JPH0646311B2 - 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.

BACKGROUND ART Conventionally, US Pat. No. 2,297,69 has been used as an electrophotographic method.
No. 1, JP-B-42-23910, and JP-B-43.
No. 24748, etc., various methods are described. In short, they apply a uniform electrostatic charge on a photoconductive insulating layer and irradiate the insulating layer with a light image to obtain a static image. An electrostatic latent image is formed, 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 heated, pressurized, or by solvent vapor. It is to fix.

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 using a two-component developer and a method using a one-component developer. Among the two-component developing methods, there are a magnet brush method using an iron powder carrier, a cascade method using a bead carrier, a fur brush method using a fur, etc., depending on the type of carrier that carries the toner.

The one-component developing method includes a powder cloud method in which toner particles are sprayed, a contact developing method in which toner particles are directly brought into contact with an electrostatic latent image surface for development (contact development, or toner development). (Also referred to as development), a jumping development method in which toner particles are not directly contacted 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 toner is brought into contact with the electrostatic latent image surface to develop the toner.

As a toner applied to these developing methods, particles obtained by finely pulverizing a dispersion of a dye and a pigment in a natural resin or a synthetic resin such as polystyrene into about 1 to 30 μm have been used. As the magnetic toner, one containing magnetic particles such as magnetite instead of or in addition to the above-mentioned dye or pigment is used. In the case of a system using a so-called two-component developer, the toner as described above is usually used by being mixed with carrier particles such as glass beads and iron powder.

Further, positive or negative electric charges are given to the toner in advance depending on the polarity of the electrostatic latent image to be developed.

In order to give an electric charge to the toner, it is possible to use only the triboelectric charge positive of the resin which is a component of the toner, but in this method the toner chargeability is small, so the image obtained by development is easily fogged and is not clear. It will be Therefore, in order to impart a desired triboelectric charging property to the toner, a charge control agent such as a dye or a pigment which enhances the charging property is added.

Examples of charge control agents known in the field of electrophotography today include the following.

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

Nigrosine, an azine dye containing an alkyl group having 2 to 16 carbon atoms (Japanese Patent Publication No. 42-1627), a basic dye (for example, CIBasic Yellow 2 (CI41000), CIBasic Yellow
3, CIBasic Red 1 (CI45160), CIBasic Red 9 (CI
42500), CIBasic Violet 1 (CI42535), CIBasic Vio
let 3 (CI42555), CIBasic Violet 10 (CI45170), C.
I.Basic Violet 14 (CI42510), CIBasic Blue 1 (CI
42025), CIBasic Blue 3 (CI51005), CIBasic Blue
5 (CI42140), CIBasic Blue 7 (CI42595), CIBasic
Blue 9 (CI52015), CIBasic Blue 24 (CI52030), C.
I.Basic Blue 25 (CI52025), CIBasic Blue 26 (CI4
4045), CIBasic Green 1 (CI42040), CIBasic Green
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.), CISolvent.
Black 3 (CI26150), High the Yellow G (CI11680), C.
I.Mordant Black 11, CI Pigment Black 1, Gilsonite, Asphalt, etc.

Quaternary ammonium salts such as benzyl-dimethyl-hexadecyl ammonium chloride, decyl-trimethyl ammonium chloride, organotin compounds such as dibutyltin oxide, metal salts of higher fatty acids, glass, mica,
Inorganic fine powder such as zinc oxide, EDTA, metal complex of acetylacetone, etc.

Polyamine resins such as amino group-containing vinyl polymers and amino group-containing condensation polymers.

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

Metal complex salts of monoazo dyes described in JP-B Nos. 41-20153, 43-27596, 44-6397 and 45-26478.

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

C of salicylic acid, naphthoic acid and dicarboxylic acid described in JP-B Nos. 55-42752, 58-41508, 59-7384 and 59-7385.
Metal complexes of o, Cr, Fe and the like.

Sulfonated copper phthalocyanine pigment.

