JPS61162053A - Toner for electrostatic charge image development - Google Patents

Abstract

PURPOSE:To obtain the title toner capable of truely developing and transferring a latent image and of maintaining initial characteristics of the toner when it is continously used for a long period and of giving no change to a coagulation of the toner and to an electrostatic charge characteristics by incorporating a specific compd. to a binding resin. CONSTITUTION:The title toner contains in the binding resin, the compd. shown by the formula wherein R1 is each >=11C an unsubstd. or a substd. alkyl, aralkyl or aryl group, R2, R3 and R4 may be the same or a different group, and are each <=8C unsubstd. or substd. alkyl, aralkyl or substd. alkyl, aralkyl or aryl group, A<-> is an anion. Said compd. has a thermal and a periodical stabilities and a less hygroscropic property. When said compd. is compounded to the developer, the obtd. developer makes a good charge controlling agent which gives an excellent developer having electron photographic properties. The compounding amount of the compd. is preferably 0.5-5pts.wt. in an inner addition, and 0.01-10pts.wt. in an outer addition on the basis of 100pts.wt. the binding resin.

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, U.S. Patent No. 2.297.89
No. 1, Special Publication No. 1972-23910 and Special Publication No. 1973-
Various methods are described in Japanese Patent Publication No. 24748, etc., but these methods basically apply a uniform electrostatic charge on a photoconductive insulating layer and irradiate the insulating layer with a light image to remove the electrostatic charge. A latent image is formed, and then the latent image is developed and visualized using a fine powder called toner using the technology, and the powder image is transferred to paper or the like as necessary, and then fixed by heat, pressure, or solvent vapor. It is something to do.

The developing methods applied to these electrophotographic methods include:
They can be broadly classified into dry development method and wet development method. 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.

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 liters 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.

Nigrosine, azine dyes containing an alkyl group having 2 to 16 carbon atoms (Japanese Patent Publication No. 42-1827), basic dyes (e.g. G, 1.Ba5ic Yellow 2 (C, L
41000), C, 1, Ba5ic Yellow
3, C, 1, Ba5ic Red 1 (G, 1.4
5180), C,1,Ba5ic Red 9 (
G.I.

42500), C, 1, Ba5ic Violet 1
(C, L 42535), G, 1. Ba5ic V
iolet 3 (C, 1, 42555) C, 1, B
a5icViolet 10 (C, 1, 45170)
,G,1. Ba5ic Violet 14 (C, 1
,42510), C,1,Ba5ic Blue
l (G, I.

42025), G, 1. Ba5ic Blue 3
(G, 1.51005), G, I.

Bs1c Blue 5 (C, 1, 42140), G
, 1. Ba5ic Blue7 (C, 1,4259
5), C,1,Ba5ic Blue 9 (C,I
.

52015), C, 1, Ba5ic Blue 24
(C, 1, 52030), G, I.

Ba5ic Blue 25 (G, 1.52025)
,C,1,Ba5ic Blue2B (C,1,44
045), C,1,Ba5ic Green 1
(C,1°42040), C,1,Ba5ic Gre
en 4 (C, 1,42000), C, 1,4251
0, G, 1.45170, etc., lake pigments of these basic dyes (lake-forming agents include phosphotungstic acid, phosphomolybdenum phosphorus, phosphotungsten molybdic acid,
Tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.), G, 1.5olv
ent Black 3 (G, 1.2815G), Hansa Yellow G (C, 1, 11880), C, L
NordlantBlack 11. C,1,Pig
mentBlack 1, Gilt Night, Asphalt, etc.

and quaternary ammonium salts, such as pencil methyl-
Organotin compounds such as hexadecyl ammonium chloride, decyl-trimethylammonium chloride, dibutyltin oxide, metal salts of higher fatty acids, inorganic fine powders such as glass, mica, and zinc oxide, metal complexes such as EDTA and acetylacetone, and amino groups. Polyamine resins such as vinyl polymers containing polyamines and 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, 44-6397, and 45-28478.

