JPS61147261A - Electrostatic charge image developing charge donor - Google Patents

Abstract

PURPOSE:To impart proper negative chargeability by adding a metal complex of bis(salicylaldehyde)ethylenediimine or bis(slicylaldehyde)-trimethylenediimine at least on the surface of the charge donor. CONSTITUTION:A metal complex of bis(salicylaldehyde)ethylenediimine or bis(slicylaldehyde)trimethylenediimine is added at least on the surface of the electrostatic charge image developing charge donor, and it is typified by a Co(II) or Cu(II) or bis(salicylaldehyde)ethylenediimine, etc. Since the a metal complex of bis(salicylaldehyde)-ethylenediimine or bis(slicylaldehyde)-trimethylenediimine is stable thermally and against the lapse of time, when it is used, deterioration of performance due to long-time use, superior charge donor characteristics are retained, appropriate negative chargeability can be imparted to the toner, and accordingly, an image superior in thin line reproducibility can be obtained.

Description

[Detailed description of the invention] [Technical field to which the invention pertains] The present invention provides a method for imparting a charge to a toner used for developing an electrostatic image formed in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, etc. The present invention relates to a member, that is, a carrier, a sleeve, a doctor blade, and other conveyance regulators that apply a charge to toner for developing an electrostatic image, or other charge-imparting members.

[Description of prior art]

In the field of image forming technology, electrophotography includes a step of forming an electrostatic latent image (electrostatic latent image) and then visualizing it with a colored fine powder called toner;
Various electrostatic recording methods or electrostatic printing methods are conventionally known. For example, as an electrophotographic method, U.S. Patent Nos. 2 and 2
Various methods are described in Japanese Patent Publication No. 97,691, Japanese Patent Publication No. 42-23910, Japanese Patent Publication No. 43-24748, etc., but in general, various methods are described on a photoreceptor using a photoconductive substance. An electrostatic latent image is formed by the following means, and then the latent image is developed using a toner, and if necessary, after the toner image is transferred to a transfer material such as paper, heat, pressure, or solvent vapor is applied. etc. to obtain a copy.

The process of developing an electrostatic charge image (electrostatic latent image) is a process in which charged toner particles are attracted by electrostatic attraction and attached to the surface of a photoreceptor carrying an electrostatic charge image, thereby making the electrostatic charge image visible. be.

In general, methods for developing such electrostatic images using toner can be roughly divided into two methods: methods using a so-called two-component developer consisting of a mixture of l-toner and a carrier, and methods using a toner alone without being mixed with a carrier. There is a method using a one-component developer.

In the former method, toner and carrier are charged to different polarities by agitation and friction, and the charged toner visualizes an electrostatic charge image with opposite polarity, depending on the type of toner and carrier. Accordingly, there are the magnetic brush method using an iron powder carrier, the cascade method using beads and gears, the fur bluff method using fur, etc.

In the latter one-component developing method, toner particles are used in a sprayed state. Q Uder cloud method, contact development method (also called contact development method or toner development) 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 an electrostatic latent image [nl], but the toner particles are charged and flown toward the latent image surface by the electric field of the electrostatic latent image; There is also the MagneDry method, which develops by contacting the electrolatent image surface.

The toner applied to these various developing methods is a fine powder in which a colorant such as carbon black is dispersed in a binder resin made of a natural resin or a synthetic resin. For example, particles obtained by dispersing a colorant in a binder resin such as polystyrene and pulverizing the particles to about 1 to 30 μm are used as the toner. In fact, these ingredients further contain a magnetic material such as magnetite and are used as a magnetic toner.

As mentioned above, the toner used in the development method of the gods is
Depending on the polarity of the electrostatic charge image to be developed, a positive charge will be retained, but in order to make the l-ner retain a charge, the triboelectricity of the resin, which is a component of the toner, must be utilized. However, since the toner has a low chargeability with this method, the image obtained by development tends to be capricious and becomes unclear. Therefore, in order to impart the desired triboelectric chargeability to the toner, dyes, pigments, or a charge control M11 agent which increases the chargeability are added to the toner.

