JPH0731413B2 - Positively charged toner for electrostatic image development - Google Patents

Description

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

[Prior Art] Conventionally, as an electrophotographic method, various methods are described in U.S. Patent No. 2,297,691, Japanese Patent Publication No. 42-23910 and Japanese Patent Publication No. 43-24748, but in short, they are A uniform electrostatic charge is applied on the photoconductive insulating layer, and an electrostatic latent image is formed by irradiating the insulating 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. Also, the toner is
Depending on the polarity of the electrostatic latent image to be developed, positive or negative electric charge is held.

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.

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

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

Nigrosine, azine dyes containing alkyl groups having 2 to 16 carbon atoms (Japanese Patent Publication No. 42-1627), basic dyes (eg CI
Basic Yellow 2 (CI41000), CIBasic Yellow 3,
CIBasic Red 1 (CI45160), CIBasic Red 9 (C.
I.42500), CIBasic Violet 1 (CI42535), CIBa
sic Violet 3 (CI42555) CIBasic Violet 10 (CI
45170), CIBasic Violet 14 (CI42510), CIBas
ic Blue 1 (CI42025), CIBasic Blue 3 (CI5100
5), CIBasic Blue 5 (CI42140), CIBasic Blue
7 (CI42595), CIBasic Blue 9 (CI52015), C.
I.Basic Blue 24 (CI52030), CIBasic Blue 25
(CI52025), CIBasic Blue 26 (CI44045), C.
I.Basic Green 1 (CI42040), CIBasic Grenn 4
(CI42000), CI42510, CI45170 etc. Lake pigments of these basic dyes (as a laker, phosphotungstic acid, phosphomolybdic acid, phosphotungstic molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.), CISolv
ent Black 3 (CI, 26150), Hansa Yellow G (CI
11680), CIMordlant Black 11, CIPigment Black
1, Gilsonite, asphalt, etc.

Quaternary ammonium salts such as benzylmethyl-hexadecyl ammonium chloride, decyl-trimethyl ammonium chloride, organotin compounds such as dibutyltin oxide, metal salts of higher fatty acids, glass, mica, inorganic fine powders such as zinc oxide, EDTA, Polyamine resins such as amino group-containing vinyl polymers and amino group-containing condensation polymers such as metal complexes of acetylacetone.

(2) The following substances control the toner to be negatively charged.

Japanese Patent Publications No. 41-20153, No. 43-27596, No. 44-6397, and No.
Metal complex salts of monoazo dyes described in 45-26478 and the like.

Nitrohumic acid and its salts or dyes and pigments such as CI14645 described in JP-A-50-133338.

JP-B-55-42752, JP-B-58-41508, JP-B-59-73
Metal complexes of salicylic acid, naphthoic acid and dicarboxylic acid such as Co, Cr and Fe described in JP-B No. 84 and JP-B-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 complicated structure and inconsistent properties, and are poor in 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 For this reason, various methods have been conventionally used for more uniform dispersion. 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 bright 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, these charge control agents are hydrophilic, so that a high quality image cannot be obtained.

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. Further, this obstacle appears as a remarkable phenomenon when the number of times of copying is increased, 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 at room temperature and normal humidity, when the toner is stored for a long period of time, it deteriorates due to instability of the charge control agent used and often becomes unusable due to poor chargeability.

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 those which deteriorate the high temperature offset performance, increase the sticking property of the transfer paper to the roller at the time of heat roll fixing, and reduce the durable life of the roller.

Many drawbacks are found in such conventional charge control agents,
There is a strong demand in the art to improve these,
Although many improved techniques have been proposed so far, the fact is that none of them has been found to be totally satisfactory in practical use.

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

Another object of the present invention is to provide a stable triboelectrification amount between toner particles, a toner and a carrier, a toner and a toner carrier such as a sleeve in the case of one-component development, and a triboelectrification amount distribution. The purpose of the present invention is to provide a developer that is sharp and uniform and that can control the 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, fogging 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 provides the following formula [I]: (In the formula, R ₁ is a hydrogen atom, a substituted or unsubstituted alkyl group,
Represents an aryl group, an aralkyl group or an acyl group,
R ₂ , R ₃ and R ₄ are each a hydrogen atom, an alkyl group, an aryl group,
Aralkyl group, an alkoxy group, an acyl group, an amino group, a halogen atom or a nitro group, A ^- is BF ₄ ^- or PF ₆ ^-
Indicates. ), A quinolinium salt, a binder resin, a colorant, and a fixing aid, which are positively charged toners for developing electrostatic images.

In the above general formula [I], R is a hydrogen atom; an alkyl group which may be branched, such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group or a dodecyl group;
Substituted alkyl groups such as methoxyethyl group, ethoxyethyl group, butoxyethyl group, chloroethyl group, dimethylaminoethyl group; aryl groups or substituted aryl groups such as phenyl group, toluyl group, butylphenyl group, butoxyphenyl group, chlorophenyl group; Examples thereof include aralkyl groups such as benzyl group, phenethyl group and methylbenzyl group; acyl groups such as acetyl group and benzoyl group.

