JPS61212852A - Electrostatic charge image developing toner - Google Patents

Abstract

PURPOSE:To stabilize triboelectrification amt. and to render its distribution sharp and uniform, and to obtain a stable and sharp image without changing characteristics at the time of long successive uses by incorporating one of specified benzoylketone metal complex derivs. CONSTITUTION:The benzoylketone metal complex salt to be contained as a triboelectrifiability controller is represented by the formula shown on the right in which R1, R2 are each H, halogen, alkyl, araldyl, alkoxy, or the like, and both may form a ring; R3 is alkyl, aryl, or the like; M is a metal atom; X is a neutral ligand; m is 1-3; and n is 0, 2, or 4. Such a metal complex salts may be added onto the outside of the toner or into its inside, and in both cases the use of them permits triboelectrifiation to be easily controlled and stabilized, development and transfer of an image high in fidelity to a latent image, and agglomeration and fluctuation of triboelectrifiability to be prevented at the time of long successive uses, a sharp and chromatic color image to be obtained without being affected by change of temp. and humidity, and further, staining and damaging of the face of a latent image and high temp. offset trouble to the like to be prevented in a cleaning step.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a new toner for developing electrostatic images in electrophotography, electrostatic recording, electrostatic printing, and the like.

[Prior Art] Conventionally, various electrophotographic methods have been described in US Pat. No. 2,297,681, Japanese Patent Publication No. 42-23910, Japanese Patent Publication No. 43-24748, etc. In short, they impart a uniform electrostatic charge to a photoconductive insulator layer, form an electrostatic latent image by irradiating the insulator layer with a light image, and then apply the latent image to a donor in the technique. After developing and visualizing the powder image using a fine powder called a
Fixing is performed by pressurization or solvent vapor.

The developing methods applied to these electrophotographic methods include:
Broadly speaking, there are dry development methods and wet development methods. The former method is further divided into a saw method using a two-component developer and a method using a -component developer.

The two-component developing methods include, depending on the type of carrier for conveying the toner, a magnetic brush V method using an iron powder carrier, a cascade method using a bead carrier, a fur brush method using fur, and the like.

In addition, the -component type development methods include the powder cloud method, in which toner particles are sprayed, and the contact development method, in which toner particles are brought into direct contact with the electrostatic latent image surface (contact I). , or toner development), jumping development in which toner particles are not brought into direct contact with the electrostatic latent image surface, but are charged and caused to fly toward the latent image surface by the electric field of the electrostatic latent image. There is a magnetry method in which a magnetic conductive toner is brought into contact with an electrostatic latent image surface for development.

Toners applicable to these developing methods and 1. Conventionally, fine powders in which dyes and pigments are dispersed in natural or synthetic resins have been used. For example, particles obtained by dispersing a colorant in a binder resin such as polystyrene and pulverizing the particles to about 1 to 30 particles are used as toner. As the magnetic toner, one containing magnetic particles such as Magnetite I is used. In the case of a system using a so-called two-component developer, the toner is usually mixed with gear particles such as glass beads and iron powder.

Further, the I-ner is made to hold a positive or negative charge depending on the polarity of the electrostatic latent image to be developed.

In order to make the toner hold an electric charge, it is also possible to use the triboelectricity of the resin that is a component of the toner, but since the toner's chargeability is small with this method, the image obtained by development is prone to fogging and is unclear. Become something. Therefore, in order to impart desired triboelectric chargeability to the toner, dyes, pigments, and even a charge control agent are added to impart chargeability to the toner.

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

There are the following substances that control the (+) l-ner to be positively charged.

Nigrosine, azine dyes containing an alkyl group having 2 to 16 carbon atoms (Japanese Patent Publication No. 1827/1983), basic dyes (e.g. C, T, Ba5ic Yellow 2 (C, 1
, 41000), C, 1, Ba5ic Yellow
3, C,1,Ba5ic'Red 1(C,1,4
5] (io) ,C,1,Ba5ic'Red '9
(C,'I.

42500), C, 1, Ba5ic Violet 1
(C,1,42535),C,1,Ba5ic Vi
olet 3 (C, 1, 42555) C, T, B
a5icVi'olet 10 (C, 1, 45170
), C, 1, Ba5ic Violet 14 (G, 1
．． 42510), C, T, 'Ba5ic Blue
e 1 (C, I.