However, dyes and pigments or charge control agents added to these toners must be exposed to some extent on the surface of the toner in order to impart charging properties. Therefore, due to friction between the toners, collision with the carrier, friction with the electrostatic latent image carrier, etc., these additives may fall off from the surface of the toner (1-), contamination of the carrier, electrostatic latent image carrier, etc. For example, contamination of the photoreceptor belt or drum may occur. As a result, the charging property deteriorates, and as the number of durable sheets increases, the deterioration progresses, resulting in practical problems such as a decrease in image density, fine line reproducibility, and fogging.

Therefore, efforts have been made to improve the above-mentioned roughness by improving the affinity and dispersibility of the binder resin of the toner and dyes and pigments that impart chargeability or charge control agents. For example, there is a method of surface treating these additives in order to increase their affinity, but surface treatment often results in a decrease in chargeability. In order to improve the dispersibility, there is a method of mechanically applying strong air to finely disperse the toner, but this tends to reduce the proportion of the additive that appears on the toner surface and does not impart sufficient chargeability.

For these reasons, there are very limited number of charge-imparting additives that are sufficiently satisfactory for practical use, and only a small number of them have been put into practical use.

In order to obtain not only black and white images but also color images,
It is preferable for the additives added to toner to be colorless, but most of the dyes, pigments, and charge control agents conventionally used are dark-colored, so there are currently very few that are in practical use. And intensive research is continuing.

Therefore, it has been proposed that charge is not imparted by toner additives, but by means of conveyance regulation such as carriers, sleeves, doctor blades, or other charge imparting members.

Here, the charge imparting member refers to a member capable of imparting or auxiliary charge necessary for development to the toner upon contact with the toner. It is called Gunbu.

According to this method, it is not necessary to include almost any charging additive in the toner, so that the above-mentioned problems, for example, can be solved.
Since there is no contamination of the carrier, photoreceptor, etc., the charging property does not deteriorate during durability and the latent image is not disturbed. Furthermore, color toner can be easily charged.

However, in order to give a charge-imparting property to a charge-imparting member, it is necessary to have a strong charge-imparting member and to use an abrasive material that can be coated on these parts. No. Since the carrier is not replaced for a long period of time, sleeves and the like must be mechanically strong enough to make the copying machine unusable.

[Purpose of the invention]

An object of the present invention is to provide a charging part 4 which solves such problems.
'A.

Another 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 charge-imparting member whose performance does not deteriorate even after long-term use.

Still another object of the present invention is to provide a charging +1 force member that provides images with excellent fine line reproducibility and gradation.

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

[Structure of the invention]

The above-mentioned object of the present invention is achieved by providing a metal complex of bissalicylaldehyde ethylene diimine or a metal complex of bissalicylaldehyde trimethylene diimine on the surface of a charge-imparting member for developing an electrostatic image. be done.

That is, the present invention applies the above-mentioned compound to a carrier, a sleeve, a conveyor control device such as a doctor sprayer, or other charge-imparting member by coating or other means, or These charge monitoring members are molded using a moldable resin containing these compounds.

The present invention will be explained in detail below.

The present inventors have discovered that a metal complex of bissalicylaldehyde ethylenediimine or a metal complex of bissalicylaldehyde trimethylene diimine is thermally and temporally stable, and has strong charge-imparting properties when used in a charge-imparting member. I discovered what I was doing.

Typical specific examples of compounds used in the charging member of the present invention include the following, but are not limited thereto.

