JPH07117766B2 - Developer for electrostatic image development - Google Patents

Description

The present invention relates to a novel developer for developing an electrostatic charge image in electrophotography, electrostatic recording, electrostatic printing and the like.

[Prior Art] Conventionally, various methods for electrophotography have been described in US Pat. No. 2,297,691, Japanese Patent Publication No. 42-23910, Japanese Patent Publication No. 43-24748, etc. Forming a static latent image by applying a uniform electrostatic charge on the photoconductive insulator layer and irradiating the insulator layer with a light image,
Then, the latent image is developed and visualized by fine powder called toner in the art, and if necessary, the powder image is transferred to paper or the like, and then fixed by heating, pressurizing, or solvent vapor.

As a developing method applied to these electrophotographic methods,
It is roughly classified into a dry development method and a wet development method. The former is further divided into a method of using a two-component developer and a method of using a one-component developer. Depending on the type of carrier that carries the toner, the two-component developing method
Magnet brush method using iron powder carrier, beads
There are a cascade method using a carrier and a fur brush method using a fur.

Further, those belonging to the one-component developing method include a powder cloud method in which toner particles are sprayed and a contact developing method (contact developing or (Also referred to as toner development), a jumping development method in which toner particles are not brought into direct contact with the electrostatic latent image surface, but the toner particles are charged and fly toward the latent image surface by the electric field of the electrostatic latent image, magnetic conductivity. There is a magnetic dry method in which a volatile toner is brought into contact with an electrostatic latent image surface for development.

As a toner applied to these developing methods, a fine powder in which a dye or a pigment is dispersed in a natural or synthetic resin is conventionally used. For example, particles in which a colorant is dispersed in a binder resin such as polystyrene and finely pulverized to about 1 to 30 μm are used as a toner. A magnetic toner 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 before use. Further, the toner has a positive or negative charge depending on the polarity of the electrostatic latent image to be developed.

To retain the electric charge in the toner, it is possible to utilize the triboelectric charging property of the resin which is a component of the toner, but since the toner charging property is small in this method, the image obtained by development is easily fogged and unclear. Will be things. Therefore, in order to impart a desired triboelectric chargeability to the toner, a dye, a pigment or a charge control agent which imparts the chargeability is added.

The charge control agents currently known in the art include the following.

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

Nigrosine, an azine dye containing an alkyl group having 2 to 16 carbon atoms (Japanese Examined Patent Publication No. 42-1627), a basic dye (for example, CI Basic Yellow 2 (CIBasic Yellow
2) (CI41000), C-I Basic Yellow 3 (CIBasic Yellow 3), C-I Basic
Red 1 (CIBasic Red 1) (CI45160), C I Basic Red 9 (CIBasic Red 9) (CI4
2500), CI Basic Violet 1 (C.
I.Basic Violet 1) (CI42535), CI Basic Violet 3 (CIBasic Violet 3) (CI
42555), C-I Basic Violet 10
(CIBasic Violet 10) (CI45170), C
Basic Violet 14 (CIBasic Violet 14)
(CI42510), C-I Basic Blue 1
(CIBasic Blue 1) (CI42025), C-I Basic Blue 3 (CIBasic Blue 3) (CI5100)
5), C-I Basic Blue 5 (CIBasic B
lue 5) (CI42140), sea eye basic blue 7 (CIBasic Blue 7) (CI42595), sea eye basic blue 7 (CIBasic Blue 7) (CI42
595), C-I Basic Blue 9 (CIBasic
Blue 9) (CI52015), C eye basic blue 24 (CIBasic Blue 24) (CI52030), C eye basic blue 25 (CIBasic Blue 25) (C.
I.52025), C-I Basic Blue 26 (CIB
asic Blue 26) (CI44045), C eye basic green 1 (CIBasic Green 1) (CI42040),
C I Basic Green 4 (CIBasic Gree
n 4) (CI42000), CI42510, CI45170, CI Basic Blue 9 (CIBasic Blue 9), etc.). Lake pigments of these basic dyes (as the laking agent, phosphotungstic acid, phosphomolybdic acid, phosphotungstic molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.), C.I.・ Solvent Black 3 (CISo
lvent Black 3) (CI26150), Hansaye G (CI
11680), C-I Moirant Black 11 (CIM
orelant Black 11), CI Pigment Black 1 (CIPigment Black 1), Gilsonite, asphalt, etc.