Styrene oligomer with nitro group and halogen introduced. Chlorinated paraffin, melamine resin, etc.

However, as described above, the use of conventional charge control agents still has many problems to be improved. That is,
Many of these charge control agents are derived from dyes and pigments, and generally have a complicated structure, inconsistent properties, poor stability, and strong coloring properties. Recently, some of the proposed ones are different in system from the ones mentioned above, but none of them are superior in overall performance to those of the dye / pigment system, and despite many disadvantages as described below,
In most cases, dye-pigment type charge control agents are used.

That is, these charge control agents are usually added to a thermoplastic resin which is a binder resin of a toner and contained in a toner prepared through processes such as thermal melting dispersion, pulverization and classification. In the process, the dye / pigment type charge control agent described above often causes a problem. For example, as described above, these charge control agents are poor in stability as substances, and are easily decomposed or deteriorated by decomposition during thermal kneading, mechanical shock, friction, changes in temperature and humidity conditions, etc. Development that deteriorates the property is likely to occur. Further, when a toner containing these dyes and pigments as a charge control agent is developed in a copying machine, the charge control agent decomposes or deteriorates as the number of times of copying increases, causing deterioration of the toner during repeated copying operations. There is.

Further, since it is extremely difficult to uniformly disperse these charge control agents in the thermoplastic resin, there is a fatal problem that a difference in 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, a basic nigrosine dye is used by forming a salt with a higher fatty acid in order to improve compatibility with a thermoplastic resin, but unreacted resin acid or a dispersion product of the salt is often used on the toner surface. When exposed to water, it contaminates the carrier or the toner carrier, and causes deterioration of toner fluidity, fog, and reduction of image density. 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.

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

Further, many charge control agents are hydrophilic, and due to poor dispersion in these resins, the dye is exposed on the toner surface when pulverized after melt kneading. 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 toner particles, between toner and carrier, between toner and toner carrier such as toner and sleeve,
The amount of electric charge generated on the surface of the toner particles varies, and problems such as development fog, toner scattering, and carrier contamination are likely to occur. In addition, 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 a toner, the charge control agent itself adheres to the surface of the photoconductor due to long-term use, or the presence of the charge control agent promotes the adhesion of the toner (the occurrence of a filming phenomenon). In many cases, the cleaning process of the copying machine is inconvenient, such as adversely affecting the latent image formation, causing scratches on the surface of the photoconductor or a cleaning member such as a cleaning blade, or promoting wear of the member.

Furthermore, when a conventional charge control agent is used in a toner, it often causes a great influence on the heat melting property of the toner and deteriorates the fixing performance. In particular, the high temperature offset performance is deteriorated, the transfer paper is more likely to stick to the roller during heat roll fixing, and the durability life of the roller is shortened.

As described above, the conventional charge control agent has many problems, and it is strongly demanded in the technical field to solve these problems, and many improvement techniques have been proposed so far. The reality is that no practically satisfactory product has been found.

OBJECT OF THE INVENTION It is a general object of the present invention to provide a new technique for toner charge control that overcomes these problems.

A more specific object of the present invention is that the triboelectric charge amount between toner particles, between toner and carrier, between toner and toner carrier such as sleeve in the case of one-component development is stable,
Further, the triboelectric charge distribution is sharp and uniform, and the toner 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, no fog or toner scattering around the edge of the latent image, The purpose of the present invention is to provide a toner having high image density and good halftone reproducibility.

Still another object is to provide a toner that maintains the initial properties even when it is continuously used for a long period of time and does not undergo aggregation or change in charging properties.

Still another object is to provide a toner that reproduces a stable image that is not affected by changes in temperature and humidity, and particularly, a toner that has high transfer efficiency without splattering or transfer omission during transfer at high humidity and low humidity. is there.

Still another object is to provide a vivid chromatic toner.

Still another object is to provide a toner having excellent storage stability, which retains initial properties even after long-term storage.

