JPS61172152A - Toner for developing electrostatic charge image - Google Patents

Abstract

PURPOSE:To stabilize the extent of triboelectric charge, to form the sharp and uniform distribution of extent of triboelectric charge, and to make the extent of triboelectric charge suitable for a developing system used by control by using a binding resin, a coloring agent and a chelate compound of (alkyl) salicylaldimine. CONSTITUTION:This toner contains the binding resin, the coloring agent and the chelate compound of (alkyl)salicylaldimine. The chelate compound of (alkyl) salicylaldimine used as a charge controller may by the chelate compound contg. Cr, Co, Fe or Cu, and the alkylsalicylaldimine has 1-3 alkyl groups each having 1-24C, especially 1-16C atoms. The chelate compound is easily obtd. by adding an aqueous metallic salt soln. to the soln. of corresponding aldehyde in ethanol and an aqueous ammonia soln. and by heating them. The chelate compound is blended with colored fine powder contg. a binding resin and a coloring agent as essential components to obtain the desired toner.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel toner for developing electrostatic images in electrophotography, electrostatic recording, electrostatic printing, and the like.

Previously, as an electrophotographic method, U.S. Patent No. 2,297,69
No. 1, Japanese Patent Publication No. 42-23910.

Various methods are described in Japanese Patent Publication No. 43-24748, etc., but in short, these methods apply a uniform electrostatic charge to a photoconductive insulating layer and irradiate the insulating layer with a light image. An electrostatic latent image is formed by this process, and then this latent image is developed and visualized using a fine powder called toner in the art, and if necessary, the powder image is transferred to paper or the like, and then heated,
Fixing is performed by pressurization or solvent vapor.

The developing methods applied to these electrophotographic methods include:
There are two main types of development methods: dry development methods and wet development methods. The former is further divided into a method using a two-component developer and a method using a -component developer.

Two-component developing methods include a magnetic brush method using an iron powder carrier, a cascade method using a bead carrier, a fur brush method using fur, etc., depending on the type of carrier for conveying the toner.

In addition, methods belonging to the -component development method include the powder cloud method, in which toner particles are sprayed, and the contact development method (contact development, or toner development method, in which toner particles are brought into direct contact with the electrostatic latent image surface for development. Jumping development method, in which toner particles are not brought into direct contact with the electrostatic latent image surface, but are charged and flown toward the latent image surface by the electric field of the electrostatic latent image; magnetic conductivity; There is the MagneDry method, which develops by bringing toner into contact with the electrostatic latent image surface.

Toners used in these development methods have conventionally been made by dispersing dyes and pigments in natural or synthetic resins.
Particles pulverized to about 30 #L are used as toner. Furthermore, magnetic toners containing magnetic particles such as magnetite instead of or in addition to the dyes or pigments described above are used.

In the case of a system using a so-called two-component developer, the above toner is usually mixed with carrier particles such as glass beads and iron powder.

Furthermore, the toner is given a positive or negative charge in advance depending on the polarity of the electrostatic latent image to be developed.

In order to charge the toner, it is also possible to use only the triboelectricity of the resin that is a component of the toner, but with this method, the toner's chargeability is small, so the image obtained by development is prone to fogging and is unclear. Become something. Therefore, in order to impart desired triboelectric charging properties to the toner, charge control agents such as dyes and pigments that enhance the charging properties are added.

Charge control agents known today in fields such as electrophotography include the following.

(1) Things that control the toner to be positively charged: dicrosine, azine dye containing an alkyl group having 2 to 16 carbon atoms (Japanese Patent Publication No. 1627/1983), basic dye (e.g. C, 1, B
a5ic Yellow 2 (C, 1,41000)
, C,1,Ba5ic Yellow 3,C,1,
Ba5ic Red 1 (C, 1,451 [10)
, C,1,Ba5ic Red 9 (C,1,425
0G), C, I.

