JPS61160763A - Electrostatic charge applying member for developing electrostatic charge image - Google Patents

Abstract

PURPOSE:To form an electrostatic charge applying member which applies adequate negative electrostatic charge to a toner by having a specific metallic complex on the surface. CONSTITUTION:This toner has the metallic complex of salicylamine or alkylsalicylamine on the surface. The metal to constitute the metallic complex is copper, nickel, cobalt, cadmium and chromium and the alkyl group to constitute the alkylsalicylamine is an alkyl group of 1-18C which may have side chains. The representative embodiment of such compd. is exemplified by salicylamine. The compd. is extremely stable and can be easily produced by adding an aq. ethanol soln. of the salicylamine to an aq. metallic salt soln. and heating the soln. The aq. metallic salt soln. which has relatively large solubility in water is usually preferably used.

Description

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

[Prior art] As a conventional electrophotographic method, U.S. Patent No. 2,297°89
No. 1, Special Publication No. 42-23910 and Special Publication No. 43
Various methods are described in Japanese Patent No. 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 to remove the electrostatic charge. An Hs image is formed, and then the latent image is developed and visualized using a fine powder called toner in this technology, and if necessary, the powder image is transferred to paper or the like, and then heated, pressurized, or with solvent vapor, etc. This is to fix the problem.

Development methods applicable to these electrophotographic methods include:
Broadly speaking, there are 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.

The 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, the -component-based development methods include the powder cloud method, which uses toner particles in a spray state, and the electrostatic method that uses toner particles directly. Contact development method (also called contact development or toner development) in which toner particles are developed by contacting with the image surface, and the toner particles are charged and developed by the electric field of the electrostatic latent image without directly contacting the toner particles with the electrostatic latent image surface. There are a jumping development method in which the toner is caused to fly toward the latent image surface, a magnetry method in which development is performed by bringing a magnetic conductive toner into contact with the electrostatic latent image surface, and the like.

As toners applied to these developing methods, fine powders in which dyes and pigments are dispersed in natural or synthetic resins have conventionally been used.

For example, particles obtained by dispersing a colorant in an adhesive resin such as polyethylene and pulverizing the particles to about 1 to 30 IL are used as toner. As the 6ti toner, one containing magnetic particles such as magnetite is used.

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

Further, the toner is made to have a positive or negative charge depending on the polarity of the electrostatic latent image to be developed.

In order to make the toner retain an electric charge, it is also possible to use 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 toners, dyes, pigments, and even charge control agents that impart charging properties are added.

However, these additives must be present on the surface of the toner to some extent in order to impart charging properties. Therefore, the toner may be damaged due to friction between the toners, collision with the carrier, friction with the electrostatic latent image carrier, etc. These additives fall off from the surface, resulting in contamination of the carrier and the electrostatic latent image carrier, such as the photoreceptor belt or drum.

As a result, the charging property deteriorates, and as the number of images printed increases, the deterioration progresses, the image density decreases, and fine line reproducibility, fogging, etc. become practical problems.

This can be improved by improving the affinity and dispersibility of the toner binder and the dye, pigment, or charge control agent that imparts chargeability, but if surface treatment is performed to increase the affinity of these additives, In many cases, the ability to provide a charge decreases, and if mechanical shear is applied strongly and finely dispersed.

The proportion of additives appearing on the toner surface decreases, and charging properties tend to be insufficient. For these reasons, the number of charge-imparting additives that are sufficiently satisfactory for practical use is extremely limited, and only a small number of them have been put into practical use, especially in order to cope with the increasing demand for not only black and white images but also color images in the future. For this reason, it is preferable that the additive added to the toner be colorless, and there are currently almost no additives that have been put to practical use that meet this requirement.

[Problems to be Solved by the Invention] In view of the above-mentioned circumstances, the present inventors did not adopt a method of imparting charge using a toner additive, but instead used a carrier.

We conducted extensive studies to restrict transport such as sleeves and doctor blades, or to use charging materials.

In the present invention, the charge imparting member is a member that contacts the toner and imparts or auxiliary charges necessary for development. In this method, it is not necessary to contain almost any charge-imparting additive in the toner, so the above-mentioned problems such as contamination of the carrier, photoreceptor, etc. do not occur, and the chargeability decreases during image formation and the latent image will no longer be disturbed. Furthermore, color toner can be easily charged.

