JPH05165260A - Positive triboelectrification donating member for electrostatic charge image development - Google Patents

Abstract

PURPOSE:To obtain a triboelectrification donating member which gives excellent positive electrification property by incorporating a specified fluorine-contg. quaternary ammonium salt compd. into at least the surface of the member. CONSTITUTION:The triboelectrification donating member contains a fluorine- contg. quaternary ammonium salt compd. in at least the surface thereof. In formula, X is -SO2- or -CO-, R1-R4 are H, lower alkyl groups of 1-10 carbon number or aryl groups, and (n) and (m) are positive integers. This compd. may be dispersed in a solvent or dispersion medium for use, or dispersed in a resin. The resin to be used is, for example, polystyrene, polyacrylate, etc. The coating liquid thus obd. is applied on a base body by dipping, spraying, or brush coating, and dried to obtain the triboelectrification donating member. Or, the resin in which this compd. is dispersed may be molded to obtain the triboelectrification donating member.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a triboelectrification imparting member having a function of imparting triboelectrification to an electrostatic charge image developing toner used in electrophotography, electrostatic printing, etc. The present invention relates to a carrier for imparting positive triboelectrification, a transport restricting member such as a sleeve or a doctor blade, or another triboelectrification imparting member and a one-component developing device for positively charged toner having such an electrification imparting member.

[0002]

2. Description of the Related Art Conventionally, as disclosed in JP-A-61-147261, a method of developing an electrostatic charge image by using toner is roughly classified into so-called two-component system development in which toner and carrier are mixed. There is a method of using a developer, and a method of using a one-component developer which is used alone as a toner without being mixed with a carrier.

In the above-mentioned method, the toner and the carrier are agitated and frictionally charged so that they are charged to different polarities, and the electrostatically charged image having the opposite polarity is visualized by the charged toner. Depending on the type of carrier, magnet brush method using iron powder carrier,
There are a cascade method using a bead carrier, a fur brush method, and the like.

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

As the toner applied to these various developing methods, fine powder in which a colorant such as carbon black is dispersed in a binder resin made of natural resin or synthetic resin is used. For example, particles in which a colorant is dispersed in a binder resin such as polystyrene and finely pulverized to about 1 to 30 μm are used as toners. Further, a magnetic toner such as those containing a magnetic material such as magnetite is used as a magnetic toner.

As described above, the toner used in various developing methods has a positive or negative charge depending on the polarity of the electrostatic image to be developed. To retain the electric charge in the toner, it is possible to utilize the triboelectric charging property of the resin which is a component of the toner, but in this method, the toner charging property is small, so the image obtained by development is easily fogged and is not clear. Will be things. Therefore, in order to impart a desired triboelectric chargeability to the toner, a dye, a pigment or a charge control agent which imparts the chargeability is added.

However, the dye / pigment or charge control agent added to these toners must be exposed to some extent on the toner surface in order to impart chargeability. for that reason,
These additives fall off from the toner surface due to friction between toners, collision with a carrier, friction with an electrostatic latent image carrier, and contamination of the carrier, electrostatic latent image carrier such as a photoconductor belt or drum. Contamination such as occurs. As a result, the charging property is deteriorated, the deterioration progresses as the number of copies increases, the image density decreases, and fine line reproducibility and fog properties become practical problems.

Therefore, it has been attempted to improve the above problems by improving the affinity and dispersibility of the binder resin of the toner and the dye / pigment or charge control agent which imparts the charging property. For example, there is a method of surface-treating these additives in order to increase the affinity, but the surface treatment often lowers the charge imparting property. Further, in order to improve the dispersibility, there is also a method of increasing the mechanical shearing force to finely disperse the toner. However, the proportion of the additive appearing on the toner surface decreases, and the chargeability tends not to be sufficiently imparted.

From these facts, the additives for imparting electrostatic charge that are sufficiently satisfactory for practical use are very limited, and few have been put into practical use.

In order to obtain a color image as well as a black and white image, it is preferable that the one added to the toner is colorless, but most of the conventionally used dyes, pigments or charge control agents are dark colors. However, in that situation, there is almost nothing that has been put into practical use, and research is continuing.

Therefore, it has been proposed that the charging property is not improved by the additive of the toner, but is regulated by the carrier such as a carrier, a sleeve, a doctor blade or the like, or by another frictional charge imparting member.

Here, the triboelectrification imparting member means a member capable of imparting a charge necessary for development or supplementarily imparting it to the toner by contacting the toner, and hereinafter, these are collectively referred to as a triboelectrification imparting member. Called.

[0013]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a triboelectrification imparting member which has an excellent positive electrification property overcoming the drawbacks of the prior art, and yet another object is to charge vivid color toner. And a developing device for positively charging toner having such a triboelectrification imparting member, which provides image quality equivalent to the initial image even after continuous copying. The purpose is to do.