In addition, when R ₂ , R ₃ and R ₄ are other than hydrogen atom, that is,
In the case of a substituent for substituting a heterocycle, R ₂ , R ₃ and R ₄ may be a branched alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group or a dodecyl group; methoxyethyl Group, ethoxyethyl group, butoxyethyl group, chloroethyl group, substituted alkyl group such as dimethylaminoethyl group; phenyl group, toluyl group, butylphenyl group, butoxyphenyl group, aryl group such as chlorophenyl group or substituted aryl group; benzyl Group, phenethyl group, aralkyl group such as methylbenzyl group, methoxy group, ethoxy group, propoxy group, butoxy group, alkoxy group such as octoxy group; acyl group such as acetyl group, benzoyl group; fluorine atom, chlorine atom, bromine atom A halogen atom such as an iodine atom; an amino group; a nitro group.

The inventors of the present invention have found that a quinolinium salt having BF ₄ ⁻ or PF ₆ ⁻ as a counter ion is thermally and temporally stable, and when contained in a developer, it has a good quality to give a developer having excellent electrophotographic characteristics. The inventors arrived at the present invention by discovering that they are charge control agents.

The following are typical specific examples of the compound represented by the general formula [I].

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

That is, the corresponding quinoline or quinoline derivative is treated with an alkyl halide, an acyl halide, an aryl halide or the like to obtain a quinolinium halide. Next, an aqueous solution of borofluoric acid or an aqueous solution of hexafluorophosphoric acid is added dropwise to the aqueous solution to obtain a desired product by white precipitation.

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 is determined by the types of the binder resin and the fixing aid, the presence or absence of additives used as necessary, and the toner production method including the dispersion method. Although not limited thereto, it is preferably used in the range of 0.1 to 10 parts by weight (more preferably 0.5 to 5 parts by weight) with respect to 100 parts by weight of the binder resin.

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 and disazo 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-vinylphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-
Butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethacrylic acid Methyl 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-based copolymers such as polymers, styrene-acrylonitrile-indene copolymers, styrene-maleic acid copolymers, styrene-maleic acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyacetic acid Vinyl, poly Styrene, polypropylene, polyester, polyurethane, polyamide, epoxy resin, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resins, phenol resins, and the like, can be used alone or in combination.

Further, as the binder resin particularly suitable for low pressure wear, the following resins 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, iron powder, ferrite powder, magnetic powder such as nickel powder, glass beads, etc., and their surfaces treated with a resin or the like. Something is included.

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 or aluminum, cobalt,
Examples thereof include alloys of metals such as copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten and vanadium, and mixtures thereof.

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

Examples of the fixing aid include waxes such as low molecular weight polyethylene wax and low molecular weight polypropylene wax used in the examples described later.

Further, the toner of the present invention may be mixed with an additive as required. Examples of the additive 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 other conductivity-imparting agents.

To prepare the toner for developing an electrostatic image according to the present invention, the charge control agent according to the present invention is used as a vinyl-based or non-vinyl-based thermoplastic resin, a fixing aid and a pigment or dye as a colorant, and if necessary. Magnetic materials, additives, etc. were thoroughly mixed by a ball mill or other mixing machine, and then melted, kneaded and kneaded using a heat kneader such as a heating roll, kneader or extruder to make the resins compatible with each other. It is possible to disperse or dissolve a pigment or dye therein, cool and solidify, and then pulverize and classify to obtain a toner having an average particle size of 5 to 20 μm.

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 A method such as a polymerization method for obtaining a toner and a toner manufacturing method can be applied.

The toners produced by these methods can all be used for development to visualize an electrostatic charge image in electrophotography, electrostatic recording, electrostatic printing, etc. by conventionally known means, and are excellent as follows. It produces the effect.

That is, the triboelectric charge amount for 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. Therefore, the above-mentioned obstacles such as development fog, toner scattering, contamination of electrophotographic photosensitive material and copying machine are eliminated, and the toner of the present invention is extremely excellent. Agglomeration,
It is a toner that can withstand long-term storage without causing phenomena such as agglomeration and low-temperature flow, 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 copying system in which the operations of charging, exposing, developing, and transferring are continuously repeated, the effect is further expanded. Further, since there is no 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] Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto. All parts in the following formulations are parts by weight.

Example 1 Styrene / butyl acrylate (80/20) copolymer (weight average molecular weight w: about 300,000) 100 parts Carbon black (Mitsubishi # 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 cool naturally, it is roughly crushed with a cutter mill, then crushed with a fine crusher using a jet stream, and further classified with a wind force classifier to obtain a fine powder having a particle size of 5 to 20 μ (that is, , Positively chargeable 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.

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, no fog, no toner scattering around the image, and a good image with high resolution was obtained. Transfer images were continuously created using the above developer, and durability was examined.
Compared to the initial image, the transferred image after 0000 sheets is completely,
The image was solid.

Further, at the time of durability, the above-mentioned filming phenomenon related to the toner of the photoconductor was not observed at all, and no problem was found in the cleaning process. At this time, there was no trouble in the fixing step, and the fixing machine was observed at the end of the 30,000-sheet durability test, but no scratches or damage on the roller were observed, and there was almost no stain from the offset toner, and there was no problem in practice.