Quaternary ammonium salts such as benzolmethyl-hexadecylammonium chloride, decyl-trimethylammonium chloride, organic tin compounds such as dibutyltin oxide, metal salts of higher fatty acids, glass, mica, inorganic fine powders of zinc oxide, EDTA, acetylacetone Polyamine resins such as amino group-containing vinyl polymers and amino group-containing condensation polymers, such as the metal complexes of.

(2) The following is what controls the toner to be negatively charged.

Japanese Patent Publication No. 41-20153, 43-27596, 44-6397, 45-
Monoazo dye metal complex salt represented by the following general formula, described in No. 26478, etc. [Wherein M is Cr or Co, R ₁ and R ₂ are phenylene residues which are unsubstituted or substituted by a substituent, and R ₃ and R ₄ are non-coupling groups at the ortho position of the metallizable group. Represents a residue of a coupling component substituted with a substituent or a substituent, X ₁ and X ₂ are —O— or —COO—, and X ₃ and X ₄ are —O.
Represents-, -NH- or -N-alkyl-, and [A] ⁺ represents hydrogen ion, ammonium ion, aliphatic ammonium ion, alicyclic ammonium ion, heterocyclic ammonium ion alkali metal or alkaline earth metal . ] Dyes and pigments such as nitrohumic acid and its salts or CI14645 described in JP-A-50-133338.

JP-B-55-42752, JP-B-58-41508, JP-B-59-7384
Metal complexes of salicylic acid, naphthoic acid, and dicarboxylic acid such as Co, Cr, and Fe described in JP-B No. 59-7385. Sulfonated copper phthalocyanine pigment. Styrene oligomer with nitro group and halogen introduced. Chlorinated paraffin, melamine resin, etc.

Many of these charge control agents are derived from dyes and pigments,
Generally, the structure is complicated and most of them have strong coloring properties.

Among the newly proposed ones, there are some that are of a different system from these, but there is no one that outperformed the dye-pigment system in terms of overall performance, and there are still examples of dyes that are unsatisfactory. Mostly.

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

However, these dyes as charge control agents have a complex structure and inconsistent properties, and thus have poor stability. In addition, decomposition or deterioration is likely to occur due to decomposition during thermal kneading, mechanical shock, friction, changes in temperature / humidity conditions, etc., and a phenomenon in which charge controllability is deteriorated is likely to occur.

Therefore, when a toner containing these dyes as a charge control agent is developed using a copying machine, the charge control agent may be decomposed or deteriorated as the number of times of copying increases, and the toner may deteriorate during its durability.

Further, since it is extremely difficult to uniformly disperse these charge control agents in the thermoplastic resin, there is a fatal problem that the triboelectric charge amount between the toner particles obtained by pulverization causes a difference. Have Therefore, various methods have heretofore been used in order to make the dispersion more uniform. For example,
The basic nigrosine dye is used by forming a salt with a higher fatty acid in order to improve the compatibility with the thermoplastic resin.
Often, unreacted fatty acid or salt dispersion product is exposed on the toner surface and contaminates the carrier or the toner carrier, resulting in 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 in the resin, a method of mechanically pulverizing and mixing the charge control agent powder and the resin powder in advance and then hot-melt kneading is used. However, the original poor dispersion cannot be avoided, and in the current situation, sufficient charge uniformity for practical use has not yet been obtained.

Further, most of the substances generally known as the charge control agent have a dark color, and thus there is a problem that they cannot be contained in a vivid chromatic color developer.

In addition, many charge control agents are hydrophilic, and due to poor dispersion in these resins, when melt-kneaded and then crushed,
The dye is exposed on the toner surface. Therefore, when the toner is used under high humidity conditions, there is a problem that a high quality image cannot be obtained because the charge control agent is hydrophilic.

Thus, when the conventional charge control agent is used in the toner,
Between the toner particles, between the toner and the carrier, or between the toner carrier such as the toner and the sleeve, the amount of electric charge generated on the surface of the toner particles varies, and development fog, toner scattering, carrier contamination, etc. Failures are likely to occur. In addition, this obstacle appears as a remarkable phenomenon when a large number of copies are piled up, and is substantially unsuitable for a copying machine.