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

and Special Publication No. 55-42752, Special Publication No. 58-415
No. 08, Special Publication No. 59-7384, Special Publication No. 59-738
Metal complexes such as Go, Cr, and Fe of salicylic acid, naphthoic acid, and dicarboxylic acid, and sulfonated copper phthalocyanine pigments described in No. 5 and the like. Styrene oligomers with nitro groups and halogens introduced, chlorinated paraffins,
Melamine resin 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 surpassed the dye-pigment-based products in overall performance, and dyes are still used, although they are still unsatisfactory. Most are examples.

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. In addition, it is easily decomposed or deteriorated due to decomposition during thermal kneading, mechanical impact, 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 to achieve more uniform dispersion.1 For example, basic nigrosine dyes are treated with higher fatty acids and salt-formed to improve their compatibility with thermoplastic resins. However, unreacted fatty acids or salt dispersion products are often
It is exposed on the toner surface and contaminates the carrier or toner carrier, causing a decrease in the 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.

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, when pulverized after melting and mixing,
The dye is exposed on the toner surface.

Therefore, when using toner under high humidity conditions, these
Although the charge control agent 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,
Variations occur in the amount of charge generated on the surface of toner particles between toner particles, between toner and carrier, or between toner and a toner carrier such as a sleeve,
Problems such as development fog, toner scattering, carrier contamination, etc. are likely to occur, and these problems become noticeable 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 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 toner, long-term use may cause the charge control agents to adhere to the surface of the photoreceptor or promote toner adhesion, adversely affecting latent 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 these members.

Furthermore, when conventional charge control agents are used in toner, there are many that have a large effect on the thermal melting properties of the toner and degrade fixing performance.In particular, they deteriorate high-temperature offset performance, and the transfer material during heat roll fixing. There are many things that increase the clinging property to the rollers and reduce the durability life of the rollers.

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 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 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 provides a binder resin containing a compound having the following general formula % (where R1 is an unsubstituted or substituted alkyl group having 11 or more carbon atoms, an aralkyl group, or an aryl group). Indicates a group, R2,
R3 and R4 are the same or different groups, and represent an unsubstituted or substituted alkyl group, an aralkyl group, or a substituted alkyl group, an aralkyl group, or an aryl group having 8 or less carbon atoms, and 8-represents an anion) The present invention relates to a toner for developing electrostatic images characterized by containing a compound represented by:

The unsubstituted or substituted aralkyl group or aryl group (R+) includes a metal complex salt, such as an iron complex salt.

The present inventors have discovered that the compound represented by the general formula [I] is thermally and temporally stable, has low hygroscopicity, and when contained in a developer, provides a high-quality developer with excellent electrophotographic properties. It was discovered that it is a charge control agent.

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

[Compound examples] n3 (2) CH3 n3 CH3 (4) CH3 CH3-N"-G16H33Br- CH3 (5) CH3 CH3-N"-self4H2c)C1- o3 CH3-N"-C12H25C1- CH3 CH3 Quaternary Ammonia salts can be synthesized by various known methods, and Compound Examples 1 to 7 are all commercially available from Tokyo Kasei Kogyo.

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. When internally added, the amount of these compounds used is determined by the type of binder resin, the presence or absence of additives used as necessary, and the toner manufacturing method including the dispersion method, and is uniquely limited. Although not a specific amount, it is preferably 0.1 to 10 parts by weight (more preferably 0.5 to 10 parts by weight) per 100 parts by weight of the binder resin.
5 parts by weight). Also, if it is added externally.

The amount is preferably 0.01 to 10 parts by weight per 100 parts by weight of the resin, and conventionally known charge control agents may also be used in combination with the charge control agent of the present invention.

Colorants used in the present invention include carbon black, lamp black, iron black, ultramarine blue, niprolene dye, aniline blue, phthalocyanine blue, phthalocyanine green, Handy Yellow G, rhodamine 6G, lake,
Calco oil blue, chrome yellow, quinacridone,
Any conventionally known dyes and pigments such as benzidine yellow, rose bengal, triallylmethane dyes, monoazo dyes, and 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 copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer Coalescence, 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, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene- Styrenic copolymers such as maleic acid copolymers and styrene-maleic ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, polyurethane, 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, etc. Can be used in combination.

