JPH01259387A - Triboelectrostatic charge imparting member - Google Patents

Abstract

PURPOSE:To enable excellent positive electrostatic charge impartation and the formation of a sharp color toner image with a triboelectrostatic charging member which imparts the required charge to a toner by coming into contact with the toner by having a specific metal salt of indole carboxylic acid and metal salt of quinoline carboxylic acid. CONSTITUTION:The triboelectrostatic charge imparting member which is capable of stably imparting the excellent positive chargeability and of forming the sharp color image is obtd. if said member is so formed as to have at least one kind of the metal salt of the indole carboxylic acid expressed by the formula I and the metal salt of the quinoline carboxylic acid expressed by the formula II on the surface. In the formulas, R1, R2: hydrogen atom, alkyl group of 1-8C or alkoxy group; R3: hydrogen atom or alkyl group of 1-8C; M: metal atom selected from Zn, Cr, Co, Ni, and Fe.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a triboelectric charging member having the function of imparting triboelectric charge to toner for developing electrostatic images used in electrophotography, electrostatic printing, etc. The present invention relates to carriers that impart triboelectric charge to toner, conveyance regulating members such as sleeves and doctor blades, and other triboelectric charge imparting members.

Conventionally, the method of developing an electrostatic image using toner, as disclosed in JP-A No. 61-1.47261, has been roughly divided into so-called two-dimensional methods in which toner and carrier are mixed. There are two methods: using a component-based developer, and using a one-component developer where the toner is used alone without being mixed with a carrier.
There is a way to do this. In the above method, toner and carrier are stirred and rubbed to charge each other with different polarities, and an electrostatic charge image having opposite polarity is visualized by the charged toner, and the type of toner and carrier is Depending on the method, there are a magnetic brush method using an iron powder carrier, a cascade method using a bead carrier, a fur brush method, etc.

The latter one-component development method includes a powder cloud method in which toner particles are sprayed, a contact development method (also referred to as touchdown development) in which toner particles are brought into direct contact with the electrostatic latent image surface for development, and There is an induction development method in which a magnetic conductive toner is brought into contact with an electrostatic latent image surface.

Toners applicable to these various development methods include:
Fine powder is used in which a coloring agent such as carbon black is dispersed in a binder resin made of natural or 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. Further, a toner containing these components further contains a magnetic material such as magnetite is used as a magnetic toner.

As mentioned above, toners used in various developing methods are:
Depending on the polarity of the electrostatic charge image to be developed, a positive or negative charge is retained, and in order to cause the toner to retain a charge, it is also possible to utilize the triboelectricity of the resin that is a component of the toner. In this method, since the toner has a low chargeability, the image obtained by development tends to be foggy and unclear. Therefore, in order to impart desired triboelectric chargeability to the toner, dyes, pigments, or charge control agents that impart 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 toner surface in order to impart charging properties. Therefore, these additives fall off from the toner surface due to friction between the toners, collision with the carrier, friction with the electrostatic latent image holder, etc.
Contamination of the carrier, etc., and contamination of the electrostatic latent image holding member 1, such as the photoreceptor belt or drum, etc. occur. As a result, charging performance deteriorates, and as the number of running sheets increases, deterioration progresses, image density decreases, and fine line reproducibility deteriorates.
Fog and other problems become a practical problem.

Therefore, attempts have been made to improve the above-mentioned problems 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 to increase their affinity, but surface treatment often results in a decrease in chargeability. Although there is a method of finely dispersing the toner, the proportion of the additive appearing on the surface of the toner decreases and there is a tendency that sufficient chargeability cannot be imparted.

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

Also, in order to obtain not only black and white images but also color images,
It is preferable that the additives added to toner be colorless, but most of the dyes, pigments, and charge control agents conventionally used are dark-colored, and at present, very few of them are in practical use. .

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

Here, the triboelectric charge imparting member refers to a member that can contact the toner and impart or auxiliary charge necessary for development, and hereinafter these will be collectively referred to as the triboelectric charge imparting member.

However, conventional triboelectric charging members are not only incapable of stably imparting excellent positive or negative chargeability to toner, but also difficult to form clear color toner images.

One object of the present invention is to provide a triboelectric charge imparting member that overcomes the conventional drawbacks and imparts excellent positive chargeability, and a further object is to provide a triboelectric charge imparting member that is suitable for forming vivid color toner images. It is an object of the present invention to provide a triboelectric charge imparting member which provides an image quality equivalent to that of an initial image even under environmental changes or even after continuous copying.