Still another object is to provide a toner which can be easily cleaned by a cleaning process which does not stain, wear or scratch the electrostatic latent image surface.

Still another object is to provide a toner having good fixing properties, particularly a toner free from problems such as high temperature offset.

SUMMARY OF THE INVENTION The toner for developing an electrostatic image of the present invention is developed to achieve the above-mentioned object, and more specifically, it is represented by at least a binder resin, a colorant and the following general formula [I]. It is characterized by containing a chelating compound of substituted anthranilic acid.

(In the formula, R ₁ , R ₂ , R ₃ and R ₄ are the same or different groups selected from a hydrogen atom, an alkoxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, an arylthio group and an aralkylthio group. , All are not hydrogen atoms); M represents a divalent metal atom.) That is, the present inventors have found that a chelate compound of a substituted anthranilic acid represented by the general formula [I] (hereinafter, comprehensively). Is called “substituted anthranilic acid chelate”, is thermally and temporally stable, has low hygroscopicity, and is contained in the developer,
The present invention has been accomplished by finding that it is a high-quality charge control agent that gives a developer having excellent electrophotographic characteristics.

Hereinafter, the present invention will be described in more detail. In the following description, “part” and “%” representing the quantitative ratio are based on weight unless otherwise specified.

DETAILED DESCRIPTION OF THE INVENTION The substituted anthranilic acid chelate used as the charge control agent in the present invention is represented by the above general formula [I], and the meaning of each symbol in the formula is also as described above, but a little remark is made. , The substituents R ₁ , R ₂ , R ₃ , and R ₄ are selected from the following groups. That is, a hydrogen atom (however, not all hydrogen atoms); an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an octoxy group, an aryloxy group such as a phenoxy group, a chlorphenoxy group; a benzyloxy group, Aralkyloxy groups such as methylbenzyloxy group, chlorobenzyloxy group and phenethyloxy group; alkylthio groups such as methylthio group, propylthio group and hexylthio group, phenylthio group, methylphenylthio group, ethylphenylthio group,
An arylthio group such as a chlorophenylthio group; an aralkylthio group such as a benzylthio group, a chlorobenzylthio group, and a methylbenzylthio group.

M represents a divalent metal atom, and specific examples thereof include Ni, Co, Zn, Cd, Cu, Fe, Mn, and H.
g, Pb and the like.

The following are typical specific examples of the substituted anthranilic acid chelate represented by the general formula [I].

[Example of compound] (1) (2) (3) (Four) (Five) (6) (7) (8) These compounds are synthesized by known methods.

For example, the substituted anthranilic acid chelate (nickel methoxyanthranilic acid chelate) shown as the above compound (1) is prepared as follows.

Add nickel acetate to ethyl cellosolve and stir. Fifty
Heat to ° C and slowly add 5-methoxyanthranilic acid. After reacting for 2 hours under reflux at about 130 ° C., it is dispersed in water. After 1 hour, excessive washing with water is performed until the pH of the liquid becomes neutral. Dry 9
Compound (1) is obtained by carrying out at 0 ° C.

Other compounds can be obtained by almost the same operations as above.

As a method of incorporating the above compound into the developer, there are a method of adding it inside the developer and a method of adding it externally. When internally added, the amount of these compounds used is generally determined by the type of binder resin, the presence or absence of additives used as necessary, and the toner production method including the dispersion method. However, it is preferably 0.1 to 10 parts by weight (more preferably 0.1% to 100 parts by weight of the binder resin).
5 to 5 parts by weight).

Further, when externally added, it is 0.
01 to 10 parts by weight is desirable.

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

As the binder resin of the toner, polystyrene, poly-p-
Monopolymers of styrene such as chlorostyrene and polyvinyltoluene, and their substitution products; styrene-p-chlorostyrene copolymers, styrene-propylene copolymers, styrene-vinyltoluene copolymers, styrene-vinylnaphthalene copolymers, 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-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, Styrene-vinyl methyl ketone Styrene-based copolymers such as polymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer; poly Methyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester,
Polyurethane, polyamide, epoxy resin, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, etc. They can be used alone or in combination.