[0014]

The constitution of the present invention for solving the above-mentioned problems is to provide a triboelectrification imparting member for positive charging for developing an electrostatic charge image and a positively charging toner as described in the claims. It is a developing device.

In summary, as a result of intensive studies by the present inventors, the present invention provides a triboelectrification imparting member having a fluorine-containing quaternary ammonium salt compound represented by the following general formula on at least the surface thereof. We have found that the purpose can be achieved.

[0016]

[Chemical 2]

However, X; --SO _2- , --CO--.

R ₁ , R ₂ , R ₃ , R ₄ ; H, carbon number 1-10
Lower alkyl group and aryl group of.

N: a positive integer.

M: a positive integer.

The above compound may be used by dispersing it in a solvent or a dispersion medium as it is, or may be used by dispersing it in a resin. As such a resin, general ones can be used, for example, polystyrene, polyacrylic acid ester, polymethacrylic acid ester, polyacrylonitrile, rubber resin such as polyisoprene and polybutadiene, polyethylene, polypropylene, polyester, polyurethane. , Polyamide, epoxy resin, polycarbonate, rosin, phenol resin, chlorinated paraffin, silicone resin Teflon, and derivatives thereof, copolymers thereof, and mixtures thereof.

The above-mentioned coating liquid is applied to the base material of the triboelectrification imparting member by dipping, spraying, brushing or the like and dried to obtain the triboelectrification imparting member of the present invention. Further, the resin in which the above compound is dispersed may be molded as it is to form a triboelectrification imparting member. In this case, reinforcement,
Inorganic fillers such as silica, carbon, carbon fibers, and glass fibers may be contained in order to improve the effect of preventing wear. As the base material of the carrier type frictional charge imparting member,
All known carriers can be used, and particles of metals or alloys such as iron, nickel and aluminum, particles of metal compounds such as metal oxides, and ceramic particles such as glass and silicon carbide are used. Further, as the base material of the sleeve or the blade of the frictional charge imparting member, a conventionally used sleeve or doctor blade such as a metal or alloy such as iron, aluminum or stainless steel, a non-metallic compound such as plastic or rubber can be used. ..

The present invention is based on the finding that as a result of repeating various experiments, it was confirmed that a high positive charge was obtained by using the compound of the above general formula for the frictional charge imparting member and a good copy was obtained. Is.

The compounds of the above general formula used in the present invention include the following.

[0025]

[Chemical 3]

[0026]

[Chemical 4]

[0027]

[Chemical 5]

The following are examples of the charge imparting agent which is supplementarily added to the above-mentioned frictional charge imparting member. For example, metal complex salts of monoazo dyes, nitrohumic acid and its salts, salicylic acid, naphthoic acid, and C of dicarboxylic acids.
There are metal complexes of o, Cr, Fe and the like, sulfonated copper phthalocyanine pigments, nitro groups, halogen-introduced styrene oligomers, chlorinated paraffins and melamine resins.

Next, the case where the present invention is applied to a one-component developing device will be described. The operation when the present invention is applied to the one-component developing device is considered as follows. By covering the toner supply member with the compound represented by the general formula, the positively chargeable toner in the toner tank of the developing section is smoothly replenished to the supply member, and further the toner supply member is supplied to the toner supply member from the toner conveying member. By applying a bias of 0 to 500 V positive potential, the toner on the toner supply member is smoothly accumulated on the toner conveying member without being accumulated, and the toner flow in the developing device is smoothed. The upper toner layer thickness can always be kept uniform.

The toner supply member of the present invention may be sponge-like material, fur brush-like material, or the like, but is not limited thereto. Further, as a method of coating the surface of the toner supply member with the above-mentioned fluorinated quaternary ammonium salt, the toner supply member is immersed in, or sprayed with, a coating solution prepared by dissolving or dispersing it in a solvent or a dispersion medium, if necessary. It can be applied by a method such as brush coating.

What is important in the present invention is that the toner supply member is surface-treated with a substance having a negative charging property with respect to the toner. In the case of a substance having no negative charging property, the toner is a toner. The supply member does not sufficiently negatively charge triboelectrically, the supply member is not sufficiently replenished with toner, and the toner is not sufficiently supplied to the toner conveying member, so that a uniformly charged and uniform thin toner layer cannot be obtained. More importantly, as a coating material for the surface of the toner supply member, it must be positively charged to the toner stably without being deteriorated by heat or with time even after long-term use. is there.

By applying a bias of 0 to +500 V to the toner supplying member from the toner conveying member, the toner is quickly replenished from the toner supplying member onto the toner conveying member. If the applied bias is a negative potential, the transfer of the toner onto the conveying member becomes insufficient, and +5
If it is more than 00V, toner filming on the toner conveying member occurs, and running causes fog on the image.