Structure As a result of intensive research to achieve the above object, the inventor of the present invention found the following formula - (blank space below) (However, R2 and R2 may be the same or different, and may be a hydrogen atom, an alkyl group of 01 to C, or represents an alkoxy group of 01 to C1l, R7 represents a hydrogen atom or an alkyl group of 01 to C8, and M is Zn, Cr, Co, N
Represents a metal atom selected from i and Fe. ) and at least one kind selected from the group consisting of indole carboxylic acid metal salts represented by the formula ■: (where R, , R, and M are the same as the formula ■); It has been found that the above object can be achieved by providing a positive polarity triboelectric charging member having at least the surface thereof.

The above-mentioned metal salt may be used as it is by being dispersed in a solvent or dispersion medium, or may be used by being dispersed in a resin. Common resins can be used as such resins, such as polystyrene, polyacrylic ester,
Polymethacrylic acid ester, polyacrylonitrile, rubber resins such as polyisoprene and polybutadiene, polyester, polyurethane, polyamide, epoxy resin,
These include rosin, polycarbonate, phenolic resin, chlorinated paraffin, polyethylene, polypropylene, silicone resin, Teflon, and derivatives thereof, or copolymers and mixtures thereof.

The triboelectric charge imparting member of the present invention can be obtained by applying the above coating liquid to the base material of the triboelectric charge imparting member by dipping, spraying, brushing, etc. and drying it. Further, the resin in which the above compound is dispersed may be molded as it is to form the triboelectric charging member. In this case, inorganic fillers such as silica, carbon, carbon fiber, glass fiber, etc. may be included in order to enhance reinforcement and anti-wear effects.

All known carriers can be used as the base material for the triboelectrification member in the form of a carrier, including iron, nickel,
Particles of metals or alloys such as aluminum, metal compounds such as metal oxides, and ceramic particles such as glass and silicon carbide are used. Furthermore, as the base material of the frictional charging member in the form of a sleeve or doctor blade, conventionally used sleeves and doctor blades are used, such as metals or alloys such as iron, aluminum, and stainless steel, and non-metallic compounds such as plastic and rubber. can.

The present invention is based on the knowledge that after repeated various experiments, it was confirmed that by using the metal salt of the above-mentioned formula in the triboelectric charging member, a high positive charge can be obtained and a good copy can be obtained. .

Specific examples of such metal salts suitable for use in the present invention include the following.

Na various works-dai Ha
Nα
Various - Shoichi Inu Na Jl
l-zo' dog NQ purchase-iijii Nα skin-zo nishaku Na
Note that these metal salts can be easily synthesized by known methods. For example, in the case of a metal salt of formula I, an aqueous solution of the corresponding indole carboxylic acid is synthesized, or a metal salt of formula In this case, it can be easily obtained by neutralizing an aqueous solution of the corresponding quinoline carboxylic acid with an alkali, and adding thereto an aqueous solution of the corresponding metal salt for metal exchange. An example of its synthesis is shown below.

Synthesis Example 1 0.11 Ilole of indole carboxylic acid was added to 50 m of water (
ZnSO4.
Add 0.05 mole of 7H20. The solution became cloudy, and zinc indolecarboxylic acid salt (NQI-
(1) metal salt) is obtained.

Synthesis Example 2 A zinc salt of quinolinecarboxylic acid (metal salt of Nα■-(1)) was obtained as a white precipitate in the same manner as in Synthesis Example 1, except that quinolinecarboxylic acid was used instead of indolecarboxylic acid.

The toner used in combination with the triboelectric charge imparting member of the present invention as described above may be any toner used as a conventional electrophotographic toner. That is, the toner may be either magnetic or non-magnetic. More specifically, the toner is a colored fine particle containing a coloring agent in a binder resin,
If necessary, these toners may contain magnetic powder.Furthermore, these toners may contain a small amount of charge imparting agent, such as dyes and pigments, charge control agents, etc., in order to impart more efficient charge. It's good, but you only need a much smaller amount than before. If necessary, fluidizing agents such as colloidal silica, titanium oxide,
It may also contain metal oxides such as aluminum oxide, abrasives such as silicon carbide, lubricants such as fatty acid metal salts, and the like.