Ba5ic Violet 1 (C, 1,4253
5), C,1,Ba5ic Violet3(C,
1,42555), C,1,Ba5ic Viole
t 10 (C, 1, 45170), C, 1, Ba
5ic Violet 14 (C, 1,425
10), C, I.

Ba5ic Blue 1 (C, 1, 42025)
,C,1,Ba5ic Blue 3(C,1,5
1005), C,1,Ba5ic Blue 5(
C, 1, 42140), C01, Ba5ic Blue
? (C,1,42595), C,1,Ba5ic
Blue 9 (C, 1, 52015), C, 1, Ba5
ic Blue 24 (C, 1, 52030), C
,1,Ba5ic Blue25(C,1,52025
), C,1,Ba5ic Blue2B(C,1,44
045), C,1,Ba5ic Green 1
(C, 1, 42040), C, 1, Ba5ic Gr
een 4 (C, 1,42000), C, 1,451
70, etc.), lake pigments of these basic dyes (lake-forming agents include phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdenum, tannic acid, lauric acid, gallic acid, ferricyanide, 7x rusyanide, etc.), ), C,1,5olventBlack 3
(C, 1, 28150), Hansa Yellow G (C, 1
, 1lB80) , C, 1, Mordant Bla
ck 11, C, 1, PigiIentBlack l
, Gilt Night, Asphalt, etc.

Quaternary ammonium salts, such as benzyldimethyl-hexadecyl ammonium chloride, decyl-trimethylammonium chloride, organotin compounds such as dibutyltin oxide, metal salts of higher fatty acids, inorganic fine powders of glass, mica, zinc oxide, etc. ζEDTA, acetylacetone metal complexes, etc.

Polyamine resins such as vinyl polymers containing amine 7 groups and condensation polymers containing amino groups.

(2) A device that controls toner to be negatively charged
No. 0153, No. 43-27596, No. 44-6397
Metal complex salts of monoazo dyes described in No. 45-26478.

Co, C'r, Fe, etc. metal complexes of salicylic acid, oxynaphthoic acid, guicarboxylic acid described in Japanese Patent Publications No. 55-42752, No. 58-41508, No. 59-7384, No. 59-7385, etc. .

Sulfonated copper phthalocyanine pigment.

Styrene oligomer with nitro groups and halogens introduced. Chlorinated paraffin, melamine resin, etc.

However, as mentioned above, the use of conventional charge control agents still has many problems that need to be improved. That is,
Many of these charge control agents are derived from dyes and pigments, and generally have complex structures, inconsistent properties, poor stability, and strong coloring properties. Recently, there are some products that have been proposed that are different from the above-mentioned ones, but none of them exceeds dye- and pigment-based ones in terms of overall performance, and although they have many disadvantages as listed below,
In most cases, dye and pigment-based charge control agents are used.

In other words, these charge control agents are usually added to the thermoplastic resin that is the binder resin of the toner and are contained in the toner prepared through processes such as hot melt dispersion, pulverization, and classification. In the process, the above-mentioned dye and pigment-based charge control agents often cause problems. For example, as mentioned above, these charge control agents have poor stability as substances, and are susceptible to decomposition during hot kneading and mechanical damage. It is easy to decompose or change in quality due to physical impact, friction, changes in temperature and humidity conditions, etc., and tends to cause a phenomenon in which charge controllability is deteriorated. Furthermore, if a toner containing these dyes and pigments as a charge control agent is developed using a copying machine, the charge control agent may decompose or change in quality as the number of copies increases, causing deterioration of the toner during repeated copying operations. be.

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 in the past to achieve more uniform dispersion. However, unreacted fatty acids or salt dispersion products are often exposed on the toner surface and contaminate the carrier or toner carrier, resulting in decreased toner fluidity, fogging, and
This causes a decrease in image density. 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.

Furthermore, many charge control agents are hydrophilic, and due to poor dispersion in these resins, dyes are exposed on the toner surface when the toner is crushed after melt mixing. Therefore, when the toner is used under high humidity conditions, there is a problem that a good quality image cannot be obtained because these charge control agents are hydrophilic.

