyanine blue, phthalocyanine green, /\nthe yellow G, rhodamine 6G lake,
Calco oil blue.

chrome yellow, quinacridone, benzidine yellow,
Any conventionally known dyes and pigments such as rose bengal, triallylmethane dyes, heptanoazo dyes, disazo dyes and pigments can be used alone or in combination.

The binder resin used in the present invention includes polystyrene,
Monopolymers of styrene and its substituted products such as polyp-chlorostyrene and polyvinyltoluene; styrene-p-chlorostyrene copolymers, styrene-propylene copolymers, styrene-vinyltoluene copolymers, Styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate (polymer, styrene-methyl methacrylate) Copolymer, styrene-dityl methacrylate copolymer.Styrene-butyl methacrylate copolymer, styrene-α-
Methyl chlormethacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-
butadiene copolymer, styrene-isoprene copolymer,
Styrenic copolymers such as styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene/7-maleic acid ester copolymer; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, Vinyl acetate, polyethylene, polypropylene, polyester, polyurethane, polyamide, epoxy resin, polyvinyl butyral, polyacrylic resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin,
Examples include chlorinated paraffin and paraffin wax, which can be used alone or in combination.

In particular, as binder resins suitable for pressure fixing, the following can be used alone or in combination.

Polyolefin (low molecular weight polyethylene, low molecular weight polypropylene, polyethylene oxide, polytetrafluoroethylene, etc.), epoxy resin, polyester resin, styrene-butadiene copolymer (monomer ratio 5-30:95-70)
, olefin copolymers (ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene-
methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, ionomer resin), polyvinylpyrrolidone, methyl vinyl ether-maleic anhydride copolymer, maleic acid Modified phenolic resin, phenol-modified terpene resin.

Further, when the toner of the present invention is used as a two-component developer, it is used in combination with a carrier powder.

All known carriers can be used in the present invention, including iron powder.

Examples include magnetic powders such as ferrite powder and nickel powder, glass beads, and those whose surfaces have been treated with resin or the like.

Furthermore, the toner of the present invention can contain a magnetic material and be used as a magnetic toner. The magnetic materials contained in the magnetic toner of the present invention include iron oxides such as magnetite, hematite, and ferrite, iron, cobalt, and nickel. metals such as aluminum, cobalt, copper,
Examples include alloys with metals such as lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, and vanadium, and mixtures thereof.

These ferromagnetic materials preferably have an average particle size of about 0.1 to 2 JL, and the amount to be included in the toner is about 20 to 200 parts by weight per 100 parts by weight of the resin component, particularly preferably 100 parts by weight of the resin component. 40 to 150 parts by weight.

The toner of the present invention may also contain additives as required. Examples of additives include lubricants such as Teflon and zinc stearate, abrasives such as cerium oxide and silicon carbide, and colloidal additives. Fluidity imparting agents such as silica and aluminum oxide, anti-caking agents,
Alternatively, conductivity imparting agents such as carbon black and tin oxide, fixing aids such as low molecular weight violet polyethylene, etc. may also be used.

To prepare the toner for developing an electrostatic image according to the present invention, the charge control agent according to the present invention is mixed with a vinyl or non-vinyl thermoplastic resin, a pigment or dye as a coloring agent, a magnetic material as necessary, Additives, etc. are thoroughly mixed using a ball mill or other mixer, and then melted, kneaded, and kneaded using a heat kneading machine such as a heated roll, kneader, or extruder to dissolve the resins into the mixture. A toner having an average particle size of 5 to 20p can be obtained by dispersing or dissolving a pigment or dye in the toner, cooling and solidifying it, and then crushing and classifying it.

Alternatively, the material can be obtained by dispersing the material in a binder resin solution and then spray-drying it, or by mixing the specified material into a single lid that is to constitute the binder resin to form an emulsified suspension and then polymerizing it. Methods such as a polymerization method and a toner production method for obtaining a toner can be applied.