Hereinafter, the present invention will be explained in more detail with reference to the following examples, but the present invention is not limited thereto. All parts are parts by weight.

Example 1 50g of NαI-(1) metal salt was dissolved and dispersed in toluene IQ, and this was added to a spherical ferrite carrier (average particle size 10
0 μm) was coated onto 5 kg using a fluidized bed coating device.

The toner was prepared from the following composition.

Styrene-〇-butyl methacrylate 100 parts Carbon black 10 parts The mixture having the above composition was mixed, pulverized, and classified to obtain a black toner having a particle size of 5 to 20 μm. Three parts of this toner was added to 100 parts of the carrier and mixed to obtain a developer. Next, an electrostatic charge image of 1800 V was formed on an organic photoreceptor using the above developer using Ricoh Co., Ltd. FT4060, and a copy test was conducted, and a good image was obtained. This image remained unchanged even after continuous copying of 10,000 copies.

Furthermore, when the toner charge was measured using the blow-off method, the initial charge amount was +20.5 μc/g, and the toner charge amount after running 100,000 sheets was +19.1 μc/g, which was almost the same as the initial value. There wasn't.

In addition, under a high temperature and high humidity environment of 35°C and 90% RH, and at 10°C.
Even at a low temperature and low humidity of 15% RH, images with almost no difference from normal humidity were obtained.

Example 2 & I- Using the metal salt of (3), as in Example 1,
I created a coat carrier.

A toner was prepared using the following composition.

Styrene-n-butyl methacrylate 100 parts Polypropylene 5 parts C.1, Pigment Blue 15 5 parts The mixture having the above composition was kneaded, pulverized, and classified to obtain a blue toner having a particle size of 5 to 20 μm. This toner was added to 100 parts of the carrier,
4 parts were added and mixed to obtain a developer. Next, add the above developer to
Using FT4060 manufactured by Ricoh Co., Ltd., one-80%
When an electrostatic charge image of 0.0 cm was formed and a copy test was performed, a good blue image was obtained. This image remained unchanged even after 100,000 copies were made.

Furthermore, when the toner charge was measured using the blow-off method, the initial charge amount was +20.6 μc/g, and the toner charge amount after running 10,000 sheets was +21.2 μc/g.
There was almost no difference from the initial value.

In addition, under a high temperature and high humidity environment of 35°C 90% R)I and 10
Even at a low temperature and low humidity of 15% RH, images with almost no difference from normal humidity were obtained.

Example 3 100 g of silicone resin was dissolved in toluene IQ, and 50 parts of a metal salt of NαI-(4) was further mixed therein.

This was coated on a spherical ferrite carrier in the same manner as in Example 1.

A toner was prepared using the following composition.

Styrene-2-ethylhexyl acrylate copolymer 1
00 part C, 1, pigment blue 15
Part 2 C, 1, Pigment Yellow 17
5 parts The mixture having the above composition was kneaded, pulverized, and classified to obtain a green toner having a particle size of 5 to 20 μm. Adding 2.5 parts of this toner to 1.00 parts of the carrier,
The mixture was mixed to obtain a developer. Next, when the developer was subjected to an image test using FT4060 manufactured by Ricoh, a good green image was obtained. This image remained unchanged even after continuous copying of 100,000 copies.

Furthermore, when the toner charge was measured using the blow-off method, the initial charge amount was +22.6 μc/g, and the toner charge amount after running 100,000 sheets was +20.9 μc/g.
There was almost no difference from the initial value.

In addition, under a high temperature and high humidity environment of 35°C and 90% RH, and at 10°C.
Even at a low temperature and low humidity of 15% RH, images with almost no difference from normal humidity were obtained.

Example 4 100 g of MMA resin was dissolved in toluene IQ, and 50 g of a metal salt of NαI-(5) was further mixed therein.

This was coated on a spherical ferrite carrier in the same manner as in Example 1.

A toner was prepared using the following composition.

Polyester resin 100 parts C, 1
, Pigment Red 81 5 parts C, I, Pigment Red 48 3 parts The mixture having the above composition was mixed, crushed and classified to obtain a red toner having a particle size of 5 to 20 μm. 2.5 parts of this toner was added to 100 parts of the carrier and mixed to obtain a developer. Next, a copy test was conducted using the above developer using FT4060 manufactured by Ricoh Co., Ltd. to form an electrostatic charge image of -800 V on an organic photoreceptor, and a good red image was obtained. This image did not change even after continuous copying of 10,000 copies.