However, in order to control the conveyance of carriers, sleeves, doctor blades, etc., or to make charging members possess charge imparting properties, charge imparting substances must be used.

It must be a material that has a strong charge-imparting ability and can be applied or coated to parts, and the carrier must not be replaced for a long period of time, and the sleeve must be used until the developing machine body becomes unusable. , the charge imparting member must be durable for long-term use.

An object of the present invention is to provide a charge imparting member that solves the above-mentioned problems.

A further object of the present invention is to provide a charge imparting member that imparts appropriate negative chargeability to toner.

A further object of the present invention is to provide a charged member whose performance does not deteriorate even after long-term use.

A further object of the present invention is to obtain Wf14 images with excellent 1m line reproducibility and gradation. The present invention provides an application member.

A further object of the present invention is to provide a charge imparting member suitable for coloring.

[Means for Solving the Problems] That is, the present invention is a charge-imparting member for developing electrostatic images characterized by having a metal complex of salicylamine or furkylsalicylamine on its surface.

The metals constituting the metal complex of the present invention are copper, nickel, cobalt, cadmium, chromium, etc., and the alkyl group constituting the alkylsaltylamine is an alkyl group having 1 to 18 carbon atoms that may have a y4 chain. .

Typical examples of these compounds include the following.

salicylamine, 3-methylsalicylamine, 3-ethylsalicylamine, 3-impropylsalicylamine,
3-n butylsalicylamine, 3-stearylsalicylamine, 5-methylsalicylamine, 5-ethylsalicylamine, 5-n propylsalicylamine, 5-te
rt-butylsalicylamine, 5-laurylsalicylamine, 5-stearylsalicylamine, 3,5-dimethylsalicylamine, 3,5-diethylsalicylamine, 3
゜5-di-npropyl salicylamine, 3,5-ditar
t-butylsalicylamine, 3-methyl-5-ethylsalicylamine, 3-methyl-5-tertbutylsalicylamine, 3-ethyl-5-tertbutylsalicylamine, 3-methyl-5-laurylsalicylamine, 3-ethyl -5-laurylsalicylamine, 3-methyl-5-
Examples include chelate compounds of copper, nickel, cobalt, cadmium, chromium, etc. of lauryl salicylamine and 3-ethyl-5-stearylsalicylamine.

These compounds are extremely stable and can be synthesized by known methods. Generally, it can be easily produced by adding an ethanol aqueous solution of salicylamine to an ammonia weak alkaline earth metal salt aqueous solution and heating the mixture.

As the metal salt aqueous solution, it is usually preferable to use an organic, a-free metal salt such as nitric acid, sulfuric acid, hydrochloric acid, or acetic acid, which has a relatively high solubility in water.

The above compound may be used as a charge-imparting material by being dispersed in a solvent or a dispersion medium as it is.

It may also be used after being dispersed in a resin.

In addition, ceramic powder such as silica powder, aluminum oxide, cerium saponide, and silicon carbide may be used as a filler, and conductivity imparting agents such as carbon black and tin oxide may be used to adjust conductivity. Further, in order to prevent the accumulation of spent toner on the sleeve or carrier surface, a release agent such as a fatty acid metal salt, vinylidene fluoride, etc. may be mixed and used.

Further, as the resin for dispersion, common resins can be used. For example, polystyrene, polyacrylic acid ester, polymethacrylic acid ester, polyacrylonitrile,
Rubber resins such as isoprene and butadiene, polyesters, polyurethanes, polyamides, epoxy resins, rosins, polycarbonates, phenolic resins, chlorinated paraffins, polyethylene, polypropylene, silicone resins, Teflon and their derivatives, copolymers, and mixtures are used. It is possible.

When the charge-imparting compound is mixed and deposited on the spear 7, the amount of the charge-imparting compound is 100 g -1 g per 1 kg of carrier, preferably 20 g to 5 g, and when it is deposited on the sleeve etc., the amount of the charge-imparting compound is 0.0 g per 1 cm2 of effective surface area. .01
mg-10 layer g, preferably 0.1H to 2 mg.If the amount is less than the above range, the charge imparting power and lifespan will be insufficient, and even if it is used beyond the above range, the charge imparting power, lifespan, etc. will be insufficient. Utility is saturated and useless.