As the toner used in combination with the above-described frictional charge imparting member of the present invention, those used as conventional electrophotographic toners can be used. That is, the toner may be magnetic or non-magnetic. More specifically, the toner is a colored fine particle in which a colorant is contained in a binder resin, and may contain magnetic powder if necessary. Furthermore, these toners may contain a small amount of a charge imparting agent such as a dye / pigment and a charge control agent in order to impart a more efficient charge, but the amount thereof may be considerably less than in the past. As the charge imparting agent, for example, nigrosine, carbon number 2 to 16
Azine dyes containing alkyl groups (Japanese Patent Publication No. 42-162)
7), basic dyes, lake pigments of basic dyes, C.I. I.
Solvent Black 3 Hansa Yellow G, C.I. I. Molderant Black 11, C.I. I. Pigment Black 1, Gilsonite, asphalt, quaternary ammonium salt, metal salt of higher fatty acid, metal complex of acetylacetone, vinyl polymer containing amino group, polyamine resin such as condensation polymer containing amino group, and the like.

If necessary, a fluidizing agent such as colloidal silica, a metal oxide such as titanium oxide and aluminum oxide, an abrasive such as silicon carbide, and a lubricant such as a fatty acid metal salt may be contained. ..

[0035]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. The amounts (parts) of each component described in the examples are parts by weight.

Example I-1 30 g of the exemplified compound (1) in 1 liter of toluene.
And styrene-MMA copolymer 70 g are dissolved and dispersed, and this is a spherical ferrite carrier (average particle size 100 μm) 5 k
g was coated in a fluid bed coater.

The toner was prepared from the following composition.

Styrene-n-butyl methacrylate 100 parts Polypropylene 5 parts C.I. I. Pigment Blue 15 5 parts The mixture having the above composition is kneaded, cooled, pulverized, and classified to 5-2.
A blue toner having a particle size of 0 μm was obtained.

2.5 parts of this toner was mixed with 97.5 parts of the carrier in a ball mill to obtain a developer.

Next, the above developer was set in FT4820 manufactured by our company, and an image test was carried out. As a result, a good image was obtained, and the image did not change after 100,000 images were printed.

When the toner charge amount was measured by the blow-off method, the initial charge amount was +16.9 μc / g, and the toner charge amount after running 100,000 sheets was +.
There was almost no difference from the initial value, which was 15.5 μc / g.
Also, in a high humidity environment of 35 ° C 90% RH and at 10 ° C 1
Even under a low humidity environment of 5% RH, an image equivalent to normal humidity was obtained.

Example I-2 A coated carrier was prepared in the same manner as in Example I-1, using the exemplified compound (2).

The toner was prepared from the following composition.

Cross-linked polyester (RN-201 manufactured by Kao) 100 parts Polypropylene 5 parts Quaternary ammonium salt (Orient Chemical Bontron P-51) 1 part Carbon black 10 parts Mixture of the above composition is kneaded, cooled, crushed, classified, and 5 ~ 2
A black toner having a particle size of 0 μm was obtained.

To 3 parts of this toner, the carrier 97
Parts were mixed with a ball mill to obtain a developer.

Next, the above developer was set in FT4820 manufactured by our company, and an image test was carried out. As a result, a good image was obtained, and the image did not change after 100,000 images were printed.

When the toner charge amount was measured by the blow-off method, the initial charge amount was +19.3 μc / g, and the toner charge amount after running 100,000 sheets was +18.1 μc / g, which is an initial value. Was almost the same.
Also, in a high humidity environment of 35 ° C 90% RH and at 10 ° C 1
Even under a low humidity environment of 5% RH, an image equivalent to normal humidity was obtained.

Example I-3 100 g of a silicone resin was dissolved in 1 liter of toluene, and 50 g of the exemplified compound (1) was further mixed therein. This was coated with a spherical ferrite carrier in the same manner as in Example I-1.

The toner was prepared from the following composition.

Styrene-2-ethylhexyl acrylate copolymer 100 parts Quaternary ammonium salt (Orient Chemical Bontron P-51) 0.5 part C.I. I. Pigment Blue 15 2 parts C.I. I. Pigment Yellow 17 5 parts The mixture having the above composition is kneaded, cooled, pulverized, and classified to 3-1.
A green toner having a particle size of 5 μm was obtained.

2.5 parts of this toner was mixed with 97.5 parts of the carrier in a ball mill to obtain a developer.

Next, the above developer was set in FT4820 manufactured by our company, and an image test was carried out. As a result, a good image was obtained, and the image did not change after 100,000 images were printed.

Further, when the toner charge amount was measured by the blow-off method, the initial charge amount was +22.5 μc / g, and the toner charge amount after running 100,000 sheets was +.
There was almost no difference from the initial value of 21.1 μc / g.
Also, in a high humidity environment of 35 ° C 90% RH and at 10 ° C 1
Even under a low humidity environment of 5% RH, an image equivalent to normal humidity was obtained.

Example I-4 100 g of MMA resin was dissolved in 1 liter of toluene,
Further, 50 g of the exemplified compound (2) was mixed with this.
This was coated with a spherical ferrite carrier in the same manner as in Example I-2.