420'25), G', 1. Ba5ic Blue
3 (G, 1.51005), C, T.

Bs1c Blue 5 (C, 1, 42140), C
,1,Ba5ic Blue7 (C,'r,' 42
585), C, 1, Ba5ic Blue 9 (C,
I.

520'15), C, 1, Ba5ic Blue 24
(C, 1, 52030), C, I.

Ba5ic old ue 25 (C, 1, 52025), C
,1,Ba5ic Blue26 CG,1. 44
045), C,1,Ba5ic Green
1 (C:, I.

42040), G, 1. Easy Green 4
(G, 1.42000) etc.). Lake pigments of these basic dyes (lake-forming agents include phosphotungstic acid, phosphomolybdic acid, phosphotungsten-molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.), C, 1,5olven
t Black 3 (G, 1.28150), Hansa Yellow G (C, 1,11680), G, 1.
MordantBlack II, C, T, Pi
gment Black 1, Gilt Night, Asphalt, etc.

Quaternary ammonium salts, such as benzylmethyl-hexadecyl ammonium chloride, decyl-trimethylammonium chloride, organotin compounds such as dibutyltin oxide, metal salts of higher fatty acids, glass, cloud fr't
, inorganic fine powders such as zinc oxide, metal complexes such as EDTA and acetylacetone, polyamine resins such as vinyl polymers containing amine groups, and condensation polymers containing amine groups.

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

Special Publication No. 41-20153, No. 43-27596, No. 44-839? No. 45-26478, etc., metal complex salts of monoazo dyes.

Dyes and pigments such as nitrofumic acid and its salts or C, 1,14645 described in JP-A-50-133338.

Metals such as Go, Or, and Fe of salicylic acid, naphthoic acid, and dicarboxylic acid described in Japanese Patent Publication No. 55-42752, Japanese Patent Publication No. 58-41508, Japanese Patent Publication No. 5a-73sa, Japanese Patent Publication No. 59-7385, etc. Complex. Sulfonated copper phthalocyanine pigment. Styrene oligomer with nitro groups and halogens introduced. Chlorinated paraffin, melamine resin, etc.

Many of these charge control agents are derived from dyes and pigments.
Generally, they have a complex structure, and many of them have strong colors and characteristics.

Recently, there are some newly proposed products that are different from these, but dye and pigment-based products are ranked 1.1 in terms of overall performance. There are no cases where dyes and pigments are used, although they are still unsatisfactory.

These are usually added to thermoplastic resins, thermally melted and dispersed, and then finely pulverized and adjusted to a suitable particle size as necessary before use.

However, these dyes used as charge control agents have complex structures, inconsistent properties, and poor stability. In addition, it is easily decomposed or altered due to decomposition during thermal kneading, mechanical impact, friction, changes in temperature and humidity conditions, etc., and tends to cause a phenomenon in which charge controllability is reduced.

Therefore, when a toner containing these dyes as a charge control agent is used for development in a copying machine, as the number of copies increases, the charge control agent decomposes or changes in quality, which may cause deterioration of the toner during durability.

Furthermore, since it is extremely difficult to uniformly disperse these charge control agents in thermoplastic resins, they pose the fatal problem of causing differences in the amount of frictional charge between toner particles obtained by pulverization. have. For this reason, various methods have been used to achieve more uniform dispersion. for example,
Basic nigrosine dyes are used by forming salts with higher fatty acids in order to improve their compatibility with thermoplastic resins.
Dispersion products of unreacted fatty acids or salts are often exposed on the toner surface and contaminate the carrier or toner carrier, causing a decrease in toner fluidity, capri, and image density. There is. Alternatively, in order to improve the dispersion of these charge control agents into the resin, a method has also been adopted in which charge control agent powder and resin powder are mechanically pulverized and mixed in advance and then hot melt-kneaded. However, the inherent poor dispersion cannot be avoided, and at present, sufficient uniformity of charge has not yet been obtained for practical use.

Furthermore, there is a problem in that most of the substances generally known as charge control agents are dark in color and cannot be incorporated into bright chromatic color developers.

In addition, many charge control agents are hydrophilic, and due to poor dispersion in these resins, dyes are exposed on the toner surface when crushed after melt-kneading, making it difficult to control these charges in high-humidity conditions. Since the agent is wood-philic, it has the disadvantage that good quality images cannot be obtained.