Further, under high humidity conditions, the transfer efficiency of toner images is significantly reduced, and many of them cannot be used. Even when the toner is stored for a long period of time even at room temperature and normal humidity, it often becomes unusable due to instability due to instability of the charge control agent used.

Furthermore, when a conventional charge control agent is used for toner, the charge control agent adheres to the surface of the photoconductor or promotes the adhesion of the toner due to long-term use, which adversely affects latent image formation (filming phenomenon). ), Those that cause scratches on the surface of the photoreceptor or cleaning members such as cleaning blades, or those that accelerate the wear of the members, have many adverse effects on the cleaning process of the copying machine.

Furthermore, when a conventional charge control agent is used in toner, there are not a few that greatly affect the heat melting characteristics of the toner and deteriorate the fixing performance. In particular, there are some that deteriorate the high temperature offset performance, increase the sticking property to the roller of the transfer machine at the time of heat roll fixing, and reduce the durable life of the roller.

As described above, the conventional charge control agent has many problems, and there is a strong demand in the technical field to improve them, and many improvements have been proposed so far, but they are still in practical use. Above all, the actual situation is that nothing has been found that is totally satisfactory.

An object of the present invention is to provide a new technique of toner charge control that overcomes such problems.

[Problems to be Solved by the Invention] An object of the present invention is to stabilize the triboelectric charge amount between toner particles, between toner and carrier, between toner and a toner carrier such as a sleeve in the case of one-component development. In addition, the triboelectric charge distribution is sharp and uniform, and the developer can be controlled to a charge amount suitable for the developing system used.

Still another object is a developer that faithfully develops and transfers a latent image, that is, adhesion of toner in the background area at the time of development, that is, fog and scattering of toner around the edge of the latent image, High image density is obtained,
This is to provide a developer having good halftone reproducibility.

Still another object is to provide a developer which maintains the initial characteristics even when the developer is continuously used for a long period of time and does not cause aggregation of toner or change in charging characteristics.

Still another object is to provide a developer that reproduces a stable image that is not affected by changes in temperature and humidity, especially a developer with high transfer efficiency that does not cause scattering or transfer omission during transfer at high humidity and low humidity. In offer.

Still another object is to provide a bright chromatic color developer.

Still another object is to provide a developer having excellent storage stability, which maintains the initial characteristics even after long-term storage.

Still another object is to provide a developer which can be easily cleaned in a cleaning step without causing the electrostatic latent image surface to be soiled, worn or scratched.

Still another object is to provide a developer having good fixing characteristics, particularly a developer having no problem in high temperature offset and the like.

[Means and Actions for Solving Problems] The present invention relates to a developer for electrostatic charge development, which comprises a 1,2,3-triazole derivative.

More specifically, the present invention relates to a binder resin, a colorant and the following general formula [Wherein R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are the same or different groups and are hydrogen, or an alkyl group, a cyclic alkyl group, an alkenyl group, an aryl group, an alkylene group, an aralkyl group, an aryl group. Means a substituent having a hydrocarbon as a basic skeleton or an amino group or a substituted amino group such as a secondary or tertiary amino group. ] The present invention relates to a developer for developing an electrostatic charge image, which comprises a toner containing a compound represented by the formula:

The present inventors have found that the compounds represented by any of the general formulas [1] to [6] are thermally and temporally stable, have a low hygroscopic property, and have excellent electrophotographic properties when contained in a developer. It has been found that it is a high-quality charge control agent that gives a good developer.

The following are typical specific examples of the compound represented by any of the general formulas [1] to [6].

As a method of incorporating the above compound into the developer, there are a method of adding it inside the toner particles and a method of adding it externally. When internally added, the amount of these compounds used depends on the type of binder resin,
The presence or absence of additives used as necessary, which is determined by the toner production method including the dispersion method, is not uniquely limited, but preferably 0.1 to 100 parts by weight of the binder resin. It is used in the range of 50 to 50 parts by weight (more preferably 1 to 20 parts by weight).

When adding externally, 0.01 to 40 parts by weight per 100 parts by weight of resin
Parts by weight are preferred.

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

Examples of the colorant used in the present invention include carbon black, lamp black, iron black, ultramarine blue, nigrosine dye, aniline blue, phthalocyanine blue, phthalocyanine green, Hansa 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, disazo dyes and dyes may be used alone or in combination.