The toner was prepared from the following composition.

Polyester resin (Arakawa Chemical Luna Pale 1467M) 100 parts C.I. I. Pigment Red 57 5 parts C.I. I. Pigment Red 48 3 parts The mixture having the above composition is kneaded, cooled, pulverized, and classified to 5-2.
A red toner having a particle size of 0 μm was obtained.

To 3 parts of this toner, the carrier 97
Parts were mixed with a ball mill to obtain a developer.

Next, the developer was set in FT4820 manufactured by the same company, and an image test was carried out. As a result, a good image was obtained, and the image did not change after 100,000 images were printed.

When the charge amount of the toner was measured by the blow-off method, the initial charge amount was +15.7 μc / g, and the charge amount of the toner after running 100,000 sheets was +.
There was almost no difference from the initial value, which was 14.9 μc / g.
Also, in a high humidity environment of 35 ° C 90% RH and at 10 ° C 1
Even under a low humidity environment of 5% RH, an image equivalent to normal humidity was obtained.

Example I-5 30 g of the exemplified compound (1) and 70 g of styrene-MMA copolymer were dissolved and dispersed in 1 liter of toluene, and the toner carrying member (developing sleeve) 2 shown in FIG.
Was coated by dipping and set in the developing section.

To 100 parts of the toner of Example 1, 3 parts of silicon carbide (particle size 2 μm), hydrophobic colloidal silica 0.
One part was sufficiently stirred and mixed with a speed kneader to obtain a toner.

This toner was loaded into a developing device as shown in FIG. 1, continuous copying was carried out, and an image test was carried out.
A good image was obtained. The image did not change after 50,000 images were printed.

This developing method will be described. As shown in the drawing, the toner 6 contained in the toner tank 7 is forced to the sponge roller 4 by the stirring blade 5, and the toner is supplied to the sponge roller 4. And
The toner taken into the sponge roller 4 is rotated by the sponge roller in the direction of the arrow, so that the toner conveying member 2
Transported to, rubbed, electrostatically or physically adsorbed,
The toner conveying member 2 strongly rotates in the direction of the arrow, and the elastic blade 3 forms a uniform thin toner layer and is triboelectrically charged. After that, the toner is conveyed to the surface of the electrostatic latent image carrier 1 which is in contact with or in the vicinity of the toner conveying member 2, and the latent image is developed.

The electrostatic latent image is developed by forming a latent image by exposing the organic photoconductor to 800 V of negative DC charge, and then exposing.

Further, in order to measure the specific charge amount Q / M of the toner on the toner carrying member, the toner on the toner carrying member is sucked through a Faraday cage equipped with a filter layer on the outlet side to When the Q / M was measured by a suction method specific charge amount measuring device for measuring the specific charge of the toner trapped inside, it was confirmed that the toner was sufficiently charged with +9.5 μc / g.

In addition, the charge amount in running 50,000 sheets is +
There was almost no difference from the initial value of 8.8 μc / g.

Further, image quality equivalent to normal humidity was obtained even under high and low humidity. Further, there was no toner filming on the photoconductor.

Example I-6 100 g of a silicone resin was dissolved in 1 liter of toluene, and 50 g of the exemplified compound (2) was further mixed therein. The toner carrying member 2 shown in FIG. 1 was coated with this by spraying and set in the developing section.

The toner was prepared from the following composition.

Styrene-2-ethylhexyl acrylate copolymer 100 parts Polyethylene 5 parts Quaternary ammonium salt (Orient Chemical Bondron P-51) 0.3 parts C.I. I. Pigment Red 57 5 parts C.I. I. Pigment Red 48 3 parts The mixture having the above composition is kneaded, cooled, pulverized, and classified to 5-2.
A red toner having a particle size of 0 μm was obtained.

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 with a speed kneader to obtain a toner.

When this toner was put in the developing section of the drawing and an image test was conducted in the same manner as in Example I-5, a clear and good red image was obtained.

When Q / M was measured in the same manner as in Example I-5, the initial value was +11.4 μc / g, and the value after 50,000 sheets was +9.6 μc / g, showing almost no change.

Also, image quality equivalent to normal humidity was obtained under high and low humidity.

Example I-7 30 g of the exemplified compound (5) and 70 g of a styrene-MMA copolymer were dissolved and dispersed in 1 liter of toluene and sprayed on the elastic blade (stainless steel) shown in FIG. It was coated and set in the developing section. An image test was performed in the same manner as in Example 5 using the toner of Example 6, and a clear and favorable red image was obtained. Further, when Q / M was measured in the same manner as in Example I-5, the initial value was +1.
0.2 μ / g, +50,000 μc is +9.1 μc / g,
There was almost no change.

Also, image quality equivalent to normal humidity was obtained under high and low humidity.