In this way, when conventional charge control agents are used in toner,
Between toner particles, between toner and carrier, between toner and toner carrier such as a sleeve,
This causes variations in the charge areas generated on the surface of toner particles, which tends to cause problems such as development fog, toner scattering, and carrier contamination. Further, this failure becomes a noticeable phenomenon when copying is repeated many times, resulting in a result that is practically unsuitable for copying machines.

Furthermore, under high humidity conditions, the transfer efficiency of l/ner images decreases significantly, and many of them are unusable. Even at room temperature and humidity, when the toner is stored for a long period of time, it often undergoes deterioration due to the instability of the charge control agent used and becomes unusable due to poor charging properties.

Furthermore, when conventional charge control agents are used in toners, long-term use may cause the charge control agents to adhere to the surface of the photoreceptor or promote toner sticking, which may adversely affect latent image formation (
There are many things that have a negative effect on the cleaning process of a copying machine, such as the filming phenomenon), scratches on the surface of the photoreceptor or cleaning members such as cleaning blades, and those that accelerate wear of the members.

When conventional charge control agents are used in toners, many of them have a large effect on the thermal melting properties of the toners and reduce fixing performance. In particular, there are some that worsen the anti-offset property at high temperatures, increase the clinging of the transfer material to the roller during heat roll fixing, and shorten the durable life of the roller.

As described above, conventional charge control agents have many drawbacks.
Improving these is strongly required in the relevant technical field,
Although many improved techniques have been proposed so far, the reality is that no one has yet found one that is comprehensively satisfactory in practical terms.

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

Another object of the present invention is to provide the following: between toner particles or between toner and carrier; and between toner and sleeve in case of component development; To provide a developer that has stable friction zone overlapping between special holidays, sharp and uniform triboelectric charge amount distribution, and can be controlled to a charge zone suitable for the developing system used.

Still another purpose is to develop faithfully to the latent image and to prevent the developer that performs the transfer, i.e., the sticking of i. The object of the present invention is to provide a developer which can obtain high image density without any oxidation, and has good reproducibility of half i-ton.

□ Still another object is to provide a developer that maintains its initial characteristics even when the developer is used continuously over a long period of time, and that causes no toner aggregation or change in charging characteristics.

Another objective is to develop a developer that reproduces stable images that are not affected by changes in temperature and humidity, especially a developer that has high transfer efficiency and does not cause scattering or transfer dropouts during transfer at high or low humidity. On offer.

Still another object is to provide a bright chromatic developer.

Still another object is to provide a developer with excellent storage stability that maintains its initial characteristics even during long-term storage.

Still another object is to provide a developer that does not stain, abrade, or scratch the electrostatic latent image surface and is easy to clean.

Still another object is to provide a developer that has good fixing properties, particularly a developer that does not have problems such as high-temperature offset.

[Means and effects for solving the problems 1] The present invention is an electrophotographic toner used for developing electrostatic images, which contains a metal complex of benzoyl ketones whose basic structure is represented by the general formula [I]. A toner for developing electrostatic images characterized by:

[In the formula, R1 and R2 represent a hydrogen atom,) \ rogen atom, alkyl group, aralkyl group, alkoxy group, aryloxy group, aralkyloxy group, alkylthio group, arylthio group, aralkylthio group, or nitro group, R+
, R2, and R3 may be the same or different, and R+ and R2 may form a substituted or unsubstituted ring. R3 is an alkyl group, an aryl group or an aralkyl group. Further, the alkyl chain and aryl ring in each group of R+, R2, and R3 may be substituted. X represents a metal element, and X represents a neutral coordination molecule. The intestine is an integer of 1 to 3, and n is an integer of 0 or 2.4. ] The present inventors have discovered that the metal complex of pendiylketones represented by the general formula [I] is thermally and temporally stable, has low hygroscopicity, and has excellent electrophotographic properties when contained in a developer. The present invention was achieved by discovering that this is a high-quality charge control agent that provides a good developer.

