JP3234340B2 - Negatively charged developer for electrostatic image development - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner for developing an electrostatic image and a two-component developer used in electrophotography, electrostatic printing, and the like, and more particularly to a toner developer for negatively charging.

[0002]

2. Description of the Related Art Conventionally, a method of developing an electrostatic charge image using a toner as disclosed in Japanese Patent Application Laid-Open No. 61-147261 is roughly classified into a so-called two-component developing method in which a toner and a carrier are mixed. There is a method using a developer, and a method using a one-component developer which is used alone without being mixed with a carrier.

In the above-mentioned method, the toner and the carrier are charged with different polarities by stirring and rubbing each other, and an electrostatic charge 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 used in a spray state, and a contact developing method in which toner particles are brought into direct contact with an electrostatic latent image surface for development (also referred to as a touch-down phenomenon). ), And an induction development method in which a magnetic conductive toner is brought into contact with an electrostatic latent image surface.

[0005] As a toner applied to these various developing methods, a fine powder in which a coloring agent such as carbon black is dispersed in a binder resin made of a natural resin or a synthetic resin is used. For example, particles obtained by finely pulverizing a dispersion of a colorant in a binder resin such as polystyrene to about 1 to 30 μm are used as toner. Further, those containing a magnetic material such as magnetite in addition to these components are 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 charge image to be developed. In order to retain the electric charge in the toner, it is possible to use the frictional charging property of the resin which is a component of the toner.However, in this method, since the charging property of the toner is small, an image obtained by development is easily fogged and unclear. It will be. Therefore, in order to impart a desired triboelectric charging property to the toner, a dye, a pigment, or a charge control agent that imparts charging property is added.

Conventionally, as a negative charge control agent, metal complexes of monoazo dyes, nitrohumic acid and salts thereof, metal complexes of salicylic acid, naphthoic acid, dicarboxylic acids such as Co, Cr and Fe, sulfonated copper phthalocyanine pigments, There are nitro group, halogen-introduced styrene oligomers, chlorinated paraffins, melamine resins, etc., but these dyes have complicated structures, inconsistent properties and poor stability. Further, it is easily decomposed or deteriorated due to decomposition, mechanical shock, friction, changes in temperature and humidity conditions during heat kneading, and a phenomenon that charge controllability tends to be reduced. Or, in many cases, the chargeability changes depending on the environment. Further, when a conventional toner containing the charge control agent is used for a long time, filming may occur on the photoconductor due to poor charging.

Further, there is an advantage that the storage stability and the low-temperature fixability are compatible with each other without impairing the PVC mat fusion resistance and the original color of the color material of the color toner. It is often used as a resin. However, when a polyester resin or an epoxy resin is used as a binder resin in the toner, the charge amount is low in any case, or the charge amount decreases when used repeatedly even if the charge amount is high, resulting in fog and toner scattering. There was a problem that it was difficult to do. This is because polyester resin and epoxy resin are -COOH, -O
This is presumably because functional groups such as H groups remain and hinder the maintenance of stable chargeability. Conventionally, as a mechanism of a two-component dry developer, fine toner particles are held on a relatively large particle surface by electric force generated by friction between the two particles, and when approaching an electrostatic latent image,
The attraction force in the latent image direction on the toner particles due to the electric field formed by the electrostatic latent image overcomes the bonding force between the toner particles and the carrier particles, and the toner particles are attracted to and adhered to the electrostatic latent image to form the electrostatic latent image. It is proposed that the image be visualized. Since the developer is used repeatedly while replenishing the toner consumed by the development, the carrier must always frictionally charge the toner particles with a desired polarity and a sufficient charge amount during long-term use. . However, in the conventional developer, a toner film is formed on a carrier surface by a mechanical collision such as a collision between particles or a collision between a particle and a developing machine, or heat generated by these actions, so that a so-called spent occurs, and the carrier is developed. Of the developer decreases with use time, and it is necessary to replace the entire developer.

In order to prevent such spent,
Conventionally, various resins have been proposed on the carrier surface, but no satisfactory resin has yet been obtained. For example, a carrier coated with a resin such as a styrene-methacrylate copolymer or a styrene polymer has excellent charging characteristics, but has a relatively high critical surface tension of the surface, and also causes spent during repeated copying. The life as a developer was not so long.