Further, as the binder resin suitable for giving a toner 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 7)
0), 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.

As the colorant, carbon black, lamp black,
Iron black, ultramarine, nigrosine dye, aniline blue, phthalocyanine black, phthalocyanine green, Hansa yellow G, rhodamine 6G lake, chrome yellow, quinacridone, benzidine yellow, rose bengal, triallylmethane dye, monoazo dye, disazo dye, Conventionally known dyes and pigments such as anthraquinone dyes may be used alone or in combination.

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. Examples of the magnetic material 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; or metals such as these and aluminum and cobalt;
Examples thereof include alloys with 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 μ, and the amount contained in the toner is about 20 to 200 parts by weight, and particularly preferably 100 parts by weight of the resin component relative to 100 parts by weight of the resin component. It is 40 to 150 parts by weight per part.

Further, the toner of the present invention may be mixed with additives other than the above if necessary. As the additive, for example, Teflon, lubricant such as zinc stearate, or fluidity imparting agent such as colloidal silica, titanium oxide, aluminum oxide, anti-caking agent, or conductivity imparting agent such as carbon black or tin oxide, Alternatively, there are fixing aids such as low molecular weight polyethylene.

To prepare the toner for developing an electrostatic image according to the present invention,
The charge control agent according to the present invention is sufficiently mixed with a vinyl-based or non-vinyl-based thermoplastic resin, a pigment or dye as a colorant, and if necessary, a magnetic material, additives, etc. by a ball mill or other mixer. From a heating roll, a kneader, an extruder or the like to melt and knead the resin to make them compatible with each other to disperse or dissolve the pigment or dye, and after cooling and solidifying, crush and classify and average. It is possible to obtain a toner having a 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.

Further, as described above, the toner of the present invention can also be obtained by subsequently externally adding the charge control agent to the toner formed by removing all or part of the charge control agent.

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 a conventionally known means.

EFFECTS OF THE INVENTION As described above, the toner of the present invention containing a substituted anthranilic acid chelate as a charge control agent has a uniform triboelectric charge amount between toner particles, and the charge amount is easily controlled.
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 developing fog, toner scattering, contamination of electrophotographic photosensitive material and copying machine are eliminated, and toner aggregation, agglomeration and low temperature fluidity during storage, which have been major problems in the prior art, are eliminated. It is a toner that does not cause a phenomenon and withstands long-term storage, and has excellent abrasion resistance, fixing property, and adhesiveness of a toner image.

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

Hereinafter, the present invention will be described more specifically by way of examples.

Example 1 Styrene / butyl acrylate 100 parts Copolymer (80/20) (Weight average molecular weight Mw: about 300,000) Carbon black (Mitsubishi # 44) 10 parts Low molecular weight polyethylene wax 2 parts The above compound (1) 2 parts The materials were well mixed with a blender and then kneaded with a two-roll roll 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 toner fine powder having a particle size of 5 to 20 μm. Got

A developer was prepared by kneading 5 parts of the toner with 100 parts of an iron powder carrier having an average particle size of 50 to 80 μm.

Then, on the OPC photosensitive member by a conventionally known electrophotographic method,
A negative electrostatic charge image was formed, and this was powder-developed by the magnetic brush method using the above-mentioned developer to form a toner image, which was transferred onto plain paper and heat-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 formed using the above-mentioned developer, and durability was examined.
The transferred images after 0000 sheets were also completely achromatic images compared with the initial images.

Further, during the durability test, the filming phenomenon related to the toner on the photosensitive member was not observed at all, and no problem in the cleaning process was found. Also, at this time, there was no trouble in the fixing process, at the end of the durability test of 30,000 sheets,
When the fixing device was observed, the roller was not scratched or damaged, and there was almost no stain due to the offset toner, and there was no problem in practical use.