As the binder resin used in the present invention, polystyrene,
Monopolymers of styrene such as poly-p-chlorostyrene and polyvinyltoluene and their substitution products; 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 Coal, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate 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- Maleic acid copolymer Styrene-based copolymers such as styrene-maleic acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, polyurethane, polyamide, epoxy resin, polyvinyl butyral, polyacrylic Examples thereof include acid resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, and paraffin wax, which can be used alone or in combination.

Further, as the binder resin particularly 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 to 30:95 to 70), olefin copolymer ( 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 phenol resin, phenol modified terpene resin.

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

As the carrier that can be used in the present invention, all known carriers can be used, for example, magnetic powder such as iron powder, ferrite powder and nickel powder, glass beads and the like, and their surfaces treated with resin or the like. And so on.

Further, the toner of the present invention can be used as a magnetic toner by further containing a magnetic material. The magnetic material contained in the magnetic toner of the present invention includes iron oxide such as magnetite, hematite, and ferrite. Metals such as iron, cobalt, nickel such as aluminum, cobalt, copper, iron, lead, magnesium, nickel, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium. Alloys of metals and mixtures thereof.

It is desirable that these ferromagnetic materials have an average particle size of about 0.1 to 2 .mu.m.
It is about 20 to 200 parts by weight based on 0 parts by weight, particularly preferably 40 to 150 parts by weight based on 100 parts by weight of the resin component.

Further, the toner of the present invention may be mixed with an additive as required. Examples of the additives include lubricants such as Teflon and zinc stearate, abrasives such as cerium oxide and silicon carbide, fluidity imparting agents such as colloidal silica and aluminum oxide, anti-caking agents, or carbon black and tin oxide. And the like, or 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 a vinyl-based or non-vinyl-based thermoplastic resin and a pigment or dye as a colorant, and if necessary, a magnetic material, After thoroughly mixing the additives and the like with a ball mill or other mixing machine, use a heat kneader such as a heating roll, kneader, or extruder to melt, knead, and knead the meat to make the resins compatible with each other. The pigment or dye is dispersed or dissolved, cooled and solidified, then crushed and classified to have an average particle size of 5
It is possible to obtain a toner of up to 20μ.

Alternatively, a method in which the material is dispersed in a binder resin solution and then spray-dried, or a predetermined material is mixed with a monomer to form the binder resin to form an emulsified suspension and then polymerized Polymerization method to obtain toner The method of toner manufacturing method can be applied.

The toners produced by these methods can be all used by conventional means for development for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing, etc. It has an excellent effect.

That is, the triboelectric charge amount between the toner particles is uniform, and the control of the electric charge amount is easy. Further, the toner is extremely stable without deteriorating during use so that the triboelectric charge amount does not vary or decrease. As a result, the above-mentioned obstacles such as reduced fog, toner scattering, contamination of electrophotographic photosensitive materials and copying machines are eliminated, and the toner of the present invention is extremely excellent. It is a toner that can withstand long-term storage without causing phenomena such as aggregation, agglomeration, and low-temperature fluidization, and has excellent abrasion resistance, fixability, and adhesiveness of toner images.

The excellent effect of such a toner is that when it is used in a repetitive transfer type copying system in which operations of charging, exposure, phenomenon, and transfer are continuously repeated, the effect is further expanded. Further, since there is little color tone disorder due to the charge control agent, it is possible to form a color image of excellent color when used as a color electrophotographic toner.

EXAMPLES Next, the present invention will be described with reference to examples, but the invention is not limited thereto. All parts in the following formulations are parts by weight.

Example 1 Styrene / butyl acrylate (80/20) copolymer 100 parts (weight average molecular weight w: about 300,000) carbon black (Mitsubishi I 44) 10 parts low molecular weight polyethylene wax 2 parts Compound (1) 2 parts The above materials Was thoroughly mixed with a blender and then kneaded with two rolls heated to 150 ° C. After allowing the kneaded product to naturally cool, after roughly crushing with a cutter mill, it is crushed with a fine crusher using a jet stream, and further classified with a wind force classifier, that is, fine powder having a particle size of 5 to 20 μ, that is, Toner was obtained.

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 μm.

Further, the triboelectric charge amount of the developer was measured by a usual blow-off method.