Furthermore, when the toner charge was measured using the blow-off method, the initial charge amount was +23.5 μc/g, and the toner charge amount after running 100,000 sheets was +21.8 μc/g.
There was almost no difference from the initial value.

In addition, under a high temperature and high humidity environment of 35°C 90% R)I and 10
Even at a low temperature and low humidity of 15% RH, images with almost no difference from normal humidity were obtained.

Example 5 Metal salt sog of Nll I-(1) in toluene IQ
is dissolved and dispersed, and a toner conveying member (2) shown in FIG.
) was coated by dipping and set in the developing section.

Silicon carbide (particle size 2μ) was added to 100 parts of the toner of Example 1.
m) 3 parts were sufficiently stirred and mixed in a speed kneader to obtain a silicon carbide-added toner.

When this added toner was placed in a developing device as shown in FIG. 1 and copies were made, good images were obtained. This image remained unchanged even after 50,000 copies were continuously copied.

To explain this developing method, as shown in FIG. 1, the toner 6 contained in the toner tank 7 is forcibly brought to the sponge roller 4 by the stirring blade 5, and the toner is supplied to the sponge roller 4. As the sponge roller rotates in the direction of the arrow, the toner taken into the sponge roller 4 is transported to the toner conveying member 2, where it is rubbed and electrostatically or physically adsorbed, and the toner conveying member 2 moves in the direction of the arrow. The elastic blade 3 rotates strongly to form a uniform thin layer of toner and is charged by friction. Thereafter, the toner is transported to the surface of the electrostatic image carrier 1 that is in contact with or in close proximity to the toner transport member 2, and the electrostatic image is developed.

The electrostatic charge image is created by charging the organic photoreceptor with a negative DC voltage of -800V and then exposing it to light to form a latent image, which is then developed.

In addition, in order to measure the specific charge amount (Q/M) of the toner on the toner conveying member, the toner on the toner conveying member is sucked through a Faraday cage equipped with a filter layer on the exit side, and is trapped in the Faraday cage. When the Q/M was measured using a suction method specific charge measurement device for measuring the specific charge of the toner, it was confirmed that the toner was sufficiently charged as +10.7 μc/g.

Also, the amount of charge during running of 50,000 sheets is +9.5μc/
There was almost no difference between g and the initial value.

Furthermore, image quality equivalent to that under normal humidity was obtained even under high humidity and low humidity conditions.

Example 6 100 g of a silicone resin was dissolved in 12 toluene, and 50 g of a metal salt of NαI-(8) was mixed therein.

This was spray coated on the toner conveying member (2) shown in FIG. 1, and the toner conveying member (2) was set in the developing section.

A toner was prepared using the following composition.

Styrene-2-ethylhexyl acrylate copolymer 1
00 parts polyethylene
5 parts C, 1, pigment red 81
Part 5 C, 1, Pigmen 1-Red 48
Three parts of the mixture having the above composition were kneaded, pulverized, and classified to obtain a red toner having a particle size of 5 to 20 μm. To 100 parts of this toner, 2 parts of silicon carbide (particle size: 2 μm) and 0.1 part of hydrophobic colloidal silica were sufficiently stirred and mixed in a speed kneader to obtain a silicon carbide/silica-added toner.

When this toner was placed in the developing section shown in FIG. 1 and a copy test was conducted in the same manner as in Example 5, a clear and good red image was obtained.

In addition, when Q/M was measured in the same manner as in Example 5, it was +8.3 μc/g at the initial stage and +7.1 after running 50,000 sheets.
μc/g, and there was almost no change.

Furthermore, image quality equivalent to that at normal humidity was obtained under both high and low humidity.

Example 7 50% of N11I-(10) metal salt in toluene IQ
g was dissolved and dispersed, and this was spray coated onto an elastic blade (made of stainless steel) shown in FIG. 1, which was set in the developing section.

When a copy test was conducted using the toner of Example 6 in the same manner as in Example 5, clear and good images were obtained.

In addition, when Q/M was measured in the same manner as in Example 5, the initial value was +7.5 μC/E, and the value after running 50,000 sheets was +6.8 μC/E.
c/g, and there was almost no change.