The carrier to which the above compound can be applied is not particularly limited, and includes, for example, powders or particles of metals such as iron, nickel, aluminum, copper, and alloys thereof.

Powders or particles of metal compounds, including metal oxides.

Ceramic powder or particles such as glass, SiC, BaTiO3, 5rTi03.

The surface of the above powder or particles is treated with resin, etc.

Resin powder, resin powder containing magnetic material.

etc. can be given.

Further, the sleeve to which the above compound can be applied is made of metal materials such as iron, aluminum, stainless steel, nickel, or alloys containing these metals, and ceramics.
Any material that can generally be used as a sleeve may be used, such as non-metallic materials such as plastics.

Furthermore, the toner used when using the member of the present invention can be either non-magnetic or magnetic toner, and is suitable for all methods of developing by charging the toner, regardless of whether it is a two-component development method or a -component development method. Applicable.

For example, magnetic brush development method, cascade development method, fur brush development method, so-called microtoning development method using magnetic material-containing resin powder as a carrier, development method using resin powder as a carrier, so-called jumping development method, or non-magnetic toner. It can be applied to jumping development methods, etc. that develop images.

These toners provide more efficient charging, so
It may also contain small amounts of charge-imparting substances, such as dyes, pigments, or so-called charge control agents, as well as fluidizing agents such as colloidal silica, abrasives such as cerium oxide, strontium titanate, silicon carbide, and stearic acid. It may also contain lubricants such as metal salts and vinylidene fluoride.

It may contain conductivity imparting agents such as carbon black and tin fermentation.

In order to manufacture the member of the present invention, it is preferable to hold the compound on the surface of a material or equipment that has a sufficient opportunity to come into contact with the toner before the development stage, specifically, a carrier, a sleeve, a doctor blade, etc. That is, in the carrier treatment, a usual method is employed, such as soaking the carrier core in a solution in which the compound is dissolved or dispersed in a tank, or attaching it to the surface using a spray or a fluidized bed.

In addition, when coating the sleeve, methods such as dipping, spraying, and brushing are used using the same solution.

Furthermore, the member of the present invention can be manufactured by incorporating the above-mentioned compound into a moldable resin using a known method and then molding the resin into a carrier, sleeve, doctor blade, or the like.

[Example] Example 1 100 g of salicylamine CO complex was dissolved and dispersed in methyl ethyl ketone lt, and iron powder carrier (particle size: 2
50 to 400+5esh) l kg were dispersed and stirred and mixed in a ball mill for about 30 minutes.

After drying this iron powder carrier mixture to completely remove the solvent, the agglomeration was slightly loosened to obtain an electrostatic charge developing member of the present invention.

Separately, toners were prepared with the following formulation using conventional materials and methods. No charge imparting substance was included. (The following parts indicate parts by weight).

Polystyrene (product name D-125 manufactured by Niesso Chemical) 10
0 parts Carbon black (trade name: Raven 3500, manufactured by Cabot Corporation) 6 parts The above toner material was mixed, crushed and classified to have a particle size of 1 to 30.

This toner and the carrier were mixed at a weight ratio of 10:100 to prepare a developer.

When the tripometry of this developer was measured by the blow-off method, it was -9.3 final c/g.

When this developer was used to produce an image on a Canon MP-5000 copying machine, there was no change in image density even after a durability test of 50,000 sheets, and fine line reproducibility was good.

The gradation was also good and there was no fogging at all.

Example 2 Polymethyl methacrylate resin 10 in xylene 11
0 g was dissolved, and 50 g of salicylamine Ni complex was mixed therewith. As in Example 1, the iron powder carrier IKg
A carrier having a charge imparting effect, which is a member of the present invention, was obtained.

Separately, a toner exactly the same as in Example 1 was prepared, and the toner and carrier were mixed in the same weight ratio as in Example 1 to prepare a developer.

When the tripometry of this developer was measured by the blow-off method, it was -11.0 final c/g.

When this developer was used to produce images on a Canon MP-5000 copying machine, it showed good image density, fine line reproducibility, and gradation that were completely unchanged from the initial state even after a 50,000-sheet durability test, and there was no fog. was also not recognized.

Example 3 Polymethyl methacrylate resin 10 in xylene 17
A solution was prepared by dissolving 0 g of 5-methylsalicylamine Co complex and mixing it with 50 g of 5-methylsalicylamine Co complex.

