JPS61275763A - Toner for electrostatic image development - Google Patents

Abstract

PURPOSE:To stabilize an amount of the frictional electrification of the titled toner, and to make the distribution of the frictional electrification sharp and uniform, and to enable to control the electrification amount of the titled toner to that suitable to the used development system by incorporating a specific org. tin compd. to the titled toner. CONSTITUTION:The titled toner is incorporated with the org. tin compd. shown by the formula wherein R may be branched and is 1-24C alkyl, cycloalkyl, aryl or aralkyl group, R' is methylene or 2-12C alkylene group. the prescribed compd. is thermally and timewisely stable, and is low in a moisture content, when the prescribed compd. is incorporated to the developer, the good charge controlling agent capable of forming the developer having an excellent electrophotographic characteristics is obtd. Therefore, by incorporating the prescribed compd. to the developer, the stable frictional electrification characteristics is obtd., and the development and the transfer are truly effected according to the latent image. When the titled toner is continuously used for long periods, the toner does not occur the coagulation, maintaining the primary characteristics. The clean colored picture may be obtd., without being influenced to the change of the temperature and humidity.

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.

[Prior Art] Conventionally, as an electrophotographic method, US Patent No. 2.297. [No. 1, Japanese Patent Publication No. 42-23910 and Japanese Patent Publication No. 43-24748, etc., describe various methods, but in short, these methods involve uniform electrostatic charge on a photoconductive insulating layer. and forming an electrostatic latent image by irradiating the insulating layer with a light image, and then developing and visualizing the latent image with a fine powder called toner in the art,
After transferring the powder image to paper etc. as necessary, heat, pressurize,
Alternatively, fixing is carried out using solvent vapor or the like.

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 a magnetic brush method using an iron powder carrier, a cascade method using bead carissie, a fur brush method using fur, etc., depending on the type of carrier for conveying the toner.

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. Finely pulverized particles of about 1 to 30 IL 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 hold 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.

Nigrosine, azine dyes containing an alkyl group having 2 to 16 carbon atoms (Japanese Patent Publication No. 1827/1983), basic dyes (for example, C.I. Basic Yellow 2 (C, 1, B
a5ic Yellow 2) (C, 1,41000)
, C.I. Basic Yellow 3 (G, 1.
Ba5icBello%t3), C.I.Basic Red L (c, r, Japan asic Red 1) (
G, 1.451H), C.I.Basic-L/,
Do 9 (C, 1, Ba5ic Red 9) (C, I.

42500), C.I. Basic Violet 1 (C, 1, Ba5ic Violet 1) (C,
! , 42535), C,1,Ba5icViolet 3
(C,!, 42555), C,1,Ba5ic Viol
et 10) (C, 1, 45170), C.I. Basic Bio L/-/t 14 (G, 1. Ba5
ic Violet 14) (C, I.

42510), C.I. Basic Blue l (G
, 1. Ba5ic Blue 1) (G, 1.420
25), C.I. Basic Blue 3 (C,
1, Ba5ic Blue 3) (C, 1, 51005
), C.I. Basic Blue 5 (C, t,
Ba5ic Blue 5) (C, 1, 42140)
, C, I Basic Blue (C, 1, Ba
5ic Blue 7) (C, 1, 42595), C.I. Basic Blue 9 (C, L Ba5ic
Blue 9) (C, 1, 52015), C.I. Basic Blue 24 (C, 1, Ba5ic
Blue24) (C, 1, 52030), C.I. Basic Blue 25 (C, 1, Ba5ic B
lue 25) (C, L 52025), C.I.
Basic Blue 28 (C,!, Ba5icBl
ue 2B) (C, 1, 44045), C.I. Basic Green 1 (C, 1, Ba5ic Gre
en 1) (G, I.

42040), C.I. Basic Green 4 (
C, 1, Ba5ic Green 4) ((1:, 1.
42000) etc.]. These basic dye lake pigments (lake forming agents include phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.),・I nrubento black 3
(C, 1,5olvent Black 3) (C,
L 28150).

Hansa Yellow G (C, 1, 11680), C.I. Mordant Black 11 (C, 1, Mordan
t Blackll), C,L Pigment Black 1 (C,L Pigment Black 1),
Gilt night, asphalt, etc.

Quaternary ammonium salts, such as pendino-5-methyl-hexadecyl ammonium chloride, decyl-trimethyl ammonium chloride, organotin compounds such as dibutyltin oxide, metal salts of higher fatty acids, glass, mica, inorganic fine powders such as zinc oxide, EDTA , metal complexes of acetylacetone, etc., vinyl polymers containing amino groups, condensation polymers containing amine groups, and other polyamine resins.

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

Special Publication No. 41-20153, No. 43-275913,
Metal complex salts of monoazo dyes described in No. 44-8H7, No. 45-28478, etc.