Furthermore, image quality equivalent to that at room temperature was obtained even under high humidity and low humidity.

Example 8 100 g of silicone resin was dissolved in toluene IQ, and 50 parts of a metal salt of NaI-(12) was mixed therewith.

This was spray coated onto an elastic blade (made of stainless steel) shown in FIG. 1, and set in the developing section.

When an image test was conducted in the same manner as in Example 5 using the toner of Example 6, a clear and good red image was obtained.

In addition, when Q/M was measured in the same manner as in Example 5, it was +10.3 μc/g at the initial stage and +9.1 after running 50,000 sheets.
μc/g, and there was almost no change.

Furthermore, even under high temperature and low humidity conditions, image quality equivalent to that under normal humidity conditions was obtained.

Example 9 50 parts of metal salt of NaI-(14) and 10 parts of silicone resin
0 parts, heated and melted, and the molded resin blade was attached to the elastic blade 3 shown in FIG.

A toner was prepared using the following composition.

Epoxy resin 100 parts Polypropylene 5 parts C.1, Pigment Blue 15 2 parts C.1, Pigment Yellow 17 5 parts The mixture having the above composition was mixed, pulverized, and classified to obtain a green toner having a particle size of 5 to 20 μm. For 100 parts of this toner, silicon carbide (particle size 2 μm
) and 0.1 part of zinc stearate fine powder were added thereto and thoroughly stirred and mixed using a speed kneader to obtain a toner containing silicon carbide and Zn stearate.

When a copy test was conducted using this toner in the same manner as in Example 5, a clear and good green image was obtained.

In addition, when Q/M was measured in the same manner as in Example 5, the initial value was +11.1 μc/g, and the value after running 50,000 sheets was +10.
It was 3 μc/g, and there was almost no change.

Furthermore, image quality equivalent to that at room temperature was obtained even under high humidity and low humidity.

Example 1O A resin blade was prepared in the same manner as in Example 7 using a metal salt of Na I-(i6). When a copy test was conducted in the same manner as in Example 5 using the silicon carbide/silica-added toner of Example 6, a clear and good red image was obtained.

In addition, when Q/M was measured in the same manner as in Example 5, it was +10.7 μc/g at the initial stage and +9.8 after running 50,000 sheets.
μc/g, and there was almost no change.

Furthermore, image quality equivalent to that at room temperature was obtained even under high humidity and low humidity.

Example 1I 50 parts of the metal salt of Na I-(17), 100 parts of polystyrene resin, and 30 parts of carbon black were mixed and melted by heating to form a resin blade.

A toner was prepared using the following composition.

Styrene-〇-butyl acrylate 100 parts Polyethylene 5 parts Carbon black 5 parts Charge control agent (grossine dye) 0.5 parts Mixture of the above composition was mixed, crushed, separated, and 5 to 20 μm thick.
A toner having a particle size of . To 100 parts of this toner, 3 parts of silicon carbide (particle size: 2 μm) and 0.5 parts of titanium oxide were sufficiently stirred and mixed in a speed kneader to obtain a toner containing silicon carbide and titanium oxide.

When a copy test was conducted using this toner in the same manner as in Example 5, a clear and good black image was obtained.

In addition, when Q/M was measured in the same manner as in Example 5, it was +9.4 μc/g at the initial stage and +12.1 after running 50,000 sheets.
μc/g, and there was almost no change.

Furthermore, image quality equivalent to that at normal humidity was obtained under both high and low humidity.

Example I2 50 parts of metal salt of NaI-(19), 100 parts of MMA (polymethyl methacrylate) resin and 30 parts of calcium carbonate
A resin blade was prepared in the same manner as in Example 11.

The toner was prepared from the following composition.

Polyester resin 100 parts Polyethylene 7 parts C.1, Pigment Blue 15 5 parts The mixture having the above composition was mixed, pulverized, and classified to obtain a toner having a particle size of 5 to 20 μm.

For 100 parts of this toner, silicon carbide (particle size 2 μm) 3
1 part and 0.5 parts of titanium oxide were sufficiently stirred and mixed in a speed kneader to prepare a toner containing silicon carbide and titanium oxide.

When a copy test was conducted using this toner in the same manner as in Example 5, a clear and good blue image was obtained.

Further, when Q/M was measured in the same manner as in Example 5, it was +9.4 μc/g at the initial stage and +8.9 μc/g after 50,000 sheets, and there was almost no change in Q/M.