In the general formula [I], R,, R2, is a hydrogen atom; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom; a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a dodecyl group; Alkyl groups that may be branched such as; methoxyethyl group, ethoxyethyl group,
Substituted alkyl groups such as butoxyethyl group, chloroethyl group, dimethylaminoethyl group; Aralgyl groups such as benzyl group, phenethyl group, methylbenzyl group; Alkoxy groups such as methoxy group, ethoxy group, propoxy group, butoxy group, octoxy group; Aryloxy group or substituted aryloxy group such as phenoxy group, methylphenoxy group, butoxyphenoxy group, chlorophenoxy group; aralkyloxy group such as benzyloxy group, methylbenzyloxy group, chlorobenzyloxy group, phenethyloxy group, Substituted aralkyloxy group: alkylthio group such as methylthio group, propylthio group, hexylthio group; arylthio group or substituted arylthio group such as phenylthio group, methylphenylthio group, ethylphenylthio group, chlorphenylthio group: benzylthio group, chlorbenzylthio group Representative substituents include aralkylthio groups such as methylbenzylthio groups, and substituted aralkylthio groups;

An example of R1 and R2 forming a substituted or unsubstituted ring is when R1 and R2 together with a benzene nucleus form a naphthyl group, a tetrahydronaphthyl group, a substituted naphthyl group, or a substituted tetrahydronaphthyl group in the form of 2. can be mentioned.

R3 is an alkyl group, cycloalkyl group, aryl group, or aralkyl group, or an alkyl button or aryl ring of these groups! ! ! ! It is a basic foundation. Specific examples of R3 include methyl group, ethyl group, propyl group, butyl group,
Alkyl groups that may be branched such as hexyl groups and dodecyl groups; cycloalkyl groups such as cyclopentyl groups and cyclopentyl groups; aryl groups or substituted groups such as phenyl groups, tolyl groups, butylphenyl groups, butoxyphenyl groups, and chlorophenyl groups. Aryl group; examples include aralkyl groups such as benzyl group, phenethyl group, and methylbenzyl group.

The metal elements N in general [1] include Na, Ll,
Zn, Ca, Cu, Go, Or, Mg, M
Preferred are n, Ni, AM, pb, etc.

As the neutral coordination molecule X, R20, NH3, ethylenediamine, etc. are preferable.

Typical specific examples of metal complexes of benzoylacetones represented by general formula [I] include the following.

F compound example] These compounds can be synthesized by known methods.

For example, compound (1) is produced as follows.

When lithium is reacted with benzoylacetone in ether, an anhydride is obtained, and when recrystallized from ethyl acetate containing the anhydride, an engineered hydrate is obtained.

Further, for example, compound (2) can be produced as follows.

When metallic sodium reacts with benzoylacetone in dry ether, an anhydride is obtained, and recrystallization from water-containing ethanol yields a hydrated product. Generally, the compound of No. 142 has an average particle size of 10 to 0.01 pL,
In particular, it is preferable to use the particle size in the range of 5 to 0.1 mm for toner adjustment.

There are two methods for incorporating the compound described above into the developer: a method of adding it inside the developer, and a method of adding it externally. When internally added, the amount of these compounds used is determined by the type of binder resin, the presence or absence of additives used as necessary, and the toner manufacturing method including the dispersion method, and is uniquely limited. Although it is not a specific amount, it is preferably 0.1 to 20 parts by weight (more preferably 0.1 to 20 parts by weight, more preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the binder resin).
(5 to 10 parts by weight).

In addition, when externally added, 0.0 parts by weight per 100 parts by weight of resin.
1-10 parts by weight is desirable.

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

Colorants used in the present invention include carbon black, lamp black, iron black, ultramarine blue, nigrolene dye, aniline blue, phthalocyanine blue, phthalocyanine green, Hansa Yellow G, Rotamin 6G Lake,
Calco oil blue, chrome yellow, quinacridone,
Any conventionally known dyes and pigments such as benzidine yellow, rose bengal, triallylmethane dyes, monoazo dyes, and disazo dyes and pigments can be used alone or in combination.

The binder resin used in the present invention includes polystyrene,
Monopolymers of styrene and its substituted products such as polyp-chlorostyrene and polyvinyltoluene; styrene-p-chlorostyrene copolymers, styrene-propylene copolymers,
Styrene-vinyltoluene co-ffi combination, styrene-
Vinylnaphthalene 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-
Methyl chlormethacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinylethyl ether copolymer,
Styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, methyl 1/-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer Styrenic copolymers such as polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, polyurethane, polyamide, epoxy resin, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, Examples include terpene resins, phenolic resins, aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, paraffin waxes, etc., which can be used alone or in combination.