Dyes and pigments such as nitrofumic acid and its salts or C, 1,14845 described in JP-A-50-133338.

Metal complexes of salicylic acid, naphthoic acid, guicarboxylic acid such as Go, Cr, Fe, etc. described in Japanese Patent Publication No. 55-42752, Japanese Patent Publication No. 58-41508, Japanese Patent Publication No. 59-7384, Japanese Patent Publication No. 59-7385, etc. , sulfonated copper phthalocyanine pigments, nitro groups, styrene oligomers with halogens 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 thermoplastic resins, thermally melted and dispersed, and then finely pulverized and adjusted to a suitable particle size as necessary before use.

However, these dyes used as charge control agents have complex structures, inconsistent properties, and poor stability, and are susceptible to decomposition during thermal kneading, mechanical impact, friction, changes in temperature and humidity conditions, etc. Otherwise, it is likely to change in quality and 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 pose the fatal problem of causing differences in the amount of frictional charge between toner particles obtained by pulverization. have. For this reason, various methods have been used to achieve more uniform dispersion. for example,
Basic nigrosine dyes are used by forming salts with higher fatty acids in order to improve compatibility with thermoplastic resins.

Dispersion products of unreacted fatty acids or salts are often exposed on the toner surface and contaminate the carrier or toner carrier, causing a decrease in toner fluidity, fog, and a decrease in image density. There is. 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.

Although the inherent poor dispersion can be avoided, the current situation is that charge uniformity sufficient for practical use has not yet been obtained.

Moreover, most of the substances generally known as charge control agents have a dark color, and there is a problem in that they cannot be incorporated into bright chromatic color developers.

In addition, many charge control agents are hydrophilic, and due to poor dispersion in these resins, dyes are exposed on the toner surface when crushed after melt-kneading, and under high humidity conditions, these charge control agents Since it is hydrophilic, it has 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 support such as a sleeve,
The amount of charge generated on the surface of toner particles varies, and problems such as development fog, toner scattering, and carrier contamination are likely to occur. Further, this failure becomes a noticeable phenomenon when copying is repeated many times, resulting in a result that is practically unsuitable for copying machines.

Furthermore, under high humidity conditions, the transfer efficiency of toner images decreases significantly, making many toners unusable. Due to the instability of charge control agents, they often undergo deterioration and become unusable due to poor charging properties.

Furthermore, when conventional charge control agents are used in toner, after long-term use, the charge control agents may adhere to the surface of the photoreceptor or promote toner adhesion, adversely affecting 1M image formation (
There are many things that have a negative effect on the cleaning process of a copying machine, such as the filming phenomenon), those that cause scratches on the surface of the photoreceptor or cleaning members such as cleaning blades, and those that accelerate wear of the members.

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 Increases the ability of the transfer material to cling to the roller.

There are some things that reduce 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.

[Problems to be Solved by the Invention] An object of the present invention is to provide a new technique for toner charge control that overcomes these problems.

Another object of the present invention is to stabilize the amount of 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 maintain a stable triboelectricity distribution. To provide a developer that is sharp and uniform, and whose charge amount can be controlled to suit the developing system used.

Still another objective is to develop the latent image faithfully and to use the developer that performs the transfer, that is, toner adhesion in the background area during development, to prevent fogging and toner scattering around the edges of the latent image. High image density can be obtained without
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 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 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 and effects for solving the problems] The present invention is an electrophotographic toner used for developing an electrostatic image, which is characterized by containing an organic tin compound represented by the general formula [I]. Found in toner for developing electrostatic images.

[In the formula, R represents an optionally branched alkyl group, cyclic alkyl group, aryl group, or aralkyl group of [I-e2a, and R' represents a methylene group or an alkylene group of 02 to [I2]. ] The present inventors have discovered that the organotin compound represented by the general formula [I] is thermally and temporally stable, has low hygroscopicity, and when contained in a developer, can produce a developer with excellent electrophotographic properties. The present invention was achieved by discovering that this is a high-quality charge control agent.

In general formula [I], the substituent R is a methyl group,
C1 to C24 alkyl groups which may be branched such as ethyl group, propyl group, butyl group, hexyl group, dodecyl group, hexadecyl group, octadecyl group, eicosyl group;
Cyclic alkyl groups such as cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group; Aryl groups such as phenyl group, tolyl group, butylphenyl group, butoxyphenyl group, glolphenyl group; benzyl group, phenethyl group, methylbenzyl group, etc. Typical substituents include an aralkyl group and the like.