Furthermore, image quality equivalent to that at normal humidity was obtained under both high and low humidity.

Example 13 A coated carrier was obtained in the same manner as in Example 1 except that Nan-(i) was used as the metal salt.

A developer was prepared using this coated carrier in the same manner as in Example 1, and a copy test was conducted. A good black image was obtained, and this image did not change even after 100,000 copies were continuously copied.

In addition, the initial charge amount of the toner is +17.7μc/g,
The amount of charge in running 100,000 sheets is +18.3μc/
g, there was almost no difference from the initial value. Also, 35℃90
Even under a high temperature and high humidity environment of %RH and a low temperature and low humidity environment of 10° C. and 15% RH, images with almost no difference from normal humidity were obtained.

Example 14 A coated carrier was obtained in the same manner as in Example 1, except that Ha-(3) was used as the metal salt.

A developer was prepared using this coated carrier in the same manner as in Example 2, and a copy test was conducted. A good blue image was obtained, and this image did not change even after 100,000 copies were continuously copied.

Further, the initial charge amount of the toner was +17.1 μc/g.

The amount of charge on the toner after running 100,000 sheets was +17.
It was 8 μc/g, which was almost no difference from the initial value.

In addition, under a high temperature and high humidity environment of 35°C and 90% RH, and at 10°C.
Even at a low temperature and low humidity of 15% RH, images with almost no difference from normal humidity were obtained.

Example 15 A coated carrier was obtained in the same manner as in Example 3 except that Nan-(4) was used as the metal salt.

A developer was prepared using this coated carrier in the same manner as in Example 3, and a copying test was conducted. A good green image was obtained, and this image did not change even after 100,000 copies were continuously copied.

In addition, the initial charge amount of the toner is +21.3μc/g,
The amount of charge in running 100,000 sheets is +20.7μe/
g, there was almost no difference from the initial value. Also, 35℃90
Even under a high temperature and high humidity environment of %RH and a low temperature and low humidity environment of 10° C. and 15% RH, images with almost no difference from normal humidity were obtained.

Example 16 A coated carrier was obtained in the same manner as in Example 4, except that a metal salt of 80 m-(s) was used.

A developer was prepared using this coated carrier in the same manner as in Example 4, and a copy test was conducted, and a good red image was obtained. This image remained unchanged even after continuous copying of 100,000 copies.

Further, when the charge of the toner was measured by a blow-off method, the initial charge amount was +22.6 μc/g, and the charge amount after running 100,000 sheets was +21.8 μc/g, which was almost not different from the initial value. Further, even under a high temperature, high humidity environment of 35° C., 90% RH, and a low temperature, low humidity environment of 10° C., 15% RH, images with almost no difference from normal humidity were obtained.

Example 17 A toner transport member was dip-coated in the same manner as in Example 5 using a metal salt of 80 m-(i), and set in the developing section of the apparatus shown in FIG.

A copy test was similarly conducted using the silicon carbide-added toner prepared in Example 5, and good images were obtained. This image remained unchanged even after 50,000 copies were continuously copied.

In addition, when Q/M was measured in the same manner as in Example 5, the initial value was +8.8 μc/g, and after running 50,000 sheets, it was +8.1 μc/g.
c/g, and there was almost no change.

Furthermore, image quality equivalent to that at normal humidity was obtained even under high temperature and low humidity conditions.

Example 18 A toner conveying member was dip-coated in the same manner as in Example 6 using a metal salt of 80m-(2) and set in the developing section of the apparatus shown in FIG.

Hereinafter, a copy test was conducted in the same manner as in Example 5 using the silicon carbide/silica-added toner prepared in Example 6, and a clear and good red image was obtained.

In addition, when Q/M was measured in the same manner as in Example 5, the initial value was +8.3 μc/g, and after running 50,000 sheets, it was +7.4 μc/g.
e/g, and there was almost no change.

Furthermore, image quality equivalent to that under normal humidity was obtained even under high humidity and low humidity conditions.

Example 19 An elastic blade was spray-coated in the same manner as in Example 7 using &II-(6) as the metal salt, and set in the developing section of the apparatus shown in FIG.

Hereinafter, a copy test was conducted in the same manner as in Example 5 using the silicon carbide/silica-added toner prepared in Example 6, and a clear and good red image was obtained.