[Compound example]

(1) Bissalicylaldehyde ethylenediimine C
o(1'1) (2) Bissalicylaldehyde ethylenediimine C
u (n) (3) Biszarityl aldehyde trinotyle diimide
Co(TI) (4) Bissalicylaldehyde trinotylendiimine cu, (n) (5) Bissalicylaldehyde ethylenediimine Fθ
Chloride of (III) (6) Bissalicylaldehyde ethylenediimine C
o(ITI) chloride (cavity bissalicylaldehyde ethylenediimine Cr(
III) Chloride (8) Bissalicylaldehyde ethylenediimine F
Oxide of e(III) (9) Bissalicylaldehyde ethylenediimine C
o(m) oxide (10) bissalicylaldehyde ethylenediimine Cr(m) oxide (old) bissalicylaldehyde ethylenediimine re(
r+t) nitrate 02) bissalicylaldehyde ethylenediimine F
e(III) sulfonate (13) Bissalicylaldehyde ethylenediimine Ni (+I) (14) Bissalicylaldehyde ethylenediimine Zn (II) (15) Bissalicylaldehyde) rimethylenediimine Nj (1) ( I6) Biszalytylaldehyde trimethylene diimine Zn(H) (1η Chloride of bissalicylaldehyde trimethylenediimine Fe(in) (181 Chloride of biszalytylaldehyde trimethylenediimine co(in) q9) Chloride of biszalytylaldehyde trimethylene diimine Cr (Ill) (20) Nitrate of biszalytylaldehyde trimethylene diimine Co (Ill) These compounds are very stable and are synthesized by known methods.

For example, Compound Example (1) can be obtained as follows.

Ethylenediamine-hydrate 27 in ethanol]00m#
Dissolve and heat. A solution of 97 cobalt acetate (If) tetrahydrate dissolved in 401 πl of hot water is added to this. While heating the resulting mixed solution, 7.5
After adding 7, cool.

A brown bulky precipitate forms. This is filtered under suction in a nitrogen stream and dried in a cacz 2-person desiccator. Recrystallize from hot benzene. Obtained as reddish-brown needle-like crystals.

For example, Compound Example (2) can be obtained as follows.

Bis(salicylaldehydato)copper(II) 5.1 f
/ and a small amount of ethanol, and add ethylenediamine hydrate 22 to it. When this mixed solution is evaporated on a water bath, a dull green crystalline product precipitates out very easily. This is suction filtered and washed sequentially with ethanol and water.

Yield 93 section. Recrystallize with hot chloroform. Obtained as green crystals.

Further, Compound Example (5) can be obtained as follows.

Add excess concentrated hot water solution of ammonium chloride to the concentrated ethanol solution of camphor sulfone. If left as is, the desired chloride and aluminum chloride crystals will crumble and precipitate. The crystals are separated by filtration and mixed with as much water as is necessary to dissolve the ammonium chloride.

After collecting the CaC by suction filtration, it is dried in a 42-person desiccator.

Further, Compound Example (8) can be obtained as follows.

Salicylaldehyde 57 and 50% ethylenediamine 5f
iI and iron sulfate (IT) heptahydrate 67 are dissolved in 70 ml of water and heated. A dark brown reaction product precipitates. This is filtered under suction and dried using a clay plate. For purification, dissolve this dark brown powder in hot pyridine, filter it, and add ethanol to the P solution.

Brown crystals precipitate. This is filtered with suction and dried in a desiccator containing concentrated sulfuric acid.

These compounds may be used as they are after being dispersed in a solvent or dispersion medium such as methyl ethyl ketone or xylene.
However, it may also be used after being dispersed in a resin.

As such resin, common rubbers such as 1.1" IJ styrene, polyacrylic acid ester, polymethacrylic acid varnish, polyacrylonitrile, polyethylene and polybutadiene can be used. resins, polyesters, polyurethanes, polyamides, epoxy resins, rosins, polycarbonates, phenolic resins, chlorinated polymers, polyethylene, polypropylene, silicone resins, Teflon, and derivatives thereof, or copolymers and mixtures thereof.