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

Polyolefin (low molecular weight polyethylene, low molecular weight polypropylene, polyethylene oxide, polytetrafluoroethylene, etc.), epoxy resin, polyester resin, styrene-butadiene copolymer (1,000) mer ratio 5-30:95-70)
, olefin copolymers (ethylene-acrylic acid copolymer, ethylene-acrylic ester copolymer, ethylene-
methacrylic acid copolymer, ethylene-methacrylic liquor ester copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, ionomer resin), polyvinylpyrrolidone, methyl vinyl ether-maleic anhydride copolymer, maleic acid Modified phenolic resin, phenol-modified terpene resin.

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

As carriers that can be used in the present invention, all known carriers can be used, such as powders with magnetic properties such as iron powder, ferrite powder, and nickel powder, glass beads, etc., and their surfaces coated with resins, etc. Examples include those processed with

Furthermore, the toner of the present invention can further contain a magnetic material and be used as a magnetic toner. Magnetic materials contained in the magnetic toner of the present invention include magnetite, hematite,
Iron oxides such as ferrite, metals such as iron, cobalt, and nickel, or these metals such as aluminum, cobalt,
Examples 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.

These ferromagnetic materials preferably have an average particle size of about 0.1 to 2 μl, and the amount to be included in the toner is about 20 to 200 parts by weight per 100 parts by weight of the resin component, particularly preferably on the resin component side. The amount is about 40 to 150 parts by weight based on 0 parts by weight.

Further, the toner of the present invention may be mixed with additives as necessary. Additives include, for example, lubricants such as Teflon and substearic acid, or abrasives such as cerium oxide and silicon carbide, or flowability agents such as colloidal silica and aluminum fluoride, anti-caking agents, or carbon. Examples include conductive mounting agents such as black and tin oxide, and fixing aids such as low-molecular fine 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 mixed with a vinyl or non-vinyl thermoplastic resin, a pigment or dye as a coloring agent, a magnetic material, and an additive as necessary. Additives, etc. were thoroughly mixed using a ball mill or other mixer, and then melted, kneaded, and kneaded using a heat kneader such as a heated roll, colander, or extruder to make the resins mutually dissolve. By dispersing or dissolving pigments or dyes in it, cooling and solidifying it, and then crushing and classifying it,
A toner having an average particle size of 5 to 20 g can be obtained.

Alternatively, the material can be obtained by dispersing the material in a binder resin solution and then spray-drying it, or by mixing the specified material with the monomers that should constitute the binder resin to form an emulsified suspension and then polymerizing it. Methods such as a polymerization toner production method that obtains a toner can be applied.

The toners prepared by these methods can be used for developing electrostatic charge images in electrophotography, electrostatic recording, electrostatic printing, etc. by conventionally known means, such as those described below. It produces excellent effects.

That is, the thick triboelectric charge needles between the toner particles are uniform, and the amount of charge/Xu can be easily controlled. In addition, the toner is extremely stable as it does not change in quality during use and the triboelectric charge position varies or decreases. Therefore, problems such as development fog, toner scattering, and contamination of electrophotographic photosensitive materials and copying machines as described above are eliminated, and phenomena such as toner aggregation, clumping, and low-temperature flow during storage, which were major drawbacks in the past, are eliminated. It is a toner that can be stored for a long time without causing damage, and has excellent abrasion resistance, fixing properties, and adhesive properties of H2 toner images.

These excellent effects of the toner are further magnified when used in a repetitive transfer copying system in which the operations of charging, exposure, development, and transfer are successively repeated. Furthermore, since there is no color tone disturbance caused by the charge control agent, it is possible to form color images with excellent colors by using it as a color electrophotographic toner. [Examples] The present invention will be specifically explained below with reference to Examples. However, this does not limit the invention in any way. All parts in the following formulations are parts by weight.

Example 1 Carbon black (Mitsubishi #44) 10 parts Paper molecular weight Polyethylene wax 2 parts Compound (1) 2
After thoroughly mixing the ingredients in a blender, heat the mixture to 150°C. Kneaded with a wooden roll. After the kneaded material was left to cool naturally, it was roughly pulverized using a cutter mill, then pulverized using a pulverizer using a jet stream, and further classified using an air classifier to obtain a fine powder with a particle size of 5 to 20 pL. Ta.