In addition, when Q/M was measured in the same manner as in Example 5, the initial value was +9.5 μc/g, and after running 50,000 sheets, it was +8.9 μc/g.
c/g, and there was almost no change.

Furthermore, image quality equivalent to that under normal humidity was obtained even under high humidity and low humidity conditions.

Example 20 An elastic blade was spray-coated in the same manner as in Example 8 using NαII-(14) as the metal salt, and set in the developing section of the apparatus shown in FIG.

Hereinafter, a copy test was conducted in the same manner as in Example 5 using the silicon carbide/silica-added toner prepared in Example 6, and a clear and good red image was obtained.

In addition, when Q/M was measured in the same manner as in Example 5, the initial value was +6.5 μc/g, and after running 50,000 sheets, it was +6.1 μc/g.
c/g, and there was almost no change.

Furthermore, image quality equivalent to that at normal humidity was obtained even under high temperature and low humidity conditions.

Example 21 A resin blade was molded in the same manner as in Example 9 using N11I[-(5) as the metal salt, and this was set at the elastic blade 3 of the apparatus shown in FIG. A copy test was conducted in the same manner as in Example 5 using the toner containing silicon carbide and Zn stearate prepared in Example 9, and a clear and good green image was obtained.

In addition, when Q/M was measured in the same manner as in Example 5, the initial value was +11.2 μc/g, and after running 50,000 sheets, it was +10.
It was 6 μc/g, and there was almost no change.

Furthermore, image quality equivalent to that at room temperature was obtained even under high and low humidity conditions.

Example 22 A resin blade was produced in the same manner as in Example 7 using the metal salt of Nαn-(13). When a copy test was conducted in the same manner as in Example 5 using the silicon carbide/silica-added toner of Example 6, a clear and good red image was obtained.

In addition, when Q/M was measured in the same manner as in Example 5, it was +10.3 μc/g at the initial stage and +9.6 after running 50,000 sheets.
μc/g, and there was almost no change in it.

Furthermore, image quality equivalent to that at room temperature was obtained even under high temperature and low humidity conditions.

Example 23 A resin blade was prepared in the same manner as in Example 11 using Nα■-(16) as the metal salt.

A copy test was conducted in the same manner as in Example 5 using the toner containing silicon carbide and titanium oxide prepared in Example 11, and a clear and good black image was obtained.

In addition, when Q/M was measured in the same manner as in Example 5, it was +12.3 μc/g at the initial stage and +11.
It was 8 μc/g, and there was almost no change.

Furthermore, image quality equivalent to that at room temperature was obtained even under high and low humidity conditions.

Example 24 A resin blade was produced in the same manner as in Example 12 using N1II[-(17) as the metal salt.

A copy test was conducted in the same manner as in Example 5 using the toner containing silicon carbide and titanium oxide prepared in Example 12, and a clear and good blue image was obtained.

In addition, when Q/M was measured in the same manner as in Example 5, the initial value was ÷8.7 μC/, and the value after running 50,000 sheets was +8.1 μC/.
c/g, and there was almost no change.

Furthermore, image quality equivalent to that under normal humidity was obtained even under high humidity and low humidity conditions.

Effects As explained above, according to the present invention, images with the same quality as the initial image can be obtained even after continuous copying, there is no change in the amount of charge, there is little environmental variation, and there is good chargeability even in high temperature and high humidity. can be shown.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram of a developing device used in an example of the present invention. 1... Electrostatic latent image carrier 2... Toner conveying member 3.
...Elastic blade 4...Sponge roller 5...
- Stirring blade 6... Toner 7... Toner tank

Claims (1)

[Claims] 1. The following general formula I: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R_1 and R_2 may be the same or different, and may be a hydrogen atom, an alkyl group of C_1 to C_8, or a C_1 to C_
8 represents an alkoxy group, R_3 is a hydrogen atom or C_
represents an alkyl group of 1 to C_8, and M is Zn, Cr
, Co, Ni and Fe. ) Indolecarboxylic acid metal salts and general formula II: ▲Mathematical formulas, chemical formulas, tables, etc.▼ (However, R_1, R_2, M are the same as general formula I) From the group consisting of quinolinecarboxylic acid metal salts shown by A triboelectric charge imparting member for positive polarity, characterized in that it has at least one selected type on at least its surface.