Example I-8 100 g of a silicone resin was dissolved in 1 liter of toluene, and 50 g of the exemplified compound (2) was further mixed therein. This was spray-coated on the elastic blade (made of stainless steel) shown in FIG. 1 and set in the developing section. An image test was performed in the same manner as in Example 5 using the toner of Example 6, and a clear and favorable red image was obtained.

When Q / M was measured in the same manner as in Example I-5, the initial value was +11.3 μc / g and the value after 50,000 sheets was +9.8 μc / g, showing almost no change.

Also, image quality equivalent to normal humidity was obtained under high and low humidity.

Example I-9 50 parts of the exemplified compound (1) and 100 parts of a silicone resin were mixed, heated and melted, and the molded resin blade was attached to an elastic blade (3) shown in the drawing.

The toner was prepared from the following composition.

Epoxy resin 100 parts Polypropylene 5 parts C.I. I. Pigment Blue 15 2 parts C.I. I. Pigment Yellow 175 parts The mixture having the above composition was kneaded, cooled, pulverized and classified in the same manner as in Example I-1 to obtain a green toner having a particle diameter of 3 to 20 µm.

To 100 parts of this toner, 2 parts of silicon carbide (particle size 2 μm) and 0.1 part of zinc stearate fine powder were sufficiently stirred and mixed with a speed kneader to obtain a toner.

Using this toner, an image test was conducted in the same manner as in Example I-5. As a result, a clear and good green image was obtained.

When Q / M was measured in the same manner as in Example I-5, the initial value was +8.0 μc / g and the value after 50,000 sheets was +.
It was 6.9 μc / g, and there was almost no change.

Also, image quality equivalent to normal humidity was obtained under high and low humidity.

Example I-10 A resin blade was prepared in the same manner as in Example I-9 using the exemplified compound (8). Using the toner of Example I-6,
When an image test was conducted in the same manner as in Example I-5, a clear and good red image was obtained.

When Q / M was measured in the same manner as in Example I-5, the initial value was +8.5 μ / g and the value after 50,000 sheets was +.
It was 7.7 μc / g, and there was almost no change.

Also, image quality equivalent to normal humidity was obtained under high and low humidity.

Example I-11 50 parts of the exemplified compound (12), polystyrene resin 10
0 parts and 30 parts of carbon black were mixed, and the mixture was heated and melted and molded to prepare a resin blade.

The toner was prepared from the following composition.

Styrene-n-butylmethacrylate 100 parts Polypropylene 5 parts Carbon black 10 parts Charge control agent (Nigrosine dye) 0.5 parts The mixture of the above composition is kneaded, cooled, ground and classified to 5-2.
A black toner having a particle size of 0 μm was obtained.

To 100 parts of this toner, 3 parts of silicon carbide (particle size: 2 μm) and 0.5 part of titanium oxide were sufficiently stirred and mixed with a speed kneader to obtain a toner.

Using this toner, an image test was conducted in the same manner as in Example I-5. As a result, a clear and good black image was obtained.

When Q / M was measured in the same manner as in Example I-5, the initial value was +11.6 μc / g, and the value after 50,000 sheets was +10.2 μc / g, showing almost no change.

Also, image quality equivalent to normal humidity was obtained under high and low humidity.

Example I-12 50 parts of the exemplified compound (15), 100 parts of MMA resin,
A resin blade was prepared in the same manner as in Example I-11 by mixing 30 parts of calcium carbonate.

The toner was prepared from the following composition.

Polyester resin 100 parts Polyethylene 7 parts C.I. I. Pigment Blue 15 5 parts The mixture having the above composition is kneaded, cooled, pulverized, and classified to 5-2.
A blue toner having a particle size of 0 μm was obtained.

To 100 parts of this toner, 3 parts of silicon carbide (particle size: 2 μm) and 0.5 part of titanium oxide were sufficiently stirred and mixed with a speed kneader to obtain a toner.

Using this toner, an image test was conducted in the same manner as in Example I-5. As a result, a clear and good black image was obtained.

When Q / M was measured in the same manner as in Example I-5, the initial value was +9.6 μc / g and the value after 50,000 sheets was +.
It was 8.4 μc / g, and there was almost no change.

Also, image quality equivalent to normal humidity was obtained under high and low humidity.

Example II-1 Styrene resin (D-125 manufactured by Esso) 85 parts Carbon black (# 44 manufactured by Mitsubishi Kasei Co.) 12 parts Nigrosine dye 2 parts The mixture having the above composition was sufficiently stirred and mixed in a Henschel mixer. Then, the mixture is melt-kneaded with a hot roll mill, cooled to room temperature, coarsely pulverized with a hammer mill, and then finely pulverized with an air jet mill. The fine powder obtained is classified to have a particle size of 3
A toner of ˜25 μm was obtained.

Next, the following composition was dispersed and dissolved in a ball mill at room temperature for 10 hours to form a coating solution, which was dipped into a toner supply member of sponge material, and the solvent was completely evaporated at 110 ° C.