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

Polyolefins (low molecular weight polyethylene, low molecular weight polypropylene, polyethylene oxide, polytetrafluoroethylene, etc.), epoxy resins, polyester resins, styrene
Butadiene copolymer (monomer ratio 5-30:(15-7
0), olefin copolymers (ethylene-acrylic acid copolymer, ethylene-acrylic ester copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic ester copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, ionomer resin), polyvinylpyrrolidone, methyl vinyl ether-maleic anhydride copolymer, maleic acid-modified phenol 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, such as iron powder, ferrite powder,
Examples include magnetic powder such as nickel powder, glass beads, and those whose surfaces are treated with resin or the like.

Furthermore, the toner of the present invention can further 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, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese,
Examples include alloys of metals such as selenium, titanium, tungsten, and vanadium, and mixtures thereof.

These ferromagnetic materials preferably have an average particle size of about 0.1 to 2 µl, 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 in an amount of about 20 to 200 parts by weight per 100 parts by weight of the resin component. The amount is 40 to 150 parts by weight.

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

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. Pigments or dyes are dispersed or dissolved, cooled and solidified, and then crushed and classified to obtain particles with an average particle size of 5 or more.
You can get 20 liters of toner.

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 with the monomers that should constitute the binder resin to form an emulsified suspension and then polymerizing it. Methods such as polymerization to obtain toner and toner manufacturing method can be applied.

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. In addition, the toner is extremely stable, with no variation or decrease in the amount of triboelectric charge due to deterioration during use. Therefore, the above-mentioned problems such as development fog, toner scattering, and contamination of electrophotographic photosensitive materials and copying machines can be eliminated, and since the toner of the present invention is extremely superior, It is a toner that can withstand long-term storage without causing phenomena such as agglomeration, clumping, and low-temperature flow, 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, there is no color tone disturbance caused by charge control agents, and when used as a color electrophotographic toner, it is possible to form color images with excellent colors.

[Examples] Hereinafter, the present invention will be explained in detail with reference to Examples, which do not limit the present invention in any way. All parts in the following formulations are parts by weight.

Example 1 Styrene/butyl acrylate (80/20) copolymer (weight average molecular weight M: approx. 300,000) 100 parts Carbon black (Mitsubishi 44) To part Partial molecular weight polyethylene wax 2 parts Compound (1) 2 parts Above The materials were thoroughly mixed using a blender and then kneaded using 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. Obtained.

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

Further, the amount of triboelectric charge of 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 has a density of 1.
27, which was sufficiently high, and a good image with high resolution was obtained with no fog and no toner scattering around the image. Transfer images were continuously created using the above developer and durability was examined, and the transferred images after 30,000 copies were also found to have no dark color compared to the initial 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 fixing machine was observed and there were no scratches or damage to the rollers, and there was almost no dirt from offset toner, so there were no practical problems at all. Ta.

In addition, when the environmental conditions were set to 35°C and 85%, the image density was 1.26, a value that was almost unchanged from normal temperature and humidity, and clear images were obtained without fogging or scattering, and the durability was 30,000 yen. There was almost no change up to the 0th order 15
When the transferred image was washed at a low temperature and low humidity of 10% at a temperature of 10%, the image density was as high as 1.28, solid black was developed and transferred extremely smoothly, and it was an excellent image with no voids or voids. Durability was carried out under these environmental conditions, and although copies were made continuously and intermittently, the density variation was ±0.2 up to ao and ooo 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 (1), and the developer was subjected to development, transfer,
Fixation was performed and an image was obtained in the same manner.

At room temperature, there was little fog, but the image density was low at 1.08, line drawings were scattered, and solid black was noticeably rough. Durability was investigated and the density decreased to 0.83 after 30,000 sheets.