Furthermore, various additives can be used as necessary. For example, ceramic powders such as phosphor powder, aluminum oxide, cerium oxide, and silicon carbide may be used as the filler.

In addition, a conductivity imparting agent such as carbon black or tin oxide may be added to adjust the conductivity.

Alternatively, a release agent such as a fatty acid metal salt or vinylidene fluoride may be used to prevent the spent toner from accumulating on the sleeve or carrier surface.

The amount of these materials applied to the carrier, sleeve, etc. needs to be controlled appropriately, but generally the amount of the material applied is 0.01 mW/lyn" to 10 mg.
/cm2, preferably 0.11nfl/cm”~2 m
g7am2 (it is better to be in the D range.

As the carrier used in the present invention, all known carriers can be used, and metals such as iron, nickel, aluminum, and copper, alloys, powders of metal compounds containing metal oxides, or Particles; glass, SiC, BaTi
Ceramic powders or particles such as O2, 8rTiO3, etc., whose surfaces have been treated with resin, resin powder, or resin powder that impregnates the magnetic material can be used.

Usually, 0.5 of the compound according to the present invention is added per 1 kg of carrier.
~3007, preferably 5~2007.

Furthermore, the sleeve used in the present invention can be made of metals such as iron, aluminum, stainless steel, and nickel, or non-metallic compounds such as alloys, ceramics, and plastics, which can be generally used as sleeves. .

The toner used in the present invention is effective for both non-magnetic and magnetic toners, and can be applied to any developing method that uses charged toner, whether it is a two-component development method or a -component development method. can. For example, the magnetic brush development method, the cascade development method, the fur brush development method, the so-called microtoning development method using magnetic material-containing resin powder as a carrier, the development method using resin powder as a carrier, the so-called jumping development method, or the non- This method includes a jumping development method that develops magnetic toner.

These toners need to be charged more efficiently,
Small amounts of charge-imparting substances, such as dyes, pigments, or so-called charge control agents, may be included as long as they do not adversely affect the practice of the invention, and may still include fluidizing agents such as colloidal silica, cerium oxide, titanic acid, etc. It may contain abrasives such as strontium and silicon carbide, and lubricants such as gold stearate and vinylidene fluoride. Further, it may contain a conductivity imparting agent such as carbon black or tin oxide.

Manufacturing methods in the present invention include the following methods.

For the gearia treatment, usual methods such as dousing the carrier core in a charged resin solution or dispersion solution in a tank, using a spray, or using a fluidizing bed are possible.

In addition, for the sleeve coat, use the same solution as above,
Coating can be done by any method such as dipping method, striping method, etc.

Furthermore, a charge imparting material may be contained in a moldable resin to form a carrier, a sleeve, or a doctor blade.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

[Example 1] Compound example (1) was added to 1007 ml of methyl ethyl ketone.
Dissolve and disperse, and add iron powder carrier (particle size: 250-]7
- ~400 mesh)] was dispersed and stirred for about 30 minutes in a ball mill.

This iron powder carrier mixture was dried to completely remove the solvent, and then light agglomerations were loosened.

I made a separate toner. The toner was prepared using conventional materials and by a conventional method. In particular, it is not necessary to include a charge imparting agent. Here, a toner with the following formulation was created.

Part by weight: 100 parts of styrene (trade name: D-125 manufactured by Nigel Chemical Co., Ltd.) The above materials were kneaded, crushed and classified to a particle size of 1 to 30 μm.
Align.

This toner and the carrier were mixed in a weight ratio of 10=100 to prepare a developer. When the triboelectricity of the toner of this developer was measured by the blow-off method, it was -8.8 μc/q.

When this developer was used to produce an image on a Canon Np-5000'47 photocopier, there was no change in image density even in durability test 1 of 50,000 sheets, with good fine line reproducibility and good gradation. Met. There was still no fog.