Exemplified Compound (1) 5.0 g Solvent Methanol 300 g As shown in the figure, the toner supplying member 4 was placed in a developing device including the toner conveying member 2 and the toner layer thickness regulating member 3. A developing method using this developing device will be described. As shown in the figure, the toner 6 contained in the toner tank 7 is forcibly moved to the toner supply member 4 by the stirring blade 5, and the toner is transferred to the toner supply member 4. Supplied. Then, the toner taken in by the toner supply member 4 is carried to the toner conveying member 2 by the rotation of the toner supplying member in the direction of the arrow, and is rubbed and electrostatically or physically adsorbed, and the toner conveying member 2 is It strongly rotates in the direction of the arrow, a uniform thin toner layer is formed by the toner layer thickness regulating member 3, and the toner layer is triboelectrically charged. After that, the toner is conveyed to the surface of the latent image carrier 1 which is in contact with or in the vicinity of the toner conveying member 2 and the latent image is developed.

In this embodiment, the toner is replenished to the main developing device, and the toner conveying member is supplied to the -200V toner supply member.
When a bias of 100 V was applied and the image was developed on a photoreceptor having a negative latent image, and an image was formed through a transfer / fixing process, a clear image was obtained. Subsequently, when 50,000 sheets were continuously copied, a clear image which was the same as the initial one was obtained. Further, the specific charge amount (Q
/ M) through a Faraday cage (not shown) equipped with a filter on the outlet side to suck the toner on the toner conveying member and measure the specific charge of the toner trapped in the Faraday cage. When measured with a measuring device, the specific charge amount is +12.3 (μc / g), which is a sufficient amount, and the Q / M after continuous copying of 50,000 sheets is +11.4.
(Μc / g) was almost unchanged from the initial stage. Furthermore, under high temperature and high humidity of 35 ° C ・ 90% RH, and 10 ° C ・ 1
Even under a low temperature and low humidity environment of 5% RH, image quality equivalent to that at normal temperature and normal humidity was obtained.

The triboelectrification property between the coating liquid coated on the surface of a metal plate and the toner was applied to the toner suction type specific charge amount measuring device as described above, and its charging polarity was examined. The coating liquid coated on the surface of the metal plate was negatively charged.

Example II-2 Styrene-acrylic resin (SBM-73 manufactured by Sanyo Kasei) 80 parts Carbon black (# 44 manufactured by Mitsubishi Carbon Co.) 10 parts Low molecular weight polypropylene 5 parts Quaternary ammonium salt 5 parts Mixture of the above composition Was obtained in the same manner as in Example II-1. To 100 parts of this toner, 0.1 part of colloidal silica (R-972 manufactured by Nippon Aerosil Co., Ltd.) was added.

Next, the following composition was dispersed and dissolved in a ball mill at room temperature for 10 hours to prepare a coating solution, which was dipped in a sponge-like toner supplying member, and the solvent was completely evaporated at 110 ° C.

Exemplified Compound (2) + Acrylic Resin 10 + 20 g Solvent Toluene 1000 g The toner supply member 4 was placed in the developing device in the same manner as in Example II-1. When the toner was replenished to the main developing device and a bias of -200V was applied to the toner conveying member to the -300V toner supplying member to develop it in the same manner as in Example II-1, and to perform image development, a clear image was obtained. Was obtained. 50 in a row
When 000 sheets were continuously copied, a clear image similar to the initial one was obtained. Further, the specific charge amount (Q / M) of the toner on the toner conveying member is sufficient as the initial value of +10.2 (μc / g), and the Q / M after continuous copying of 50,000 sheets is +9.5.
(Μc / g) was almost unchanged from the initial stage. Furthermore, under high temperature and high humidity of 35 ° C ・ 90% RH, and 10 ° C ・ 5
Even under a low temperature and low humidity environment of% RH, image quality similar to that at normal temperature and normal humidity was obtained.

The triboelectrification property between the coating liquid coated on the surface of a metal plate and the toner was examined by applying the toner suction type specific charge amount measuring device as described above to examine the charging polarity. The coating liquid coated on the surface of the metal plate was negatively charged.

Example II-3 Styrene-2-ethylhexyl acrylate-n-butyl methacrylate-based resin 80 parts Carbon black (# 44 manufactured by Mitsubishi Kasei Co.) 12 parts Low molecular weight polypropylene 5 parts Nigrosine dye 3 parts A mixture of the above composition was carried out. A toner was prepared in the same manner as in Example II-1. To 100 parts of this toner, 0.1 part of colloidal silica (R-972 manufactured by Nippon Aerosil Co., Ltd.) was added.

Next, the following composition was dispersed and dissolved in a ball mill at room temperature for 10 hours to prepare a coating solution, which was dipped in a toner supply member made of a sponge material, and the solvent was completely evaporated at 110 ° C.