A developer was prepared by mixing 5 parts of the fine powder with 100 parts of iron powder carrier having an average particle size of 50 to 807 tons.

Next, a negative electrostatic image is formed on the OPC photoconductor by a conventionally known electrophotographic method, and this is powder-developed using the developer described in 2 using the magnetic brush method to create a toner image, which is then printed on plain paper. It was transferred and fixed by heating. The resulting transferred image had a sufficiently high density, no fogging, and no toner scattering around the image, resulting in a good image with high resolution. - Transfer images were created successively using the developer described in Section 1 and the durability was examined, but the transferred images after 30,000 copies were also completely unchanged compared to the initial images. Ta.

Further, during durability, the above-mentioned filming phenomenon related to toner on the photoreceptor was not observed at all, and no problems were found in the cleaning process. Also, there were no troubles in the fixing process at this time, and at the end of the 30,000-sheet durability test, the fuser was disassembled and observed, and there were no scratches or damage to the rollers, and there was almost no dirt from offset toner, making it suitable for practical use. There were no problems at all.

In addition, when the environmental conditions were set to 35°C and 185%, the image density was almost the same as at room temperature and humidity, and clear images with no fogging or scattering were obtained, and the durability remained unchanged up to 30,000 sheets. . Next, a transferred and fixed image was obtained at a low temperature of 15°C and a low humidity of 10%, and the image density was sufficiently high, solid black was developed and transferred extremely smoothly, and the image was excellent with no scattering or hollow spots. Durability was carried out under these environmental conditions, and although copies were made continuously and intermittently,
After all, the density fluctuation is ±0.2 up to 30,000 sheets, which is practical.
1-Comparative Example 1 A developer was obtained in the same manner as in Example 1, except that 2 parts of nigrosine dye (Nigrosine Base EX manufactured by Orient Chemical Industry Co., Ltd.) was used instead of 2 parts of compound (1), and developed. , transfer, and fixing were performed to obtain an image in the same manner.

At room temperature and humidity, there was little fog, but the image density was low at 1.06, line drawings were scattered, and solid black was noticeably rough. Durability was investigated and the density decreased to 0.83 after 30,000 sheets.

Also, during durability, after about 10,000 sheets, toner material formed a film in the form of streaks on the surface of the photoreceptor and began to appear in the form of lines on the image. This is so-called filming, and is thought to be due to the charge control agent changing the lubricity of the toner powder.

Furthermore, during durability, the fixed image tended to get caught up in the fixing roller during the fixing process, and there was difficulty in peeling it off from the roller.

When an image was obtained under conditions of 35° C. and 85%, the image density was as low as 0.88, and fogging, scattering, and roughness increased. Transfer efficiency was also low.

When an image was obtained under conditions of 15° C. and 10%, the image density was as low as 0.91, and there was severe scattering, fogging, and roughness, and transfer omissions were noticeable. I tried to take continuous images, but 3
After about 0,000 sheets, the density became 0.53, making it impractical.

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

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

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

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

Example 4 A developer was obtained in the same manner as in Example 1, except that 2 parts of Compound (Grade) was used instead of 2 parts of Compound (1), and development, transfer, and
Fixation was performed and an image was obtained in the same manner.

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

Example 5 Triiron tetroxide EPT-500 (manufactured by Toda Kogyo) 600 parts Low-wrinkle polypropylene wax 2 parts Compound (1) 2
The materials listed in Part 1 were thoroughly mixed in a blender and then kneaded with two rolls heated to 150°C. After letting the kneaded mixture cool naturally,
After coarsely pulverizing it with a cutter mill, it was pulverized using a pulverizer using a jet stream, and further classified using an air classifier to obtain a fine powder with a particle size of 5 to 20 pL.

Next, 0.4 parts of hydrophobic colloidal silica R-972 (manufactured by Ippon Aerosil Co., Ltd.) was mixed with 100 parts of the fine powder using a sample mill to prepare a - component magnetic toner.

When this toner was applied to a commercially available copying machine (trade name NP-1502, manufactured by Canon ■) and an image was produced, good results almost the same as in Example 1 were obtained.