R' is a methylene group or an alkylene group of 02 to G+2. C2~[The alkylene group of I2 is C2~G1?
It is a divalent atomic group that is generated by removing two hydrogen atoms bonded to different 2@ carbon atoms in an aliphatic saturated hydrocarbon. When it has a valence, trimethylene-GHz
GHz GHz- and tetramethylene-[I2 CH2[
This includes cases where an aliphatic hydrocarbon has free valences at both carbon ends, such as polymethylene such as I20H2-.
In the case of 03 or more, a polymethylene group having free valences at both carbon ends is preferred.

Typical specific examples of the organic tin compound represented by the general formula [I] include the following.

[Compound example] These compounds are synthesized by known methods.

That is, the corresponding disubstituted organic tin oxide is dispersed using benzene, toluene, or xylene as a solvent, and the corresponding alcohol having an ether bond is allowed to act on it. Tin alkoxide is synthesized by the dehydration reaction of alcohol and tin oxide. The reaction is carried out by boiling the dispersion solution and removing the water produced as an azeotrope during the reaction.

Generally, the above compound has an average particle size of 10-0.01 IL,
In particular, it is preferable to prepare the toner with a particle size in the range of 5 to 0.1 μm.

Methods for incorporating the above compound into the developer include a method of adding it inside the developer and a method of adding it externally. If internally added, what is the amount of these compounds to be used?

It is determined by the toner manufacturing method including the type of binder resin, 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, it is used in a range of 0.5 to 10 overlapped 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 desirable.

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

Coloring materials used in the present invention include carbon black, lamp black, iron black, ultramarine blue, nigrosine dye, aniline black, phthalocyanine blue, phthalocyanine green, /\nthe yellow G, rhodamine 6G lake, calco oil blue, chrome yellow, Any conventionally known dyes and pigments such as quinacridone, benzidine yellow, 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 poly-p-chlorostyrene and polyvinyltoluene; styrene-p-chlorostyrene co-ffi combination, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene Copolymer, styrene-ethyl acrylate copolymer.

Styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-methyl chloromethacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, Styrenic copolymers such as styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, and styrene-maleic acid ester copolymer; polymethyl methacrylate ,
Polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, polyurethane, polyamide, epoxy resin, polyvinyl butyral, polyacrylic resin, rosin, modified rosin, terpene resin, phenolic resin, aliphatic or alicyclic resin Hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin,
Examples include 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, Bohan ester resin, styrene-butadiene copolymer (monomer ratio 5-30:95-70)
, olefin copolymers (ethylene-acrylic ugly copolymer, ethylene-acrylic acid ester copolymer, ethylene-
Methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, iono-resin), polyvinylpyrrolidone, methylvinylnityl-maleic anhydride copolymer Coalescence, 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.

As carriers that can be used in the present invention, all known carriers can be used. For example, magnetic powders such as iron powder, ferrite powder, nickel powder, glass beads, etc., and their surfaces treated with resin etc. Examples include things that have been done.

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 IL, and are contained in the toner in an amount of 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 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 added to a vinyl or non-vinyl thermoplastic resin, a pigment or dye as a coloring agent, and a magnetic material as necessary. The resins are thoroughly mixed using a ball mill or other mixer, and then melted, kneaded, and kneaded using a heat kneader such as a heated roll, kneader, or extruder to make the resins mutually dissolve. Pigment or dye is dispersed or dissolved, cooled and solidified, then crushed and classified to obtain an average particle size of 5 to 20.
You can get the same amount of toner.

Alternatively, after dispersing the material in a binder resin solution.

Methods such as a method for obtaining toner by spray drying, or a polymerization method for obtaining a toner by mixing a predetermined material with the Ii polymer that constitutes the binder resin to form an emulsified suspension and then polymerizing the toner are applicable. I can do it.

The toners prepared by these methods can be used for developing to visualize electrostatic images in electrophotography, electrostatic recording, electrostatic printing, etc. by conventionally known means, and have the following advantages: It produces a certain effect.

That is, the amount of frictional charge between toner particles is uniform, and the amount of charge can be easily controlled. Furthermore, 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 any damage, and the abrasion resistance of toner images.
It also has excellent fixing and adhesive properties.

The excellent effects of these toners include charging, exposure, development,
When used in a repetitive transfer type copying system in which the transfer operation is continuously repeated, the effect is further enhanced. Furthermore, since there is no color tone disturbance caused by a charge control agent, it is possible to form color images with excellent colors when used as a color electrophotographic toner.

[Examples] The present invention will be specifically explained below using Examples, but these are not intended to limit the present invention in any way. All parts in the following formulations are parts by weight.

Example 1 Carbon black (Mitsubishi 1144) 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°C. After the kneaded material was left to cool naturally, it was 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 g. Ta.

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

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, and no toner scattering around the image, resulting in a good image with high resolution. Transfer images were continuously created using the above developer to examine durability.

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 this time, and 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, so it was practically perfect. There were no problems.