Then, a negative electrostatic image is formed on the OPC photosensitive member by a conventionally known electrophotographic method, and this is powder-developed by the magnetic brush method using the above developer to form a toner image, which is transferred to plain paper. Heated and fixed. The obtained transferred image had a sufficiently high density of 1.28, no fog, no toner scattering around the image, and a good image with high resolution was obtained. Transfer images were continuously prepared using the above-mentioned developers and durability was examined. The transferred images after 30,000 sheets were completely achromatic images as compared with the initial images.

Further, at the time of durability, the above-mentioned filming phenomenon relating to the toner on the photosensitive member was not observed at all, and no problem was found in the cleaning process. At this time, there were no troubles in the fixing process, and the fixing machine was observed at the end of the durability test for 30,000 sheets, but no scratches or damage on the rollers were observed, and there was almost no stain due to the offset toner, and there was no problem in practice.

Also, when the environmental conditions were 35 ° C and 85%, the image density was
It was a value of 1.18, which was almost unchanged from room temperature and normal humidity, a clear image was obtained without fogging and scattering, and durability was hardly changed up to 30,000 sheets. Next, when a transferred image was obtained at a low temperature and low humidity of 10 ° C. and 10%, the image density was high at 1.29, and the solid black was developed and transferred very smoothly, and was an excellent image without scattering or hollow spots. Durability was carried out under these environmental conditions, but copying was carried out continuously and at intervals, but again the density fluctuation was ± 0.2, which was sufficient for practical use up to 30,000 sheets.

Comparative Example 1 A developer was obtained in the same manner as in Example 1 except that 2 parts of the Nigrosine dye was used instead of 2 parts of the compound (1), and development, transfer, and
An image was similarly obtained by fixing.

Fog was small at room temperature and normal humidity, but the image density was low at 1.06, and line drawings were scattered, and solid black was noticeable. When the durability was examined, the density decreased to 0.83 after 30,000 sheets.

In addition, at the time of running, from around 10,000 sheets, the toner material formed a thin streak-like film on the surface of the photoreceptor and appeared as lines on the image. This is so-called filming, and it is considered that the charge control agent changes the lubricity of the toner powder.

In addition, at the time of endurance, a fixed image tends to be easily caught in the fixing roller in the fixing step, and there is a difficulty in peeling off the roller.

Image density was 0.88 when images were obtained at 35 ℃ and 85%.
It became low and fog, splattering, and rubbing increased. The transfer efficiency was also low at 69%.

When an image was obtained at 10 ° C and 10%, the image density was as low as 0.91 and scatter, fog, and rustling were noticeable. I made continuous images, but it was 30,0
The density became 0.53 at around 00 sheets, which was not practical.

Example 2 A developer was prepared in the same manner as in Example 1 except that 3 parts of the compound (2) was used instead of 2 parts of the compound (1).
An image was similarly obtained by fixing.

The detailed results are shown in Tables 1 and 2, and almost the same satisfactory results 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 the compound (3) was used instead of 2 parts of the compound (1), and development, transfer and fixing were performed, and an image was similarly obtained.

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 the compound (4) and 2 parts were used in place of the compound (1) and 2 parts, and development, transfer and fixing were performed, and an image was similarly obtained.

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

Example 5 Styrene / butyl acrylate (80/20) copolymer 100 parts (weight average molecular weight w: about 300,000) Iron trioxide EPT-500 (manufactured by Toda Kogyo) 60 parts Low molecular weight polypropylene wax 2 parts Compound (1 ) 2 parts The above materials were mixed well with a blender and then kneaded with two rolls heated to 150 ° C. After allowing the kneaded product to naturally cool, after roughly crushing with a cutter mill, it is crushed with a fine crusher using a jet stream, and further classified with a wind force classifier, that is, fine powder having a particle size of 5 to 20 μ, that is, Toner was obtained.

Next, 100 parts of the fine powder was mixed with 0.4 part of hydrophobic colloidal silica by a sample mill to prepare a one-component magnetic toner.

The triboelectric charge amount of this toner was measured by a usual blow-off method.

When this toner was applied to a commercially available copying machine (trade name: NP-150Z, manufactured by Canon Inc.) and an image was produced, the same good effect as in Example 1 was obtained.

Example 6 A developer was obtained in the same manner as in Example 5 except that the compound (2) and 3 parts were used in place of the compound (1) and 2 parts in Example 5, and development, transfer and fixing were performed, and the same procedure was followed. I got an image.