Further, when the environmental conditions were 35 ° C. and 85%, the image density was a value almost unchanged from normal temperature and normal humidity, a clear image was obtained without fog and scattering, and the durability was 30,000.
There was almost no change until 0 sheets. Next 15 ° C, 10%
When a transfer image was obtained at low temperature and low humidity, the image density was sufficiently high, and solid black was developed and transferred very smoothly, and was an excellent image with no scattering or voids. A durability test was conducted under these environmental conditions. After copying continuously and intermittently, the density fluctuation was ± 0.2, which was sufficient for practical use up to 30,000 sheets.

Comparative Example 1 A developer was prepared in the same manner as in Example 1 except that 2 parts of Nigrosine dye (Nigrosine base EX manufactured by Orient Chemical Industry) was used instead of 2 parts of the compound (1) to develop, transfer,
Fixing was performed and an image was similarly obtained.

Fog was small at room temperature and normal humidity, but the image density was low at 1.06, line images were scattered, and solid black was noticeable.
The durability was examined, but the density was 0.83 at 30,000 sheets.
And fell.

Further, during the durability test, the toner material formed a thin streak-like film on the surface of the photoconductor from around 10,000 sheets 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.

Further, at the time of endurance, a fixed image was likely to be caught in the fixing roller in the fixing step, and the peeling property from the roller was difficult.

When an image was obtained under the conditions of 35 ° C. and 85%, the image density was as low as 0.88, and fog, scattering, and rubbing increased. The transfer efficiency was also low.

When an image was obtained under the conditions of 15 ° C. and 10%, the image density was as low as 0.91, and scattering, fog, and rustling were seriously noticeable. Continuous images were output, but 3
The density became 0.53 after about 10,000 sheets, which was not practical.

Example 2 Instead of 2 parts of the compound (1), the compound (2) 3
A developer was obtained in the same manner as in Example 1 except that parts were used, 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 3 Instead of 2 parts of the compound (1), the compound (3) 2
A developer was obtained in the same manner as in Example 1 except that parts were used, 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 Instead of 2 parts of the compound (1), the compound (4) 2
A developer was obtained in the same manner as in Example 1 except that parts were used, 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 100 parts (80/20) copolymer (weight average molecular weight Mw: about 300,000) Iron trioxide trioxide EPT-500 60 parts (manufactured by Toda Kogyo) Low molecular weight polypropylene wax 2 parts The compound ( 1) 2 parts The above materials were well mixed with a blender and then kneaded with a two-roll roller 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 having a particle size of 5 to 20 μm. It was

Next, 100 parts of the fine powder was mixed with hydrophobic colloidal silica R
-972 (manufactured by Nippon Aerosil Co., Ltd.) was mixed with 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 In Example 5, 3 parts of the compound (2) was used instead of 2 parts of the compound (1).

A developer was obtained in the same manner as in Example 5 except for the above, and development, transfer and fixing were carried out to obtain an image in the same manner.

Detailed results are shown in Tables 1 and 2, but almost the same 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 the compound (3) was used instead of 2 parts of the compound (1), and development, transfer and fixing were performed, and the same procedure was performed. 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.

Comparative Example 2 A developer was obtained in the same manner as in Example 5 except that 2 parts of benzyl-dimethyl-hexadecyl ammonium chloride was used instead of 2 parts of the compound (1) in Example 5, and an image was obtained by the same method. It was Fog was small at room temperature and normal humidity, but the image density was low at 0.81 and line images were scattered, and 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.

When an image was obtained under the conditions of 35 ° C. and 85%, the image density was as low as 0.72, and fog, scattering, and rubbing increased, and it was unusable. The transfer efficiency was also low.

When an image was obtained under the conditions of 15 ° C. and 10%, the image density was as low as 0.73, and scattering, fog, and rubbing were noticeably observed. Continuous images were output, but 3
When the number of sheets was 10,000, the density was 0.59, which was not practical.

