JPS61143769A - Electrostatic charge image developing toner - Google Patents

Abstract

PURPOSE:To obtain a toner stable, and sharp in distribution in the amt. to be triboelectrified among toner particles, carrier particles, and a toner carrying sleeve, and controllable to said amt. appropriate to a developing system by incorporating a specified compd. in the toner. CONSTITUTION:The compd. to be added is represented by formual I or II in which R1, R2 are each alkyl, aralkyl, or aryl, or a hetero ring optionally substd. by any of said group; and A is Cl, Br, I, NO<->3, SO<2->4, or SO<2->3. It is thermally stable and also stable for a long time, small in hygroscopicity, and the external or internal addition to a developer permits superior charge control action to be exhibited, high-fidelity development and transfer of an electrostatic latent image to be made, an image high in density and good in halftone reproducibility, and a sharp chromatic color image to be obtained, and the obtained toner to be prevented from agglomeration, change of characteristics due to repeated uses, and high-temp. offset trouble, and to be superior in storage stability, and not affected by high temp. and high 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. R1, Special Publication No. 42-23910,
Various methods are described in Japanese Patent Publication No. Sho 43-24748, etc., but these methods basically involve applying a uniform electrostatic charge onto a photoconductive insulating layer and irradiating the insulating layer with a light image. An electrostatic latent image is formed by this process, and then this latent image is developed and visualized using a fine powder called toner using the KATO technology.After transferring the powder image to paper etc. as necessary, heating, pressure, or Fixing is performed using solvent vapor or the like.

Development methods applicable 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, the -component-based development methods include the powder cloud method, in which toner particles are sprayed, and the contact development method, in which toner particles are brought into direct contact with the electrostatic latent image surface for development. (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; There is the MagneDry method, which develops by bringing a conductive 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 g 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 currently known in the art include the following.

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

Nigrosine, azine dyes containing an alkyl group having 2 to 16 carbon atoms (Japanese Patent Publication No. 42-1627), basic dyes (e.g. G, 1.Ba5ic Yellow 2 (C, 1
, 41000), C, 1, Ba5ic Yellow
3, C, 1, Ba5ic Red 1 (G, 1.
45180), C,1,Ba5ic Red 9
(C, I.

42500), C, 1, Ba5ic Violet 1
(C,L 42535), C,1,Ba5ic Vi
olet 3 (C,1,42555) C,l Ba
5icViolet 10 (C, 1, 45170),
C, 1, Ba5ic Violet 14 (G, 1.4
2510), C,1,Ba5ic Blue 1
(G, I.

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

Bs:c Blue 5 (C, 1, 42140), C
,1,Ba5ic Blue 7(C,1,42595
), size binding C, 1, Ba5ic Blue 9 (C,
1,52015), C,1,Ba5ic Blue 2
4 (G, 1°52030), C, 1, Ba5ic B
lue 25 (C, 1, 52025), G, 1. B
a5ic Blue 2B (C:, 1.44045)
,C,1,Ba5icGreen 1 (C,1,42
040), G, 1. Ba5ic Green 4 (C
:,I,42000),C,1,42510,C,1
, 45170, etc.). Lake pigments of these basic dyes (lake-forming agents include phosphorous tungsten, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.), G , 1.5olvent
Black 3 (C, 1, 26150), Hansa Yellow G (G, r.

111380), C, 1, Morcla, nt Bla
ck 11, C, 1, PigventBlack 1
, Gilnite, Asphalt, etc.

and quaternary ammonium salts, such as benzylmethyl-
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, etc. Polyamine resins such as vinyl polymers containing amino groups and condensation polymers containing amino groups.

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

Seven azo dye metal complex salts, described in Japanese Patent Publications No. 41-20153, No. 43-27596, No. 44-6397, No. 45-28478, etc., JP-A-50-133
Dyes and pigments such as nitrofumic acid and its salts or G, 1°14645 described in No. 338.

and Special Publication No. 55-42752, Special Publication No. 58-415
No. 08, Special Publication No. 59-7384, Special Publication No. 58-738
Metal complexes such as Go, Or, and Fe of salicylic acid, naphthoic acid, and guicarboxylic acid, and sulfonated copper phthalocyanine pigments described in No. 5 and the like. Styrene oligomer with nitro groups and halogens introduced. Chlorinated paraffin.

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 dye-pigment-based products in terms of overall performance, and there are still examples of dyes using dyes, although they are still unsatisfactory. Almost.

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 as charge control agents are
The structure is complex, properties are inconsistent, and stability is poor.In addition, it is easily decomposed or deteriorated due to mechanical shock, friction, changes in temperature and humidity conditions, etc. during thermal kneading, and charge controllability is reduced. This phenomenon is likely to occur.