Toners produced by these methods can be used for developing to visualize electrostatic images in electrophotography, electrostatic recording, electrostatic printing, etc. by any conventionally known means, and can be used as follows: It has excellent effects.

That is, the amount of frictional charge between toner particles is uniform, and the amount of charge can be easily controlled. In addition, the toner is extremely stable, with no variation or decrease in the amount of triboelectric charge due to deterioration during use. Therefore, problems such as development fog, toner scattering, and contamination of electrophotographic photosensitive materials and copying machines as described above are eliminated, and phenomena such as toner aggregation, clumping, and low-temperature flow during storage, which were major drawbacks in the past, are eliminated. It is a toner that can withstand long-term storage without causing damage, and also has excellent abrasion resistance, fixing properties, and adhesive properties of toner images.

These excellent effects of the toner are further magnified when used in a repetitive transfer copying system in which the operations of charging, exposure, development, and transfer are successively repeated. Furthermore, since there is little color disturbance caused by the charge control agent, it is possible to form color images with excellent colors when used as a color electrophotographic toner.

〔Example〕

The present invention will be specifically explained below with reference to Examples, but this is not intended to limit the present invention in any way. All parts in the following formulations are by weight.

Example 1 Styrene/butyl acrylate (80/20) copolymer 100 parts (weight average molecular acid Mw: approximately 300,000) Carbon black (Mitsubishi #44) 10 parts Paper molecular weight polyethylene wax 2 parts Compound (1)
2 parts The above materials were thoroughly mixed in a blender and then kneaded with two rolls heated to 150"0. The mixed material was allowed to cool naturally, then coarsely pulverized with a cutter mill, and then finely pulverized with a jet airflow pulverizer. The powder was pulverized using a wind classifier and further classified using an air classifier to obtain a fine powder having a particle size of 5 to 204 mm.

A developer was prepared by mixing 5 parts of fine powder with 100 parts of iron powder carrier having an average particle size of 50 to 80 JL.

First, the amount of triboelectric charge of the toner in the developer was measured by a conventional blow-off method.

Next, by a conventionally known electrophotographic method,
A negative electrostatic image was formed, and this was powder-developed using the above-mentioned developer using a magnetic brush method to create a toner image, which was transferred to plain paper and heat-fixed. The resulting transferred image had a sufficiently high density, no fogging, no flying toner around one image, and a good image with high resolution. Transfer images were continuously created using the above developer and durability was examined.

The transferred image after 30,000 sheets is also compared with the initial image,
It was a completely unremarkable image.

Further, during durability, the above-mentioned filming phenomenon related to toner on the photoreceptor was not observed at all, and no problems were found in the cleaning process. Also, there were no troubles in the fixing process (at the end of the 30,000-sheet durability test, the fuser was disassembled and observed, but there were no scratches or damage to the rollers, and there was almost no dirt from offset toner, making it suitable for practical use. There were no problems at all.

In addition, when the environmental conditions were set to 35°C and 85%, the image density was almost the same as at room temperature, and clear images with no fogging or scattering were obtained, and the durability remained almost unchanged up to 30,000 sheets. Next, a transferred and fixed image was obtained at a low temperature of 15°C and a low humidity of 10%, and the image density was sufficiently high, solid black was developed and transferred extremely smoothly, and the image was excellent with no scattering or hollow spots. Durability was carried out under these environmental conditions, and even though copies were made continuously and intermittently, the density variation was ±0.2 up to 30,000 sheets, which was sufficient for practical use.

Comparative Example 1 A developer was obtained in the same manner as in Example 1, except that 2 parts of Nigrosine dye (Nigrosine Base EX manufactured by Orient Chemical Industry Co., Ltd.) was used instead of 2 parts of Compound (Tech), and development, transfer, and fixing were carried out in the same manner. I got the image.

At room temperature and humidity, there was little fog, but the image density was low at 1.06, line drawings were scattered, and solid black was noticeably rough. Durability was investigated and the density decreased to 0.83 after 30,000 sheets.