On the other hand, a carrier coated with a silicon resin having a low surface tension has been proposed. However, since the silicon resin has a low mechanical strength, it is strongly stirred, for example, in a high-speed copying machine, or the inside of a developing section is not provided. With long stirring in
When the carrier particles collide with the inner wall of the developing unit or the surface of the photoreceptor, or collide with each other, the silicone resin coating layer is worn and peeled off with time, and the triboelectric charge is changed from the charge between the toner and the silicone resin. Since the charge changes between carrier core particles, there has been a problem that the charge amount of the developer cannot be kept constant and the image quality deteriorates. In addition, when the carrier particles are coated with a silicone resin, the electrical resistance of the silicone resin itself is high, so that when used as a developer, there is a disadvantage that the image quality is inferior due to an edge phenomenon or a charge accumulation phenomenon.

[0011] The disadvantages of such coated carriers can be ameliorated by dispersing a conductive substance in the coating layer. That is, when a certain degree of conductivity is imparted to the carrier, the carrier acts as a developing electrode, and the developing is performed in a state where the developing electrode and the surface of the photoreceptor to be developed are in close contact with each other. Even a large area black part is faithfully reproduced as the original.

Conventionally, carbon, tin oxide or the like has been used as such a conductive material. However, when such a conductive material is dispersed in a coating layer of a carrier, the following disadvantages have occurred.

Generally, the toner and the carrier are charged when they come into contact with each other. In this case, when the electric resistance of the carrier decreases, the charge generated in the toner is attenuated through the carrier, and the charge amount cannot be maintained. Further, there has been a problem that the conductive material is separated from the coating layer due to use over time, and the charge amount is changed. In order to solve this problem, Japanese Patent Application Laid-Open No. 62-182759 discloses that carbon is improved by treating it with aminosilane, amino-modified silicone oil, or the like. Was.

[0014]

SUMMARY OF THE INVENTION According to the present invention, the frictional charging between toner particles or between toner and carrier, the toner in the case of one-component development, and a charging member such as a developing sleeve or a blade are stable, and It is an object of the present invention to provide a toner that has a triboelectric charge distribution that is sharp and uniform, has a good charge rising property and environmental stability, and can be adjusted to a charge quantity suitable for a developing system to be used. The purpose of the present invention is to provide a vivid color toner, and to provide a toner having the same image quality as an initial image even during continuous use. Still another object is that there is no background dirt or toner scattering, there is no deterioration in image quality due to edge development or charge accumulation phenomenon, and the carrier coating layer does not peel off even during continuous use, and there is no detachment of the conductive fine powder, so friction does not occur. An object of the present invention is to provide a two-component developer which is stable in charge and can provide an image having high fidelity equivalent to that of an initial image.

[0015]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a toner containing a binder resin, a colorant and a charge control agent as main components has a perfluoroalkenyl polyvinyl phenyl represented by the following general formula I: By incorporating ether as a charge control agent, it was possible to obtain a negatively chargeable toner for developing an electrostatic image which improved the above-mentioned conventional disadvantages.

Formula I

[0017]

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However, Rf: a perfluoroalkenyl group of C ₆ -C ₉ , F ₁₁ -F ₁₇ n; a positive integer The polymer has good charging characteristics even if the binder resin is a polyester resin or an epoxy resin, It is most suitable as a toner charge control agent for fixability. When the polymer and the fluorinated quaternary ammonium salt compound represented by the general formula II are used in combination as a charge control agent, a toner having better negative chargeability, particularly a color toner, can be obtained.

Formula II

[0020]

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[0021] _{However, X; -SO 2 -, -} CO-.

R ₁ , R ₂ , R ₃ , R ₄ ; H, C 1-10
A lower alkyl group or an aryl group.

Y: I, Br m; Positive integer P: Positive integer Further, the silicone resin coating layer of the carrier contains a conductive fine powder and a silane coupling agent, and the conductive fine powder is carbon black. There is an electron which is durable because the silane coupling agent is an aminosilane coupling agent, does not degrade image quality due to an edge phenomenon or a charge accumulation phenomenon, and exhibits stable triboelectricity even when used over time. A photographic two-component developer was obtained.

The present invention also maintains the advantages of the conventional silicone resin-coated carrier by coating the surface of the core particles with a silicone resin containing a conductive fine powder and a silane coupling agent. By imparting conductivity to the carrier, the phenomenon of charge accumulation on the carrier, peeling of the coating layer, and desorption of the conductive fine powder can be effectively suppressed. In particular, an aminosilane coupling agent having a primary and / or secondary amino group is preferable from the viewpoint of controlling the negative charge of the toner.