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 the compound (3) and 2 parts were used in place of the compound (1) and 2 parts in Example 5, and development, transfer and fixing were performed, and the same procedure was followed. I got an image.

Although the detailed results are shown in Tables 1 and 2, 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 the compound (1) in Example 5, and an image was similarly obtained. Fog was small at room temperature and normal humidity, but the image density was as low as 0.81 and line drawings were scattered, and the solid black was noticeable. When the durability was examined, the density decreased to 0.48 after 30,000 sheets.

Further, the filming phenomenon at the time of endurance and the problem in the fixing step were almost the same as those in Comparative Example 1 and were not the same.

Image density was 0.72 when images were obtained under the conditions of 35 ℃ and 85%.
It became low and fogging, scattering, and rubbing increased, and it was not usable. The transfer efficiency was also low at 63%.

When an image was obtained under the conditions of 10 ° C and 10%, the image density was as low as 0.73, and scattering, fog, and rubbing were noticeably observed. I made continuous images, but 30,000
At the time of printing, the density was 0.59, which was not practical.

Example 8 Styrene / butyl acrylate (80/20) copolymer 100 parts (weight average molecular weight w: about 300,000) Copper phthalocyanine blue pigment 5 parts Low molecular weight polypropylene wax 2 parts Compound (1) 2 parts The above material is blended. After mixing well, they were kneaded with two rolls heated to 150 ° C. After allowing the kneaded product to naturally cool, after roughly crushing with a cutter mill, it is crushed with a fine crusher using a jet stream, and further classified with a wind force classifier, that is, fine powder having a particle size of 5 to 20 μ, that is, Toner was obtained.

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

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

Using this developer, an image was produced by the developing device shown in FIG. 1, and a good image showing a vivid blue color was obtained. After producing 1500 sheets, the toner / carrier was 10 g /
Even at 50g, there is almost no change in image density,
After that, a good image was obtained even when images were output up to 30,000 sheets while replenishing the toner.

The main developing method will be described. In FIG. 1, 1 is an electrostatic image carrier, 2 is a toner carrier, 3 is a hopper, 52 is a magnetic brush of a magnetic particle-toner mixture, 58 is a toner thickness regulating blade, and 50 is a toner thickness regulating blade. Is a fixed magnet, 6 is a developing bias, and 5 is 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 to coat the 2 evenly in a thin layer. Next, the toner carrier 2 and the electrostatic image carrier 1 are opposed to each other with a gap larger than the toner layer thickness, and the toner 5 on 2 is fly-developed onto the electrostatic image on 1.

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

[Effects of the Invention] The following effects are obtained by the present invention.

(1) The developer of the present invention has a stable triboelectric charge amount between toner particles or between a toner and a carrier, in the case of a one-component phenomenon, between a toner and a toner carrier, and has a sharp and uniform triboelectric charge amount distribution. Therefore, it is possible to control the charge amount suitable for the phenomenon system used.

(2) A developer capable of performing development and transfer faithful to a latent image.

(3) It is a developer which can maintain initial properties even after continuous use for a long period of time, does not cause toner aggregation and changes in charging properties, and has excellent storage stability.

(4) A developer that gives a stable and bright chromatic image that is not affected by changes in temperature and humidity.

[Brief description of drawings]

FIG. 1 is an illustration of an example of a developing device to which the positively chargeable toner according to the present invention can be applied. 1 ... electrostatic image carrier, 2 ... toner carrier, 5 ... toner, 50 ... magnet, 52 ... magnetic brush, 58 ... regulating blade.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Katsuhiko Tanaka 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (56) References JP-A-59-78365 (JP, A)

Claims (2)

[Claims] 1. A binder resin, a colorant and the following formula (1),
(2), (3), (4), (5) or (6) [Wherein R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are the same or different groups and are hydrogen, or an alkyl group, a cyclic alkyl group, an alkenyl group, an aryl group, an alkylene group, an aralkyl group, an arylene group. Means a group having a hydrocarbon as a basic skeleton, an amino group, or a substituted amino group of a secondary amino group or a tertiary amino group. ] A developer for electrostatic charge image development comprising a toner containing a 1,2,3-triazole derivative represented by 2. The developer for developing an electrostatic image according to claim 1, wherein the toner further contains a low molecular weight polyethylene wax or a low molecular weight polypropylene wax.