Also, during durability, the toner material formed a film in the form of thin stripes on the surface of the photoreceptor before and after the photoreceptor, and appeared as lines on the image. This is so-called filming, and is thought to be due to the charge control agent changing the lubricity of the toner powder.

Furthermore, during durability, the fixed image tended to get caught up in the fixing roller during the fixing process, and there was difficulty in peeling it off from the roller.

When an image was obtained under conditions of 35° C. and 85%, the image density was as low as 0.88, and fogging, scattering, and roughness increased. Transfer efficiency was also low.

When an image was obtained under conditions of 15° C. and 10%, the image density was as low as 0.91, and there was severe scattering, fogging, and roughness, and transfer omissions were noticeable. I tried to take continuous images, but
After about 30,000 sheets, the density became 0.53, making it impractical.

Example 2 A developer was obtained in the same manner as in Example 1 except that 3 parts of compound (2) was used instead of 2 parts of compound (1), and an image was obtained in the same manner by performing development, transfer, and fixing.

The detailed results are shown in Tables 1 and 2, and satisfactory results almost the same as in Example 1 were obtained.

Example 3 A developer was obtained in the same manner as in Example 1 except that 2 parts of compound (3) was used instead of 2 parts of compound (1), and development, transfer, and
Fixation was performed and an image was obtained in the same manner.

The detailed results are shown in Tables 1 and 2, and almost the same satisfactory results as in Example 1 were obtained.

Example 4 A developer was obtained in the same manner as in Example 1 except that 2 parts of compound (4) was used instead of 2 parts of compound (1), and development, transfer, and
Fixation was performed and an image was obtained in the same manner.

The detailed results are shown in Tables 1 and 2, and almost the same satisfactory results as in Example 1 were obtained.

Example 5 Styrene/butyl acrylate (80/20) copolymer 100 parts (L weight average molecular weight Mwz approximately 300,000) Triiron tetroxide EPT-500 (Toda Kogyo type) 60 parts Paper molecular weight Polypropylene wax 2 parts Compound (1) Two parts of the above materials were thoroughly mixed in a blender and then kneaded with two rolls heated to 150°C. After the kneaded material is allowed to cool naturally, it is roughly pulverized using a cutter mill, then pulverized using a pulverizer using a jet stream, and further classified using an air classifier to obtain a fine powder with a particle size of 5 to 20 mm. Obtained.

Next, hydrophobic colloidal silica R was added to 100 parts of the fine powder.
0.4 part of -972 (manufactured by Nippon Aerosil Co., Ltd.) was mixed in a sample mill to prepare a -component magnetic toner.

First, the frictional electrostatic stitching of this toner was measured using a normal blow-off method.

When this toner was applied to a commercially available copying machine (trade name: MP-1502, manufactured by Canon ■) and an image was printed, good results similar to those of Example 1 were obtained.

Example 6 A developer was obtained in the same manner as in Example 5, except that 3 parts of compound (2) was used instead of 2 parts of compound (1), and development, transfer, and fixing were carried out in the same manner. I got it.

Detailed results are shown in Tables 1 and 2, and almost the same satisfactory results as in Example 5 were obtained.

Example 7 A developer was obtained in the same manner as in Example 5, except that 2 parts of compound (3) was used instead of 2 parts of compound (1), and development, transfer, and fixing were carried out in the same manner as in Example 5. I got it.

The detailed results are shown in Tables 1 and 2, and almost the same satisfactory results as in Example 5 were obtained.

Comparative Example 2 In place of 2 parts of compound (1) in Example 5, 2 parts of dimethyl-benzyl-hexadecyl ammonium chloride
A developer was obtained in the same manner as in Example 5, except that the developer was used, and an image was obtained in the same manner. At room temperature and humidity, there is little fog, but the image density is 0.
．． At 81, the line drawings were scattered and the solid black was noticeably rough. I checked the durability, but the density was 0 after 30,000 sheets.
．． It dropped to 48.