Dip a developing sleeve (stainless steel) for Canon MP-400RE in this solution, and coat the surface of the sleeve with 5
The amount of methylsalicylamine Co complex attached is 0.1 mg/
A member of the present invention was obtained by coating so as to have am2 to 0.8 mg/as2.

This sleeve was placed in the original developing machine.

The toner has the following formulation to prevent general crosstalk and pulverization.

Through a process such as classification, the particle size was adjusted to lIL to aoIL.

Poly(styrene-butyl methacrylate) F%l-30
0,000 too part release side type agent Product name PE-130: Manufactured by Bequist Co., Ltd.) 4 parts Magnetic powder (Product name BL-200: Manufactured by Titan Kogyo Co., Ltd.) 60 parts Using this toner, image was created with Canon MP-400RE. We did a durability test. After 50,000 sheets of durability, there was little change in the image from the beginning, good fine line reproducibility, 5 gradations, and no fogging.

Furthermore, when the surface potential of the toner on the sleeve was measured after the end of the durability test, it was found to be -33V, confirming that the toner was completely negatively charged.

Example 4 A solution was prepared by dissolving 80 g of polycarbonate resin in xylene 17 and further combining 20 g of 3,5-ditartbutylsalicylamine old complex.

A developing sleeve (made of aluminum) of a developing machine with a blue cartridge for Canon PC-20 was dipped in this solution, and the amount of 3.5-ditart butylsalicylamine N1fi attached to the sleeve surface was 0.1a + g/C 2 ~
A member of the present invention was obtained by coating with 0.5 mg/c Sodium 2.

This sleeve was placed in the original developing machine.

On the other hand, the toner was prepared according to the following formulation, and the particle size was 1IL~3.
Arranged at the end of 0.

Poly(styrene-butyl methacrylate) VhII=1
50,000 100 parts Mold release agent (trade name PE-130: manufactured by Bequist) 4 parts Blue colorant (phthalocyanine pigment) 6 parts Using this toner, using a developing machine equipped with the above sleeve, PC-2
0 was modified to enable reversal development, and durable images were produced.

100g of toner was charged and a test was conducted until the toner ran out, but a clear blue image with good 1m line reproducibility and gradation was obtained without any change in the image. Furthermore, the surface potential of the toner on the sleeve was measured and found to be -42V, confirming the charge imparting effect.

Examples 5 to 11 Electrostatic charge developing members of the present invention were obtained using the compounds described in Examples 5 to 11 in Table 1 in the same manner as Examples 1 to 4,
Performance evaluation was performed in the same manner as in Examples 1 to 4, respectively.

Regarding the solvent 1 dispersant used for each compound, component configuration, performance test method, performance evaluation, etc.
Table 1 includes the cases of Examples 1 to 4. As shown in the performance evaluation column, all the electrostatic charge developing members obtained using each compound exhibited good performance.

In addition, the method is abbreviated as "" in the table.

MEK・・・・・・Methyl ethyl ketone PMMA
...Polymethyl methacrylate resin PS...
・・・・・・・・・Polystyrene (product name [) -1
25: Esso Chemical) P S E 300,000...Poly(styrene-butyl methacrylate) Mw300,000 P S B 150,000...Poly(styrene-butyl methacrylate)) 1w150,000 PC...・・・・・・・・・Polycarbonate resin C
B...Carbon black (trade name: Raven 3500, manufactured by Capot Co., Ltd.) As the mold release agent and magnetic powder, those having the trade names described in Example 3 were used.

Image density: Fine line reproducibility 9 Gradation quality is expressed as 0 for good and Δ for fair.

Table 1 (Continued) Performance evaluation [■] Image output test [Effect of the invention] By using the charge imparting member of the present invention, the image obtained by developing an electrostatic charge image in electrophotography, electrostatic recording, electrostatic printing, etc. The image has very little change in density over a long period of time, has good fine line reproducibility and gradation, and has little fog.

It can also be effectively used for color development, and extremely clear images can be obtained.

Claims (1)

[Scope of Claims] 1. A charge-imparting member for developing electrostatic images, characterized in that it has a metal complex of salicylamine or alkyl salicylamine on its surface. 2. The compound according to claim 1 is a carrier,
The charging member for developing an electrostatic image according to claim 1, which is coated on a sleeve or a doctor blade.