In this way, when conventional charge control agents are used in toner,
Variations occur in the amount of charge generated on the surface of toner particles between toner particles, between toner and carrier, or between toner and a toner carrier such as a sleeve, resulting in development fog, toner scattering, carrier contamination, etc. Failures are likely to occur, and these failures become noticeable when copies are made many times, resulting in a result that is practically unsuitable for copying machines.

Furthermore, under high-temperature conditions, the transfer efficiency of toner images decreases significantly, making many toner images unusable.Even at room temperature and humidity, when the toner is stored for a long time, Due to the instability of the control agent, it often undergoes deterioration and becomes unusable due to poor charging properties.

Furthermore, when conventional charge control agents are used in toner, after long-term use, the charge control agents themselves adhere to the surface of the photoreceptor, or their presence promotes toner adhesion (occurrence of filming phenomenon). .

This often causes inconveniences in the cleaning process of the copying machine, such as adversely affecting the formation of latent images, causing scratches on the surface of the photoreceptor or cleaning members such as cleaning blades, or accelerating abrasion of the members.

Furthermore, when conventional charge control agents are used in toners, they often have a large effect on the thermal melting properties of the toner and reduce fixing performance. In particular, they worsen high-temperature offset performance, and when heat roll fixing is performed, transfer material There are disadvantages such as increased clinging to the roller and reduced durability of the roller.

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

A general object of the present invention is to provide a new technique for toner charge control that overcomes these problems.

A more specific object of the present invention is to stabilize the amount of triboelectric charge between toner particles, between a toner and a carrier, or between a toner and a toner carrier such as a sleeve in the case of component development;
Another object of the present invention is to provide a toner that has a sharp and uniform triboelectric charge distribution and can be controlled to a charge amount suitable for the developing system used.

Still another object is to use a developer for faithfully developing and transferring the latent image, i.e., without toner adhesion in the background area during development, without fogging, and without toner scattering around the edges of the latent image. To provide a toner with high image density and good halftone reproducibility.

Still another object is to provide a toner that maintains its initial characteristics even when used continuously over a long period of time, and that does not agglomerate or change its charging characteristics.

Another objective is to provide a toner that reproduces stable images unaffected by changes in temperature and humidity, and especially toner that has high transfer efficiency and does not cause scattering or transfer omissions during transfer at high or low humidity. be.

Still another object is to provide a bright chromatic toner.

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

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

Still another object is to provide a toner having good fixing properties, especially a toner that does not suffer from high temperature offset or the like.

The toner for developing an electrostatic image of the present invention has been developed to achieve the above-mentioned object. It is characterized by containing.

That is, the present inventors have discovered that the above-mentioned salicylaldimine or alkyl salicylaldimine chelate compounds (hereinafter, when these are collectively referred to as "(alkyl)
Salicylaldimine chelate) not only exhibits excellent charge control properties when included as a charge control agent in toner, but also is stable under heating and use over time, has low hygroscopicity, and The present invention was completed based on the finding that it has a property of being essentially colorless or light-colored, which is extremely effective for achieving the above-mentioned object.

The present invention will be explained in more detail below. In the following description, "1 part" and "r%" expressing quantitative ratios are based on weight unless otherwise specified.

1 In the present invention, (alkyl) used as a charge control agent
Salicylaldimine chelates include, in addition to salicylaldimine, alkyl salicylaldimines having 1 to 3 alkyl groups having 1 to 24 carbon atoms, particularly 1 to 16 carbon atoms;
Specifically, 3-methylsalicylaldimine, 3-ethylsalicylaldimine, 3-n-butylsalicylaldimine, 3-stearylsalicylaldimine, 5-methyl
\Salicylaldimine, 5-ethylsalicylaldimine, 5-t-butylsalicylaldimine, 5-laurylsalicylaldimine, 3,5-dimethylsalicylaldimine, 3.5-diethylsalicylaldimine, 3-methyl-5-ethylsalicylaldimine, 3-methyl-5-t
-butylsalicylaldimine, 3-ethyl-5-n-butylsalicylaldimine, 3-methyl-5-laurylsalicylaldimine, 3-ethyl-5-stearylsalicylaldimine, 3,5-di-t-butylsalicylaldimine, etc. , nickel, zinc, chromium, cobalt, iron, copper, etc., and among them, chelate compounds of chromium, cobalt, iron, and copper.