In addition, the above-mentioned filming phenomenon during durability and problems in the fixing process were almost the same as those in Comparative Example 1. When an image was obtained under the conditions of 35° C. and 85%, the image density was 0.72. This resulted in an increase in fogging, scattering, and roughness, making it unsuitable for two uses. Transfer efficiency was also low. When an image was obtained under the conditions of 15° C. and 10%, the image density was as low as 0.73, and there was severe scattering, fogging, roughness, and transfer omissions were noticeable. Continuous image formation was performed, but the density became 0.58 after 30,000 sheets, making it impractical.

Example 8 Styrene/butyl acrylate (80/20) copolymer 100 parts (weight average molecular weight M: approx. 300,000) Copper phthalocyanine blue pigment 5 parts Low molecular weight polypropylene wax 2 parts Compound (1) 2 parts The above materials were blended After mixing well, the mixture was kneaded using two rolls heated to 150°C. After allowing the mixture to cool naturally, it is roughly pulverized using a cutter mill, then pulverized using a pulverizer using a jet stream, and further classified using an air classifier to obtain a fine powder with a particle size of 5 to 20 JL. Ta.

Next, 50 g of magnetic particles having a particle size of 50 to 80 mm were mixed with 100 parts of the fine powder to prepare a developer.

When images were developed using this developer using the development method described below, good images with a bright blue color were obtained, and after producing 1500 images, the toner/carrier was 10
Even when the weight was 750 g, there was almost no change in the image temperature, and after that, while replenishing toner, images were printed up to 30,000 sheets, and good images were obtained.

This developing method will be explained using FIG. 1.

The carrier-toner mixture formed on the toner carrier 2 is circulated by the magnetic brush 52 by rotating the toner carrier 2, and the toner in the hopper 3 is taken in and coated in a uniform thin layer on the carrier 2. Then, the toner carrier 2 and the electrostatic image carrier l are opposed to each other with a gap larger than the thickness of the toner layer, and the toner 5 on the carrier 2 is developed by flying onto the electrostatic charge image on the electrostatic image carrier l. let

The thickness of the toner layer is controlled by the size of the magnetic brush 52, the amount of magnetic particles, and the regulating blade 58. The gap between the electrostatic image carrier 1 and the toner carrier 2 may be made larger than the thickness of the toner, and the developing bias 6 may be applied.

The evaluation results of each example and comparative example are shown in Tables 1 and 2. In Table 1, O indicates good, 0Δ indicates slightly good, Δ indicates slightly poor, and × indicates poor.

〔Effect of the invention〕

As described above, the toner of the present invention containing the above-mentioned compound as a charge control agent has a uniform frictional charge between toner particles, and the amount of charge can be easily controlled. In addition, it is an extremely stable toner that does not change in quality or decrease in triboelectric charge (, l) during use. Therefore, it does not cause problems such as development fog, toner scattering, and contamination of electrophotographic photosensitive materials and copying machines as described above. In addition to being removed, toner aggregation, agglomeration, and low-temperature fluidity development during storage, which were major problems in the past, are avoided, allowing for long-term storage, and the toner image has excellent wear resistance, fixing properties, and adhesion. It's also excellent.

These excellent effects of the toner are further magnified when used in a repetitive transfer copying system in which the operations of charging, exposure, development, and transfer are successively repeated. Furthermore, since there is little color tone disturbance caused by the charge control agent, it is possible to form a color image with desired colors by using it as a color electrophotographic toner.

[Brief explanation of drawings]

FIG. 1 is an explanatory diagram of an example of a developing device to which the positively chargeable toner according to the present invention can be applied. l... Electrostatic image holder, 2... Toner carrier, 3...
...hopper, 5...toner. 6...Bias, 50...Magnet. 52...Magnetic brush, 58...Regulation blade.

Claims (1)

[Claims] A toner for developing electrostatic images characterized by containing triarylstibine oxide.