Exemplified Compound (3) 5.0 g Solvent Ethanol 300 g The toner supply member 4 was placed in the developing device in the same manner as in Example II-1. The toner was replenished to the main developing device, a bias of -100 V was applied to the toner feeding member of -450 V and a toner supplying member was developed in the same manner as in Example II-1, and an image was formed. A clear image was obtained. Was obtained. 50 in a row
When 000 sheets were continuously copied, a clear image similar to the initial one was obtained. Further, the specific charge amount (Q / M) of the toner on the toner conveying member is sufficient as the initial value of +11.1 (μc / g), and the Q / M after continuous copying of 50,000 sheets is +10.
2 (μc / g), which was almost unchanged from the initial stage. Furthermore, under high temperature and high humidity of 35 ° C ・ 90% RH, and 10 ° C ・
Even under a low temperature and low humidity environment of 15% RH, image quality equivalent to that at normal temperature and normal humidity was obtained.

The triboelectrification property between the toner coated with the coating liquid on the surface of a metal plate and the toner was examined by applying the toner suction specific charge amount measuring device as described above, and the charging polarity was examined. What coated the liquid on the surface of the metal plate,
It was negatively charged.

Comparative Example II-1 An image was produced using the same apparatus and toner as in Example II-1 except that the coating material of Example II-1 was not used as the coating material of the toner supply member 4, and from the initial stage Continuous copy 100
A clear image was obtained up to 00, but 20000
The image density started to decrease after one sheet, the image density further decreased after 50,000 sheets, and an afterimage was generated, and a uniform thin toner layer was not formed on the toner conveying member.

When the Q / M of the toner on the toner conveying member was measured in the same manner as in Example II-1, the initial value was +1.
0.2 (μc / g), +3.2 (μc after 20,000 sheets
/ G), and after 50,000 sheets, it was +1.2 (μc / g).

Comparative Example II-2 Using the same apparatus and toner as in Example II-1, a bias of −250 V was applied to the toner conveying member and a bias of −300 V was applied to the toner supplying member, and similar image formation was performed. A clear image was obtained from the initial stage up to 10,000 continuous copies, but after 20,000 sheets, the image density began to decrease, and after 50,000 sheets, the image density further decreased, and afterimages and the like occurred. In this case, a uniform thin toner layer was not formed, and toner filming occurred on the surfaces of the toner layer thickness regulating member and the toner conveying member.

When the Q / M of the toner on the toner conveying member was measured in the same manner as in Example II-1, the initial value was +1.
1.3 (μc / g), after 20,000 sheets +5.7 (μc
/ G), and after 50,000 sheets, it was +2.6 (μc / g).

Example II-4 The same apparatus and toner as in Example 1 except that the Exemplified Compound (3) was used as a coating material for the toner supply member 4 instead of the Exemplified Compound (1) of Example II-1. When a bias of -200V was applied to the toner feeding member to the toner feeding member and a voltage of -200V was applied, development was performed in the same manner as in Example 1 and image formation was performed, and a clear image was obtained. When 50,000 sheets were continuously copied, a clear image similar to the initial one was obtained. Further, the specific charge amount (Q
/ M) is sufficient as the initial value of +12.4 (μc / g),
Q / M after continuous copying of 50,000 sheets is +11.6 (μc /
It was almost the same as g). 35 more
High temperature and high humidity of ℃ ・ 90% RH and 10 ℃ ・ 15% RH
Even under the low temperature and low humidity environment, image quality equivalent to that at normal temperature and normal humidity was obtained.

The triboelectrification property between the coating liquid coated on the surface of a metal plate and the toner was examined by applying the toner suction specific charge amount measuring device as described above, and the charging polarity was examined. What coated the liquid on the surface of the metal plate,
It was negatively charged.

Example II-5 An apparatus similar to Example II-2 except that the exemplified compound (8) was used as a coating material for the toner supply member 4 in place of the exemplified compound (2) of Example II-2. A bias of −300 V was applied to the toner feeding member with a toner by a toner supply member of −150 V, and the toner was developed in the same manner as in Example II-2, and an image was formed. A clear image was obtained. 500 in a row
When 00 sheets were continuously copied, a clear image similar to the initial one was obtained. Further, the specific charge amount (Q / M) of the toner on the toner conveying member is sufficient at the initial +8.8 (μc / g), and the Q / M after continuous copying of 50,000 sheets is +8.1 (μ).
c / g) was almost unchanged from the initial stage. Furthermore, under high temperature and high humidity of 35 ° C ・ 90% RH, and 10 ° C ・ 15%
Even under a low temperature and low humidity environment of RH, image quality equivalent to that at normal temperature and normal humidity was obtained.

The triboelectrification property between the coating liquid coated on the surface of a metal plate and the toner was examined by applying the toner suction specific charge amount measuring device as described above to examine the charging polarity. What coated the liquid on the surface of the metal plate,
It was negatively charged.