Example 6 A developer was obtained in the same manner as in Example 5, except that 3 parts of compound (2) was used instead of 2 parts of compound (1), and development, transfer, and fixing were carried out in the same manner. I got it.

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

Example 7 A developer was obtained in the same manner as in Example 5, except that 2 parts of compound (3) was used instead of 2 parts of compound (1), and development, transfer, and fixing were carried out in the same manner as in Example 5. I got it.

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

Comparative Example 2 A developer was obtained in the same manner as in Example 5, except that 2 parts of benzylmethyl-hexadecyl ammonium chloride was used instead of 2 parts of Compound (1) in Example 5, and an image was obtained in the same manner. At room temperature and humidity, there is little fog, but the image density is 0.8
1 and the line drawings were scattered, and the solid black was noticeably rough. I checked the durability, and the density was 0.4 at 30,000 sheets.
It dropped to 8.

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

When an image was obtained at 35° C. and 185%, the image density was as low as 0.72, and fogging, scattering, and roughness increased, making it unusable. 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 there was severe scattering, fogging, roughness, and transfer omissions were noticeable. Continuous image formation was performed, but the density became 0.58 after 30,000 sheets, making it impractical.

Example 8 Copper phthalocyanine blue pigment 5 parts Low molecular weight polypropylene wax 2 parts Compound (1) 2 parts The above materials were thoroughly mixed in a blender and then kneaded with two rolls heated to 150°C. After the kneaded material was left to cool naturally, it was roughly pulverized using a cutter mill, then pulverized using a pulverizer using a jet stream, and further classified using an air classifier to obtain a fine powder with a particle size of 5 to 20 pL. Ta.

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

When this developer was used to develop an image using the developing method shown in Figure 1, a good image with a bright blue color was obtained. However, there was almost no change in the image density, and after that, while replenishing I.
Even after printing up to 10,000 images, good images were obtained.

Water development method 1 To explain the details, in Figure 1, ■
is an electrostatic image carrier, 2 is a toner carrier, 3 is a hopper, 5
2 is a magnetic brush made of a carrier toner mixture, 58 is a toner thickness regulating blade, 50 is a fixed magnet, 6 is a developing bias, and 5 is a toner.

That is, the magnetic brush 52 formed on the toner carrier 2 is circulated by rotating the toner carrier 2, takes in the toner in the hopper 3, and uniformly coats the toner 2-1 with a thin layer. Next, the toner carrier 2 and the electrostatic image carrier 1 are placed facing each other with a gap larger than the thickness of the toner layer 2, and the
The toner 5 is developed by flying onto the electrostatic charge image 1" and 2.

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

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

\、 Table 1 Table 2 [Effect of the invention] The effects obtained by the present invention are as follows.

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

(2) The developer is capable of faithfully developing and transferring a latent image, maintains its initial characteristics even when used continuously over a long period of time, and does not cause toner aggregation or change in charging characteristics.

(3) A developer that can reproduce stable images that are not affected by changes in temperature and humidity, and that can also produce images in vivid chromatic colors.

(4) It is a developer that does not stain, rub or scratch the electrostatic latent image surface, has an easy cleaning process, has excellent fixing properties, and has no problem with high-temperature offset, etc.

[Brief explanation of drawings]

FIG. 1 is an explanatory diagram of an example of a developing device to which the positively chargeable toner according to the present invention can be applied. 1... Electrostatic image holder, 2... Toner carrier, 5...
・Toner, 50...Magnet, 52...Magnetic brush, 5
8...Regulation blade.

Claims (1)

[Scope of Claims] An electrophotographic toner for developing an electrostatic image, characterized in that it contains a metal complex of benzoyl ketones whose basic structure is represented by the general formula [I]. toner. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] [In the formula, R_1, R_2 are hydrogen atoms, halogen atoms,
It represents an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, an arylthio group, an aralkylthio group, or a nitro group,
R_1 and R_2 may be the same or different,
R_1 and R_2 may form a substituted or unsubstituted ring. R_3 is an alkyl group, an aryl group or an aralkyl group. Further, the alkyl chain and aryl ring in each group of R_1, R_2, and R_3 may be substituted. M represents a metal element, and X represents a neutral coordination molecule. m is an integer from 1 to 3, n
represents an integer of 0, 2, or 4. ]