[Example 2] Polymethyl methacrylate) resin 10
(1?) was dissolved and 507 grams of Compound Example (2) was further mixed therein. This was mixed with the same iron powder carrier as in Example 1.
- By drying, a gear carrier with a charge imparting member was obtained.

Hereinafter, in the same manner as in Example 1, the toner and the carrier were mixed to form a developer and 1-. The toner charge of this developer was -10.1 .mu.C/g.

Well, when I produced an image in the same way as in Example 1, I found that
50. (Even in a durability test of 100 sheets, the image density, fine line reproducibility, and gradation were as good as the initial ones, and there was no fog.

[Example: 3] Polymethyl methacrylate-1, resin 1 in 7 ml
Prepare a bath solution in which 00f is dissolved and 507% of Compound Example (3) is mixed. A developing sleeve (made of stainless steel) for Canon NP-400RE was tipped into this solution, and O was added to the sleeve-42.
I wore a coat from Ro2. Set this sleeve into the original developing machine.

)・Gner is made using the general kneading and pulverizing method according to the following recipe.

Part by weight Poly(styrene-butyl methacrylate-1.) 10
0 parts MW2 300,000 Mold release agent (trade name PE-130 manufactured by Hoechst Co., Ltd.) 4 parts Magnetic powder (trade name BT, -200: manufactured by Titanium Kogyo Co., Ltd.)
Make 60 copies 1. Use toner and adjust the particle size to 11-30μ.

Using this L-ner, an image reproduction durability test was conducted with Canon NP-4QQRE. 50,000 copies in existence for 1 year.
There was no change in the image from the beginning, fine line reproducibility and gradation were good, and there was no fogging.

I measured the surface potential of the sleeve.36
It was confirmed that the toner with V was completely negatively charged.

[Example 4] Polycarbonate 1/resin 807 was dissolved in kiln 11.
~A solution was prepared by further mixing 209 compounds of Compound Example (4).

In this solution, dip the developing sleeve (aluminum group) of the developing machine of the Canon N PC-20 blue cartridge, and add 0.11n91/cm"~0.
, 5 mW/lyn" coating. This sleeve was used in the original developing machine for 7 l-1~.

On the other hand, l.ner was prepared according to the following recipe.

Part by weight Poly(styrene-butyl methacrylate) 100
Part M~v=150, (100 Ni-type agent (trade name PK-130. Manufactured by Hoechst)
Part 4 Blue layer coloring agent (phthalocyanine Kisaragi)
Make 6 copies and adjust the particle size of the toner from 1μ to 30μ. Using this toner, a PC-20 was modified to be capable of reversal development using a developing machine with a sleeve attached, and durable images were produced. As a result, there is no change in the image when the toner runs out, and a clear blue image with good fine line reproducibility and gradation is obtained. Further, the surface potential of the toner on the sleeve was measured and found to be -42V, indicating that it was negatively charged.

[Summary of effects of the invention]

According to the present invention, it is not necessary to contain almost any additives that affect chargeability in the toner, so there is no possibility of contaminating the carrier or the photoreceptor, and therefore there is no possibility that the chargeability will decrease during durability or that the latent image will be disturbed. Strong.

Furthermore, since the metal complexes of bis-salicylaldehyde ethylene diimide and metal complexes of bis-salicylaldehyde trimethylene diimide used in the present invention are thermally and temporally stable, when these compounds are used, long-term A charge imparting member whose performance does not deteriorate during use can be obtained. Furthermore, these compounds have excellent chargeability,
When development is performed using a charge imparting member using these compounds, images with excellent fine line reproducibility and gradation can be obtained.

Furthermore, according to the present invention, it is not necessary to contain almost any additive in the first colorant, so that color images with excellent colors can be formed.

Claims (1)

[Claims] A charge-imparting member comprising a metal complex of bissalicylaldehyde ethylene diimine or a metal complex of bissalicylaldehyde trimethylene diimine on at least its surface.