Further, during durability, after about 10,000 copies, 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. 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 at 35° C. and 85%, the image density was as low as 0.88, and fogging, scattering, and roughness increased. The transfer efficiency was also as low as 69%.

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 3
After about 0,000 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 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) 80 parts Low 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 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 l. 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.

Further, the amount of triboelectric charge of this toner was measured by a conventional blow-off method.

When this toner was applied to a commercially available copying machine (trade name: MP-150Z, manufactured by Canon ■) and an image was produced, good results almost the same as in 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 A developer was obtained in the same manner as in Example 5, except that 2 parts of benzylmethyl-hexadecyl ammonium chloride was used instead of 2 parts of Compound (1) in Example 5, and an image was obtained in the same manner. At room temperature, there is little fog, but the image density is 0.8
1 and the line drawings were scattered, and the solid black was noticeably rough. I checked the durability, and the density was 0.4 after 30,000 sheets.
It dropped to 8.

Furthermore, the above-mentioned filming phenomenon during durability and problems in the fixing process were almost the same as those in Comparative Example 1, and were undesirable.

Further, when an image was obtained under conditions of 35° C. and 85%, the image density was as low as 0.72, and fogging, scattering, and roughness increased, making it unusable.

The transfer efficiency was also as low as 63%. When images were obtained under conditions of 15° C. and 10%, the density of each image was as low as 0.73, and there was severe scattering, fogging, roughness, and noticeable transfer omissions.

Continuous image formation was performed, but the density became 0.59 after 30,000 sheets, 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 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 l. Obtained.

Further, the amount of triboelectric charge of the fine powder was measured by a conventional blow-off method.

Next, 50 g of carrier iron powder having a particle size of 50 to 80 l 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,
Good images were obtained even after printing up to 10,000 images.

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 made of a carrier toner mixture, 58 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 heated 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 z surface. The carrier 2 and the electrostatic image holder 1 are opposed to each other with a gap greater than the thickness of the toner layer, and the toner 5 on the z layer is developed by flying onto the electrostatic charge image on the 1 layer.

The thickness of one layer of the toner is 52, the size of the magnetic brush, Table 2: 0 Good, 0 Δ Slightly Good, Δ Slightly Poor, X Poor [Effects of the Invention] The effects obtained by the present invention are as follows.

(1) The amount of triboelectric charge between toner particles or between toner and carrier, or between toner and a toner carrier such as a sleeve in the case of -component development, is stable, and the distribution of triboelectricity is sharp and uniform, and the developer used This is a developer that can control the amount of charge to suit the system.

(2) The developer is capable of faithfully developing and transferring a latent image, maintains its initial characteristics even when used continuously over a long period of time, and has no toner aggregation or change in charging characteristics.

(3) It is a developer that can reproduce stable images unaffected by changes in temperature and humidity, and can produce images with high transfer efficiency and vivid chromatic colors even under high temperature and high humidity conditions as well as low temperature and low humidity conditions.

(4) The developer has excellent storage stability over a long period of time, does not stain the electrostatic latent image surface, does not cause scratches due to abrasion, is easy to clean, and has good fixing properties.

[Brief explanation of the drawing]

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. 1... Electrostatic image holder, 2... Toner carrier, 5...
・Toner, 50...Magnet, 52...Magnetic brush, 5
8...Regulation blade.

Claims (3)

[Claims] (1) The following general formula ▲mathematical formula, chemical formula, table, etc. is included in the binder resin▼ (In the formula, R_1 represents an unsubstituted or substituted alkyl group, aralkyl group, or aryl group having 11 or more carbon atoms, and R_
2, R_3 and R_4 are the same or different groups, and represent an unsubstituted or substituted alkyl group, aralkyl group, or aryl group having 8 or less carbon atoms, and A^- represents an anion). A toner for developing an electrostatic image, comprising: (2) Claim 1, wherein R_1 is a metal complex salt of an unsubstituted or substituted aralkyl group or aryl group.
Developing toner described in section. (3) The developing toner according to item 2, wherein the metal complex salt is an iron complex salt.