Also, when the environmental conditions were set to 35 ° C and 85%, the image density was a value that was almost unchanged from room temperature and normal humidity, and a clear image was obtained without fog or scatter, and durability was hardly changed up to 30,000 sheets. It was Next, when a transferred image was obtained at a low temperature and low humidity of 15 ° C. and 10%, the image density was sufficiently high, and solid black was developed and transferred extremely smoothly, and was an excellent image without scattering and voids. Durability was performed under this environmental condition, but it was copied continuously and at intervals, but still 30,000
The density fluctuation was ± 0.2 from sheet to sheet, 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 in place of 2 parts of the compound (1), and development, transfer and fixing were carried out. Got the image to.

At room temperature and normal humidity, there was little fog, 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.

Also, at the time of endurance, from around 10,000 sheets, the toner material formed a thin streak-like film on the surface of the photoconductor 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.

When the image was obtained under the conditions of 15 ℃ and 10%, the image density was 0.
It was as low as 91, and scatter, fog, and rubbing were noticeable. Although continuous images were printed, the density became 0.53 after about 30,000 sheets, making it unusable.

Example 2 A developer was obtained 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), development, transfer, and
An image was similarly obtained by fixing.

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), development, transfer, and
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 4 A developer was obtained in the same manner as in Example 1 except that 2 parts of the compound (4) was used instead of 2 parts of the compound (1), development, transfer, and
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 5 Styrene / butyl acrylate (80/20) copolymer (weight average molecular weight w: about 300,000) 100 parts 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 cool naturally, it is roughly crushed with a cutter mill, crushed with a fine crusher using a jet stream, and further classified with an air classifier to obtain a fine powder with a particle size of 5 to 20μ. It was

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.

When this toner was applied to a commercially available copying machine (trade name: NP-150Z, manufactured by Canon Inc.) and image formation was performed, good results almost similar to those in Example 1 were obtained.

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

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

Example 7 A developer is obtained in the same manner as in Example 5 except that 2 parts of the compound (3) is used instead of 2 parts of the compound (1), and development, transfer and fixing are performed, and an image is similarly obtained. Got

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 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. 15 ℃,
When an image was obtained under the condition of 10%, the image density was as low as 0.73, and scattering, fog, and rubbing were noticeably observed. The continuous image was printed, but the density was reduced to 30,000 sheets.
It became 0.59, which is not practical.

Example 8 Styrene / butyl acrylate (80/20) copolymer (weight average molecular weight w: about 300,000) 100 parts 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 cool naturally, it is roughly crushed with a cutter mill, crushed with a fine crusher using a jet stream, and further classified with an air classifier to obtain a fine powder with a particle size of 5 to 20μ. It was

Next, to 100 parts of the fine powder, carrier iron powder having a particle size of 50 to 80 μ
0 g was mixed to obtain a developer.

When an image was formed using this developer by the developing method shown in FIG. 1, a good image showing a vivid blue color was obtained. After 1500 sheets were formed, the toner / carrier was 10 g /
It became 50 g, but there was almost no change in image density,
After that, images were printed up to 30 million sheets while reinforcing the toner, but good images were obtained.

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 made of a carrier toner mixture, 58 is a toner thickness regulating blade, and 50 is fixed. A magnet, 6 is a developing bias, and 5 is a toner.

That is, the magnetic brush 52 formed on the toner carrier 2 is circulated by rotating the toner carrier 2, and the toner in the hopper 3 is taken in 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 carrier 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.

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

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

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

(2) A developer capable of faithful development and transfer to a latent image, maintaining initial characteristics even when continuously used for a long period of time, and having no toner aggregation and no change in charging characteristics.

(3) A developer that can reproduce a stable image that is not affected by changes in temperature and humidity and that can obtain a bright chromatic image.

(4) It is a developer which has an easy cleaning process which does not stain, rub or scratch the electrostatic latent image surface and which has excellent fixing characteristics and which does not have a problem particularly in high temperature offset.

BRIEF DESCRIPTION OF THE 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 front page (56) Reference JP-A-56-11461 (JP, A) JP-A-49-51951 (JP, A) JP-A-59-111154 (JP, A) JP-A-59- 177571 (JP, A)

Claims (3)

[Claims] 1. The following formula [I]: (In the formula, R ₁ represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an aralkyl group or an acyl group,
R ₂ , R ₃ and R ₄ are each a hydrogen atom, an alkyl group, an aryl group,
Aralkyl group, an alkoxy group, an acyl group, an amino group, a halogen atom or a nitro group, A ^- is BF ₄ ^- or PF ₆ ^-
Indicates. ) A positively chargeable toner for developing an electrostatic charge image, containing a quinolinium salt represented by the formula (3), a binder resin, a colorant and a fixing aid. 2. The positively chargeable toner for developing an electrostatic charge image according to claim 1, wherein the fixing aid is wax. 3. The binder resin comprises a styrene-based copolymer,
The first fixing agent comprises a low molecular weight polyethylene wax or a low molecular weight polypropylene wax.
Item 4. A positively chargeable toner for developing an electrostatic charge image according to item.