Example II-6 An apparatus similar to Example II-2 except that the exemplified compound (12) was used as a coating material for the toner supply member 4 instead of the exemplified compound (2) of Example II-2. With toner, a bias of −400V was applied to the toner feeding member to −400V to the toner supplying member, the development was performed in the same manner as in Example II-2, and the image was formed. As a result, a clear image was obtained. Then 50
When 000 sheets were continuously copied, a clear image similar to the initial one was obtained. Further, the specific charge amount (Q / M) of the toner on the toner conveying member is sufficient at the initial +9.5 (μc / g), and the Q / M after continuous copying of 50,000 sheets is +8.6.
(Μc / g) was almost unchanged from the initial stage. Furthermore, under high temperature and high humidity of 35 ° C ・ 90% RH, and 10 ° C ・ 1
Even under a low temperature and low humidity environment of 5% RH, image quality equivalent to that at normal temperature and normal humidity was obtained.

The triboelectrification property between the coating liquid coated on the surface of a metal plate and the toner was examined by applying the toner suction specific charge amount measuring device as described above to check the charging polarity. What coated the liquid on the surface of the metal plate,
It was negatively charged.

Example II-7 An apparatus similar to Example II-1 except that the exemplified compound (15) was used as a coating material for the toner supply member 4 instead of the exemplified compound (1) of Example II-1. A bias of −200 V was applied to the toner feeding member with a toner feeding member of −200 V, and the toner was developed in the same manner as in Example II-1 to perform image development. As a result, a clear image was obtained. 50 in a row
When 000 sheets were continuously copied, a clear image similar to the initial one was obtained. Further, the specific charge amount (Q / M) of the toner on the toner conveying member is sufficient at the initial stage +9.5 (μc / g), which is Q / M after continuous copying of 50,000 sheets +8.3 (μ).
c / g) was almost unchanged from the initial stage. Furthermore, under high temperature and high humidity of 35 ° C ・ 90% RH, and 10 ° C ・ 15%
Even under a low temperature and low humidity environment of RH, image quality equivalent to that at normal temperature and normal humidity was obtained.

The triboelectrification property between the coating liquid coated on the surface of a metal plate and the toner was examined by applying the toner suction specific charge amount measuring device as described above to check the charging polarity. What coated the liquid on the surface of the metal plate,
It was negatively charged.

[0129]

As described above, according to the present invention, an image having the same quality as the initial image can be obtained even after continuous copying.
A clear color image can be obtained with no change in the positive charge amount and little environmental change.

Further, by coating the toner supply section with the compound of the general formula, its surface energy is reduced,
The toner is prevented from fusing and the toner is triboelectrically charged, so that the environmental stability is improved and the toner replenishment property to the toner conveying member is improved.

[Brief description of drawings]

FIG. 1 is an explanatory view of an example of a developing device using a positive charging frictional charge imparting member of the present invention.

[Explanation of symbols]

 1 Electrostatic Latent Image Carrier 2 Toner Conveying Member 3 Elastic Blade 4 Sponge Roller 5 Stirring Blade 6 Toner 7 Toner Tank

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Fumihiro Sasaki 1-3-6 Nakamagome, Ota-ku, Tokyo Stock company Ricoh Co., Ltd. (72) Chiharu Mochizuki 1-3-6 Nakamagome, Ota-ku, Tokyo Shares Inside the Ricoh Company (72) Inventor Masafumi Takeshita 6-2-1 Kano-cho, Chuo-ku, Kobe-shi, Hyogo Incorporated company Neos (72) Inventor Koji Yano 1-1 Oike-cho, Konishi-cho, Koga-gun, Shiga Prefecture Stock Company Neos Institute

Claims (5)

[Claims] 1. A triboelectric charging member for positive charging for electrostatic image development, which comprises at least a surface of a fluorinated quaternary ammonium salt compound represented by the following general formula. [Chemical 1] _{However, X; -SO 2 -, -} CO-. R ₁ , R ₂ , R ₃ , R ₄ ; H, a lower alkyl group having 1 to 10 carbon atoms, an aryl group. n; a positive integer. m; a positive integer. 2. The triboelectric charge imparting member for positive charging for electrostatic image development according to claim 1, wherein the triboelectric charge imparting member is carrier particles. 3. The triboelectric charging member for positive charging for electrostatic image development according to claim 1, wherein the triboelectric charging member is a cylindrical sleeve. 4. The triboelectric charging member for positive charging for electrostatic image development according to claim 1, wherein the triboelectric charging member is a doctor blade. 5. A developing device having at least a toner conveying member and a toner layer thickness regulating member, rotatably supported while being in contact with the toner conveying member, and supplying toner onto the toner conveying member. In the apparatus, at least the surface of the toner supply member is coated with the fluorine-containing quaternary ammonium chloride represented by the general formula of claim 1, and the toner supply member has a positive potential of 0 to 500 V higher than that of the toner transport member. Developing device for positively chargeable toner, characterized in that the bias is applied.