Therefore, when a toner containing these dyes as a charge control agent is developed using 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.
Basic nigrosine dyes are used by forming salts with higher fatty acids in order to improve their 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, capri, and image density. There is. Alternatively, in order to improve the dispersion of these charge control agents into the resin, a method has been adopted in which the charge control agent powder and the resin powder are mechanically pulverized and mixed in advance, and then hot melt kneaded. 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, the charge control agents may be used after melt-kneading.

When crushed, the dye is exposed on the toner surface.

Therefore, when using toner under high humidity conditions, these
Since the charge fj control agent is hydrophilic, there is a problem in that a good quality image 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 toner support such as a sleeve,
Problems such as development fog, toner scattering, and carrier contamination are likely to occur, and these problems become more noticeable when copies are made many times, resulting in results that are not suitable for actual 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 the members.

Furthermore, when conventional charge control agents are used in toner, there are many that have a large effect on the heat-melting properties of the toner and reduce fixing performance, especially high-temperature offset performance, and transfer There are some that increase the stickiness of the rollers and reduce the durability life of the rollers.

As described above, there are many problems with conventional charge control agents, and there is a strong demand in the technical field to improve these, and although many improvement techniques have been proposed so far,
The reality is that nothing that is comprehensively satisfactory in practical terms has yet been found.

[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 resides in a developer containing a compound represented by the following general formula [I].

In the formula, R1 and R2 represent hydrogen, or an alkyl, aralkyl, or aryl group having no substituent or having a substituent, and optionally, an alkyl, aralkyl, or aryl group having no substituent or having a substituent in the heterocycle. can have one or more aryl groups, A
is C1, Br.

1 , NO3-, SO42-, or 5032-.

The present inventors have discovered that the compound represented by the general formula [11] is thermally and temporally stable, has low hygroscopicity, and when contained in a developer, has a high quality charge that provides a developer with excellent electrophotographic properties. It was found to be a control agent.

Typical specific examples of the compound represented by the general formula [11] include the following.

Compound example] These compounds are synthesized by known methods.

That is, piperindine (■) or pyrrolidine (■
) (all reprinted from Tokyo Kasei Kogyo),
It is synthesized according to the following formula by reacting with an alkyl halide or dialkyl sulfate.

There are two ways to incorporate compounds into the developer: one is to add them inside the developer, and the other is to add them externally.If they are added internally, the amount of these compounds used, the type of resin, and the amount used as necessary. It is determined by the toner manufacturing method including the presence or absence of added Au and the dispersion method, and is not uniquely limited, but preferably 0.1 to 1 Oii parts per 100 parts by weight of the binder resin. (more preferably 0.5-5
'parts by weight).

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.

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

1 Coloring materials used for light include carbon black, lamp black, iron black, ultramarine blue, negro dye, aniline blue, phthalocyanine blue, phthalocyanine green, Hansa yellow G, rhodamine 8G, lake, calco oil blue, chrome yellow, Any conventionally known dyes and pigments such as quinacridone, benzidine yellow, rose bengal, triallylmethane dyes, monoazo dyes, disazo dyes, and 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 resins , 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., singly or in combination. It can be used as

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.

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

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, metals such as iron, cobalt, and nickel, and these metals such as aluminum, cobalt, copper, lead, magnesium, tin, Examples include alloys of metals such as zinc, antimony, beryllium, bismuth-1, 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.

Further, the toner of the present invention may be mixed with additives as necessary. Examples of additives include lubricants such as Teflon and zinc stearate, abrasives such as cerium oxide and silicon carbide, flow agents such as colloidal silica and aluminum oxide, anti-caking agents, and carbon black. Conductivity imparting agents such as tin oxide,
Alternatively, there are fixing aids such as low molecular weight polyethylene.

The electrostatic image developing toner according to the present invention is prepared by using a vinyl-based charge control agent according to the present invention.

Non-vinyl thermoplastic resin, pigments or dyes as colorants, magnetic materials, additives, etc. as required are thoroughly mixed in a ball mill or other mixer, and then heated in a heat kneader such as a heated roll, niegoo, or extruder. Pigments or dyes are dispersed or dissolved in the mixture by melting, kneading and kneading to make the resins mutually soluble, and after cooling and solidifying, the particles are crushed and classified to obtain a toner with an average particle size of 5 to 20 JL. I can do 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 with the monomers that should 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.

The toners produced 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 has the following effects.