The above-mentioned (alkyl) salicylaldimine chelate is
It can be synthesized by a known method, and can be easily obtained, for example, by adding an aqueous metal salt solution to an ethanol solution of salicylaldehyde or alkyl salicylaldehyde and aqueous ammonia and heating the mixture.

In general, (alkyl)salicylaldimine chelates are
It is preferable to prepare the toner with an average particle size of 10 to 0.01 g, particularly 2 to 0.1 g.

The above-mentioned (alkyl) salicylaldimine chelate can be used in toners containing binder resin and colorant as essential components (
The toner of the present invention can be obtained by blending it into a colored fine powder). As for the blending form, there is a so-called internal addition form in which the compound is encapsulated in the toner uniformly or in a capsule form, and a so-called internal addition form in which the compound is mixed and attached to the toner. Any of the so-called externally added forms can be adopted.

When internally added, the amount of (alkyl) salicylaldimine chelate 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. Although not limited to, it is preferably 0.1 parts by weight per 100 parts by weight of the binder resin.
It is used in a range of 20 parts by weight (more preferably 0.5 to 10 parts by weight).

In addition, when externally added, 0.
01 to 20 parts by weight is desirable.

Note that, if necessary, a conventionally known charge control agent may 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 and its substituted products such as chlorostyrene and polyvinyltoluene: styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, 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 chloromethacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinylethyl ether copolymer, Styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer, etc. Styrene'-based copolymer; polymethyl methacrylate,
Polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, polyurethane, polyamide, epoxy resin, polyvinyl butyral, polyacrylic resin, rosin, modified rosin, terpene resin, phenolic resin, aliphatic or alicyclic resin Examples include hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, and paraffin waxes, which can be used alone or in combination.

Further, in order to provide a toner particularly suitable for pressure fixing, the following binder resins can be used alone or in combination.

HolJ olefin (low molecular weight polyethylene, low molecular weight polypropylene, polyethylene oxide, polytetrafluoroethylene, etc.), epoxy resin, polyester resin, styrene-butadiene copolymer (monomer ratio: 5-30:9
5-70), olefin copolymers (ethylene-acrylic acid copolymers, ethylene-acrylic acid ester copolymers,
Ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-vinyl acetate copolymer,
ionomer resin), polyvinylpyrrolidone, methyl vinyl ether-maleic anhydride copolymer, maleic acid-modified phenol resin, phenol-modified terpene resin.

Colorants include carbon black, lamp black,
Iron black, ultramarine, nigrosine dye, aniline blue, phthalocyanine blue, phthalocyanine green, Hansa yellow G, rhodamine 6G lake, chrome yellow, quinacridone, benzidine yellow, rose bengal, anthraquinone dye, tri7lylmethane dye, monoazo, disazo Conventionally known dyes and pigments such as dyes and pigments may be used alone or in combination.

Furthermore, the toner of the present invention can further contain a magnetic material and be used as a magnetic toner. Examples of the magnetic material contained in the magnetic toner of the present invention include iron oxides such as magnetite and ferrite; iron oxides such as iron, cobalt, and nickel; Metals or alloys of these metals with metals such as aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, and mixtures thereof, etc. can be mentioned.

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

Further, the toner of the present invention may contain additives other than those mentioned above, if necessary. Examples of additives include lubricants such as Teflon and zinc stearate, or colloidal silica, titanium oxide, aluminum oxide, etc. Examples include fluidity imparting agents, anti-caking agents, conductivity imparting agents such as carbon black and tin oxide, and fixing aids such as low molecular weight polyethylene.