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 humidity, clear images with no fogging or scattering were obtained, and the durability remained unchanged up to 30,000 sheets. When a transferred and fixed image was obtained at a low temperature of 15° C. and a low humidity of 10%, the image density was sufficiently high, the solid ring was developed and transferred very smoothly, and the image was excellent without any 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 Compound (1 part 2 parts) 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, and an image was obtained in the same manner by performing development, transfer, and fixing.

At room temperature and humidity, there is little fog, but the image density is 1. The OB and low line drawings were scattered, and the solid rings were noticeably rough. Durability was investigated and the density decreased to 0.83 after 30,000 sheets.

Further, during the durability test, the toner material formed a film in the form of thin stripes on the surface of the photoreceptor and began to appear as lines on the image from around 0 to 00 pages. This phenomenon is called filming, and is thought to be due to the charge control agent changing the lubricity of the toner powder, and there is a tendency for the toner powder to be easily filmed in, making it difficult to remove it 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, roughness, and noticeable transfer defects. I tried to take continuous images, but
After about 30,000 sheets, the kyphosis density was 0.53, which made 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 the 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 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 Triiron tetroxide EPT-500 (manufactured by Toda Kogyo) 60 parts Paper molecular weight Polypropylene wax 2 parts Compound (1) 2
After thoroughly mixing the above materials in a blender, they were kneaded with two rolls heated to 150°C. After the kneaded material was left to cool naturally, it was 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, 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.

When this toner was applied to a commercially available copying machine (trade name: MP-1502, manufactured by Canon ■) and an image was produced, 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.

The 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 benzyl-dimethyl-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. Durability was investigated, and the density decreased to 0.48 after 30,000 sheets.

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 increased fogging, scattering, and roughness, making it unusable. 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. I tried to take continuous images, but
At the time of 30,000 sheets, the density was 0.59, making it impractical.

Example 8 Copper phthalocyanine blue pigment 5 parts Low molecular weight polypropylene 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°C. After the kneaded material is left 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 l. Obtained.

Next, 50 g of carrier iron powder having a particle size of 50 to 8 QJL was mixed with 100 parts of the fine powder to prepare a developer.

When this developer was used to develop an image using the developing method shown in Figure 1, a good image with a bright blue color was obtained. However, there was almost no change in the image density, and after that, while replenishing toner,
Even after printing up to 10,000 images, good images were obtained.

To explain this developing method, in FIG. 1, l is an electrostatic image holder, 2 is a toner carrier, 3 is a hopper, and 52
5 is a magnetic brush using a carrier toner mixture, 5 is a toner thickness regulating blade, 50 is a fixed magnet, 6 is a developing bias, and 5 is a toner.

That is, the magnetic brush 52 formed on the toner carrier 2 is circulated by rotating the toner carrier 2, and the toner in the hopper 3 is taken in and coated in a thin layer uniformly on the hopper 2.Then, the toner is carried. The body 2 and the electrostatic image holding body 1 are opposed to each other with a gap larger than the thickness of the toner layer 1, and the toner 5 on 2 is caused to fly and develop onto the electrostatic charge image on 1.

The thickness of one layer of toner is the size of a 52 magnetic brush.

That is, it is controlled by the amount of carrier and 58 regulating blades. The gap between 1 and 2 may be made larger than the thickness of the toner layer, and a developing bias of 6 may be applied.

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

table! Effects of L invention] The effects obtained by the present invention are as follows.

(1) Between toner particles or between toner and carrier.

- In component development, the amount of charge between the toner and a toner carrier such as a sleeve is stable, and the distribution of triboelectric charge is sharp and uniform, and the amount of charge is controlled to be appropriate for the developing system used. It is a developer that can be used.

(2) The developer is capable of faithfully developing and transferring Ws images, maintains its initial characteristics even when used continuously over a long period of time, and does not cause toner aggregation or change in charging characteristics.

(3) A developer that can reproduce stable images that are not affected by changes in temperature and humidity, and that can also produce images in vivid chromatic colors.

(4) It is a developer that does not stain, rub or scratch the electrostatic latent image surface, has an easy cleaning process, has excellent fixing properties, and has no problem with high-temperature offset, etc.

[Brief explanation of drawings]

The first UgJ 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. 1... Electrostatic image holder, 2... Toner carrier, 3...
・Hopper, 5... Toner, 6... Bias power supply, 50... Magnet, 52... Magnetic brush, 58... Regulation blade.

Claims (1)

[Scope of Claims] An electrophotographic toner used for developing an electrostatic image, the toner containing an organic tin compound represented by the general formula [I]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] [In the formula, R represents a C_1 to C_2_4 optionally branched alkyl group, cyclic alkyl group, aryl group, or aralkyl group, and R' is a methylene group or C_2～C_1
Indicates the alkylene group of _2. ]