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, the above-mentioned problems such as development fog, toner scattering, and contamination of electrophotographic photosensitive materials and copying machines are eliminated, and since the toner of the present invention is extremely excellent, for example, it is possible to eliminate problems such as storage, which was a major problem in the past. It is a toner that can withstand long-term storage without causing phenomena such as agglomeration, clumping, and low-temperature flow of the toner inside, and also has excellent abrasion resistance, fixing properties, and adhesion 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.

[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 #44) 10 parts Low molecular weight polyethylene wax 2 parts Compound example (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.

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 JL.

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 charge 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 printed paper and heat-fixed. The resulting transferred image has a density of 1.
33, which was sufficiently high, and there was no fogging at all, and a good image with high resolution was obtained without toner scattering around the image. Transfer images were continuously created using the above developer and their durability was examined, and the transferred images after 30,000 copies were also completely dull compared to the initial images.

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 durability test for ao and ooo sheets, I checked the fuser machine and found no scratches or damage to the roller, and there was almost no dirt from offset toner, so there were no practical problems at all. There wasn't.

In addition, when the environmental conditions were set to 35°C and 85%, the image density was 1.27, 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 15 degrees Celsius.
When a transferred image was obtained at a low temperature and low quality of 10%, the image density was as high as 1.36, solid black was developed and transferred extremely smoothly, and the image was excellent with no splatters or voids. 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 copies, 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 Example (1).
Fixation was performed and an image was obtained in the same manner.

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.

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 68%.

When an image was obtained under the conditions of 15° C. and 10%, the image density was as low as 0.31, and there was severe scattering, fogging, 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 Example (2) was used instead of 2 parts of Compound Example (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 substantially similar to those of Example 1 were obtained.

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

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 Example (4) was used instead of 2 parts of Compound Example (1), and images were obtained in the same manner by performing development, transfer, and fixing.

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 (Toda Kogyo type) 60 parts Low molecular weight polypropylene wax 2 parts Compound example (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 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 IL. Ta.

Next, hydrophobic colloidal silica R was added to 100 parts of the fine powder.
-972 (manufactured by Nippon Aerosil Co., Ltd.) was mixed in a sample mill to prepare a -component magnetic toner, and 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 Copy A (trade name NP-1502, 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 Example (2) was used instead of 2 parts of Compound Example (1), and development, transfer, and fixing were carried out in the same manner. Got the image.

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 Example (3) was used instead of 2 parts of Compound Example (1), and development, transfer, and fixing were carried out in the same manner. Got the image.

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 Example (1), and an image was obtained in the same manner. At room temperature and humidity, 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 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 0.53 after 30,000 sheets, making it impractical.

Example 8 Copper phthalocyanine blue pigment 5 parts Low molecular weight polypropylene wax 2 parts Compound example (
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 JL. Ta.

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

Next, 50 g of magnetic particles having a particle size of 50 to 80 IL were 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 magnetic particle-toner mixture, 58 is a plate for regulating toner thickness, 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 hover of 3 is taken in and coated in a thin layer uniformly on 2.Then, the toner is carried. The body 2 and the electrostatic image holding body 1 are made to face each other with a gap larger than the thickness of one toner layer, and the toner 5 on 2 is
The image is developed by flying onto the electrostatic charge image above.

The thickness of the toner layer is controlled by the size of the magnetic brush 52, ie, the amount of magnetic particles, and the regulating blade 58. l and 2
A developing bias of 6 may be applied by making the gap between the toner and the toner layer larger than the thickness of the toner layer.

The evaluation results of each example and comparative example are shown in Tables 1 and 2.

Table 1 Table 2 ■ □1 degree 5θ [Effects of the invention] (1) Between toner particles or between toner and carrier, -
In the case of component development, the developer has a stable triboelectric charge between the toner and the sleeve, a sharp and uniform triboelectric charge distribution, and can be controlled to an appropriate charge for the developing system used.

(2) A developer capable of faithfully developing and transferring a latent image. Therefore, high image density can be obtained and halftone reproducibility is good.

(3) The developer maintains its initial characteristics even after long-term continuous use, and there is no change in toner aggregation or charging characteristics.

(4) A developer that can reproduce stable images unaffected by changes in temperature and humidity, has excellent storage stability, and produces images with vivid chromatic colors.

(5) The developer is easy to clean, has good fixing properties, and has no problems with high-temperature offset.

[Brief explanation of the drawing]

FIG. 1 is a schematic partial cross-sectional view for explaining 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 (1)

[Claims] (1) The following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1 and R_2 are hydrogen, or alkyl without or with a substituent, represents an aralkyl or aryl group, and optionally can have one or more unsubstituted or substituted alkyl, aralkyl or aryl groups in the heterocycle; A is Cl, Br, I, NO_3 -, SO_4^2-
, or an anion of SO_3^2-.