In order to produce the toner for developing an electrostatic image according to the present invention, the (alkyl) salicylaldimine chelate charge control agent according to the present invention is combined with the above-described binder resin and a pigment or dye as a colorant, if necessary. According to the requirements, magnetic materials, additives, etc. are thoroughly mixed using a ball mill or other mixer, and then melted and kneaded using a heat kneader such as a heated roll, kneader, or extruder to make the resins mutually dissolve. A toner having an average particle size of 5 to 20 JL can be obtained by dispersing or dissolving a pigment or dye in the toner, cooling and solidifying it, and then crushing and classifying it. Alternatively, the material can be obtained by dispersing the material in a binder resin solution and then spray-drying it, or by mixing the specified material with the monomers that should constitute the binder resin to form an emulsified suspension and then polymerizing it. Methods such as a polymerization method and a toner production method for obtaining a toner can be applied.

Furthermore, as described above, the toner of the present invention can also be obtained by externally adding a charge control agent to a toner that has been formed by removing all or part of the charge control agent.

Toners prepared by these methods can be used for developing to visualize electrostatic images in electrophotography, electrostatic recording, electrostatic printing, etc. by any conventionally known means.

``Mamerikou'' As described above, the toner of the present invention containing (alkyl) salicylaldimine chelate as a charge control agent has a uniform amount of frictional charge between toner particles, and the amount of charge can be easily controlled. In addition, the toner is extremely stable as it does not change in quality during use and the amount of triboelectric charge does not vary or decrease.

This eliminates problems such as development fog, toner scattering, and contamination of electrophotographic materials and copying machines as described above, as well as eliminating toner aggregation during storage, which was a major problem in the past.
It is a toner that can withstand long-term storage without causing agglomeration or low-temperature fluidity phenomena, and the toner image has excellent abrasion resistance, fixing properties, and adhesion. , and when used in a repetitive transfer type copying system in which the transfer operation is repeated continuously, the effect is further enhanced. Further, since there is little color tone disturbance caused by the charge control agent, it is possible to form color images with excellent colors when used as a color electrophotographic toner.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples.

"Styrene/butyl acrylate 100 parts copolymer (
80/20) (Weight average molecular weight Mw: approx. 300,000) Carbon black (Mitsubishi #44) 10 parts Low molecular weight polyethylene wax 2 parts Co chelate of salicylaldimine 2 parts After mixing the above materials well in a blender, heat at 150°C. The wires were mixed with two rolls heated to . After allowing the mixture to cool naturally, it is coarsely pulverized with a cutter mill, then pulverized with a pulverizer using a jet stream, and further classified with an air classifier to obtain fine toner powder with a particle size of 5 to 20 IL. I got it.

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

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

Next, by a conventionally known electrophotographic method,
A negative electrostatic image was formed, and this was powder-developed using the above-mentioned developer using a magnetic brush method to create a toner image, which was transferred to plain paper and heat-fixed. The resulting transferred image has a density of 1.
30, which was sufficiently high, and there was no fogging at all, and a good image with high resolution was obtained without toner scattering around the image. Transfer images were continuously created using the above developer and their durability was examined, and the transferred images after 30,000 copies were also completely dull compared to the initial images.

Further, during the durability test, 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 fusing process at this time, and when the 30,000-sheet durability test was completed, the fusing machine was observed and there were no scratches or damage to the rollers.
There was almost no staining due to offset toner, and there was no problem in practical use.

In addition, when the environmental conditions were set to 35℃ and 85%, the image density was 1.29, a value that was almost unchanged from room temperature, and clear images were obtained without fogging or scattering, and the durability was 30,000 sheets. There was almost no change until 15℃ at the 0th order.
, when a transferred image was obtained at a low temperature and low humidity of 10%,
The image density was as high as 1.29, and solid black was developed and transferred extremely smoothly, resulting in an excellent image with no scattering or hollow spots. A durability test was conducted under these environmental conditions. I copied it continuously and intermittently, but it was still 30. .