Example 8 Styrene / butyl acrylate 100 parts (80/20) copolymer (average molecular weight Mw: about 300,000) Copper phthalocyanine blue pigment 5 parts Low molecular weight polypropylene wax 2 parts The compound (1) 2 parts The above material is blended. After mixing well, the mixture was kneaded with two rolls heated to 150 ° C. After allowing the kneaded material 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 toner fine powder having a particle size of 5 to 20 μm. Obtained.

Next, 100 parts of the toner was mixed with 50 g of magnetic particles having a particle diameter of 50 to 80 μm to obtain a developer.

This developer is stored in the developer container 1 of the developing device shown in the accompanying drawings.
And developed. That is, in this apparatus, a cylindrical toner carrier 2 made of stainless steel, the surface of which is roughened so as to substantially close the container, is accommodated in the lower opening of the container 1, which has a peripheral speed of 66 mm in the direction of arrow a.
It was rotated at 1 / sec. On the other hand, at the outlet of the container 1 on the downstream side in the rotation direction of the sleeve 2, an iron blade 3 having a tip at a position of 200 μm from the sleeve surface is arranged, and a fixed magnet 4 is arranged in the sleeve 2. The N pole, which is the main magnetic pole, was arranged so that the angle θ between the line connecting the sleeve and the sleeve center and the sleeve center and the tip of the blade 3 was 30 °. Under these conditions, the sleeve 2
As the toner rotates, a magnetic brush 5 is formed in the container 1 by the carrier iron powder contained in the developer, and the magnetic brush 6 takes in the toner 6 distributed preferentially to the upper method and the surface of the sleeve 2. The toner is circulated along the periphery of the sleeve 2 below the container 1 while being supplied to the toner, and a thin layer 16 of toner is formed on the surface of the sleeve 2 that has passed the blade 3.

In this example, the thickness thus formed is about 80 μ.
a thin toner layer of 600 m on the photosensitive drum 7, which faces the developing portion (closest portion) at an interval of about 300 μm and rotates in the direction of arrow b at a peripheral speed of about 60 mm / sec.
A negative electrostatic image of V, -1500V was developed. At this time, the power source 8 has a frequency of 800 Hz and a peak-to-peak value of 1.4 KV
Then, a bias voltage having a center value of −300 V was applied between the sleeve 2 and the photosensitive drum 7.

When images were printed out in this way, good images with a vivid blue color were obtained, and even after the 1500 sheets were printed, even if the toner / carrier ratio became 10 parts / 50 parts, almost no image density was obtained. No change was observed, and after that, images were printed up to 30,000 sheets while replenishing the toner, but good images were obtained.

Normal temperature-normal humidity (25 ° C., 60%) in the above Examples and Comparative Examples
The evaluation results under various environmental conditions of RH), high temperature and high humidity (35 ° C., 85% RH), and low temperature and low humidity (15 ° C., 10% RH) are summarized in Tables 1 and 2 below.

[Brief description of drawings]

The drawing is a schematic cross-sectional view of an example of a developing device suitable for applying the toner according to the present invention. 1 ... Developer container, 2 ... Toner carrier, 3 ... Doctor blade, 4 ... Fixed magnet, 5 ... Magnetic brush, 6 ...
... toner, 7 ... electrostatic latent image carrier, 16 ... thin layer toner.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor, Yoji Kawagishi, 8-1, Sanrahito-cho, Neyagawa-shi, Osaka Orient Chemical Industry Co., Ltd. (56) References Japanese Patent Publication No. 5-60098 (JP, B2)

Claims (1)

[Claims] 1. An electrostatic charge image developing toner comprising at least a binder resin, a colorant, and a substituted anthranilic acid chelate compound represented by the following general formula [I]. (In the formula, R ₁ , R ₂ , R ₃ , and R ₄ are the same or different groups selected from a hydrogen atom, an alkoxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, an arylthio group, and an aralkylthio group (however, , Not all hydrogen atoms); and M represents a divalent metal atom.)