The density variation up to 00 sheets was ±0.2, which was sufficient for practical use.

Stop ttz 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 CO chelate of salicylaldimine, and development, transfer, and fixing were carried out. Images were obtained similarly. At room temperature, there was little fog, but the image density was low at 1.06, line drawings were scattered, and solid black was noticeably rough. Durability was investigated, and the density decreased to 0.83 after 30,000 sheets.

Further, during the durability test, the toner material formed a film in the form of thin stripes on the surface of the photoreceptor before and after the io and ooo sheets, and began to appear as lines on the image. This is so-called filming, and is thought to be due to the charge control agent changing the lubricity of the toner powder.

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

When an image was obtained under conditions of 35° C. and 85%, the image density was as low as 0.88, and fogging, scattering, and roughness increased. The transfer efficiency was also as low as 69%.

Images were taken at 15°C and 10%.

Image density is low at 0.91, with scattering and capri.

It was very rough and the transfer was noticeable. Continuous image output,
However, after about 30,000 sheets, the density was 0.53, making it impractical.

A developer was obtained in the same manner as in Example 1, except that 3 parts of Cu chelate of salicylaldimine was used instead of 2 parts of Co chelate of salicylaldimine, and an image was obtained in the same manner by performing development transfer fixing.

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

Kasha 1” Instead of 2 parts of Co chelate of monosalicylaldimine,
A developer was obtained in the same manner as in Example 1, except that 2 parts of Co chelate of 3-ethylsalicylaldimine was used, and an image was obtained in the same manner by performing development, transfer, and fixing.

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

Instead of 2 parts of Co chelate of 10 mouth salicylaldimine, 3 parts
A developer was obtained in the same manner as in Example 1 except that 2 parts of Fe chelate of ,5-di-t-butylsalicylaldimine was used.
Developing, transferring, and fixing were performed to obtain images 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.

Support 1” Styrene/butyl acrylate 100 parts (8Q/2
0) Copolymer (weight average molecular weight MW: approximately 300,000) Triiron tetroxide E PT-50060 parts (manufactured by Toda Kogyo) 2 parts low molecular weight polypropylene wax 2 parts CO chelate of salicylaldimine The above materials were mixed well in a blender. Thereafter, the mixture was kneaded using two rolls heated to 150°C. After allowing the mixture to cool naturally, it is roughly pulverized using a cutter mill, then pulverized using a pulverizer using a jet stream, and further classified using an air classifier to obtain a fine powder with a particle size of 5 to 20 l. Obtained.

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

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

When this toner was applied to a commercially available copying machine (trade name NP-1502, manufactured by Canon Co., Ltd.) and an image was produced, good results similar to those of Example 1 were obtained.

Length” mouth 11 In Example 5, C of salicylaldimine.

A developer was obtained in the same manner as in Example 5, except that 3 parts of Cu chelate of salicylaldimine was used instead of 2 parts of chelate, and an image was obtained by performing development, transfer, and fixing in the same manner.

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

Mitate-kari 1 In Example 5, C of salicylaldimine.

A developer was obtained in the same manner as in Example 5, except that 2 parts of Co chelate of 3-ethylsalicylaldimine was used instead of 2 parts of chelate, and an image was obtained in the same manner by performing development, transfer, and fixing.

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

Co chelate of salicylaldimine in Example 5
A developer was obtained in the same manner as in Example 5, except that 2 parts of benzyldimethyl-hexadecyl ammonium chloride was used instead of 1 part, and an image was obtained in the same manner. At room temperature, there is little fog, but the image density is low at 0.8, and line drawings are scattered.
The solid black was noticeably rough. I checked the durability, but it was 30
,000 sheets, the temperature decreased to 0.48.

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

When an image was obtained under conditions of 35° C. and 85%, the image density was as low as 0.72, and fogging, scattering, and roughness increased, making it unusable. The transfer efficiency was also as low as 63%.

When an image was obtained under the conditions of 15° C. and 10%, the image density was as low as 0.73, and there was severe scattering, fogging, roughness, and transfer omissions were noticeable. I tried to take continuous images, but 3
At the time of 0,000 sheets, the density was 0.59, making it impractical.

Styrene/butyl acrylate 100 parts (80/2
0) Copolymer (average molecular weight MW: approx. 300,000) Copper phthalocyanine blue pigment 5 parts Low molecular weight polypropylene wax 2 parts CO chelate of salicylaldimine 2 parts The above materials were thoroughly mixed in a blender and then heated to 150°C in two rolls. There was a mix-up. After allowing the mixture to cool naturally, it is roughly pulverized using a cutter mill, then pulverized using a pulverizer using a jet stream, and further classified using an air classifier to obtain fine toner powder with a particle size of 5 to 20 IL. Obtained.

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

Next, 50 parts of carrier iron powder having a particle size of 50 to 801 L was mixed with 100 parts of the toner to prepare a developer.

This developer is stored in the developer container 1 of the developing device shown in the attached drawing.
The developing operation was carried out by putting the film in a . That is, in this device, a cylindrical toner carrier 2 made of stainless steel with a roughened surface is housed in a lower opening of a container 1 so as to substantially close the lower opening, and the toner carrier 2 has a circumferential speed of 66 m in the direction of arrow a.
Rotated at m/sec. On the other hand, at the outlet portion of the sleeve 2 of the container 1 on the downstream side in the rotational direction, 2001L is provided from the sleeve surface.
An iron blade 3 with its tip at position m is arranged, and a fixed magnet 4 is arranged inside the sleeve 2, and a line connecting its main magnetic pole, the N pole, with the center of the sleeve °,
The angle θ between the center of the sleeve and the tip of the blade 3 is 30"
It was arranged so that Under these conditions, as the sleeve 2 rotates, the developer is contained in the developer in the container 1.

A magnetic brush 5 is formed by the carrier iron powder, and this magnetic brush 5 takes in the toner 6 preferentially distributed above the magnetic brush 5 and supplies it to the surface of the sleeve 2 while circulating it along the periphery of the sleeve 2 below the container l. A thin layer 16 of toner is then formed on the surface of the sleeve 2 that has passed through the blade 3.

In this example, the thickness thus formed is approximately 801 mm.
Due to the thin toner layer Lm, a dark area on the photoreceptor drum 7, which faces each other at an interval of about 3001 Lm and rotates in the direction indicated by the arrow at a circumferential speed of about 60 mm/sec, in the developing section (nearest section) -
A negative electrostatic image of 600V and -1500V was developed. At this time, a bias voltage having a frequency of 800 Hz, a peak-to-peak value of 1.4 KV, and a center value of 1,300 V was applied between the sleeve 2 and the photosensitive drum 7 by the power source 8.

When the image was printed in this way, a good image with a bright blue color was obtained, and even after printing 1,500 images, the toner/carrier ratio was 10:750.
There was almost no change in image density, and good images were obtained even after printing up to 30,000 sheets while replenishing toner.

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

BRIEF DESCRIPTION OF THE 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. Φ magnetic brush, 6. Toner, 7. Fist electrostatic latent image carrier. 16... Thin layer toner.

Claims (1)

[Scope of Claims] 1. A toner for developing an electrostatic image, comprising a binder resin, a colorant, and a chelate compound of salicylaldimine or alkylsalicylaldimine. 2. The electrostatic image developing device according to claim 1, wherein the chelate compound of salicylaldimine or alkylsalicylaldimine is contained in a proportion of 0.1 to 20 parts by weight based on 100 parts by weight of the binder resin. toner. 3. The toner for developing electrostatic images according to claim 1, wherein the chelate-forming metal is Cr, Co, Cu, or Fe.