The amount of the compound represented by the general formula I used as a charge control agent in the present invention depends on the kind of the binder resin, the presence or absence of additives used as necessary, and the method for producing a toner including the dispersion method. Although it is determined by the formula, it is not limited to a specific one, but it is preferably used in the range of 1 to 20 parts by weight with respect to 100 parts by weight of the binder resin. Preferably, the range is 2 to 10 parts by weight. If the amount is less than 1 part by weight, the negative charge of the toner is insufficient, which is not practical. If the amount exceeds 20 parts by weight, the chargeability of the toner is too large, and the electrostatic attraction with the carrier is increased, so that the fluidity of the developer is reduced and the image density is reduced.

The number average molecular weight of the polymer represented by the general formula I is preferably in the range of about 3,000 to 10,000. This polymerization reaction is usually carried out in an atmosphere of an inert gas such as nitrogen gas at about 70 ° C. depending on the reactivity of the reaction components and the reaction system.
Perform at １００100 ° C. for about 4 to 24 hours. The reaction system is not particularly limited, and may be any of solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization, radiation polymerization and the like, but a particularly preferable system is a solution polymerization method.

In the solution polymerization, the reaction components are dissolved in an appropriate organic solvent, and an organic peroxide (for example, benzoyl peroxide, di-t-butyl peroxide, t-butyl perisobutyrate, an azo compound such as 2,2 '-Azobisisobutyronitrile, methyl-2,2'-azobisisobutyrate, etc.) or by irradiation with ionizing radiation. Suitable organic solvents are fluorinated organic solvents such as trichlorotrifluoroethane, tetrachlorodifluoroethane, meta-xylene hexafluoride and para-xylene hexafluoride. Next, a synthesis example of the polymer will be described.

<Synthesis Example 1>

[0029]

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In a reaction flask, 120 g of poly (4-hydroxystyrene) (Mw = 4000-6000) was dissolved in 500 g of dimethylformamide, and 500 g of meta-xylene hexafluoride and 330 g of hexafluoropropene oligomer (dimer) were added thereto. 121.40 g of triethylamine was added dropwise with stirring, and the reaction was carried out at room temperature for 24 hours. After completion of the reaction, 300 g of water was added to the reaction solution,
The reaction solution was separated and the lower layer was taken out and washed thoroughly with water, dilute hydrochloric acid and water in that order. After washing, the treated solution was dropped into 2 liters of vigorously stirred methanol to precipitate a product. The precipitate was dried to obtain 383 g (yield: 96%) of compound (1).

From the IR measurement of the compound (1), disappearance of the hydroxyl group and existence of the perfluoroalkenyl group were confirmed. Further, typical specific examples of the compound represented by the general formula II used as a negative charge control agent together with the compound represented by the general formula I include the following, all of which are white or pale yellow. Is shown.

[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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Examples of the binder resin used in the present invention include styrene such as polystyrene, poly-p-chlorostyrene and polyvinyltoluene, and homopolymers of substituted styrenes;
Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-
Methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer Coalesce, styrene-butyl methacrylate copolymer,
Styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer Styrene-based copolymers such as styrene-maleic acid copolymer, styrene-maleic acid ester copolymer; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester,
Polyurethane, polyamide, epoxy resin, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, and the like, They can be used alone or as a mixture.

Particularly, as examples of binder resins particularly suitable for pressure fixing, the following can be used alone or in combination. Polyolefin (low molecular weight polyethylene, low molecular weight polypropylene, polyethylene oxide, polytetrafluoroethylene, etc.), epoxy resin, polyester resin, styrene-butadiene copolymer, (monomer ratio 5 to 30: 9
5-70), olefin copolymer (ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer,
Ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, ionomer resin), and polyvinylpyrrolidone resin.

Particularly, the polyester resin used in the present invention is obtained by condensation polymerization of an alcohol and a carboxylic acid. Examples of the alcohol include polyethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-propylene glycol,
Diols such as neopentyl glycol and 1,4-butenediol, and ethers such as 1,4-bis (hydroxymethyl) cyclohexane, bisphenol A, hydrogenated bisphenol A, polyoxyethylenated bisphenol A, and polyoxypropylene bisphenol A Bisphenols, dihydric alcohol units obtained by substituting these with a saturated or unsaturated hydrocarbon group having 3 to 22 carbon atoms, other dihydric alcohol units, sorbitol,
1,2,3,6-hexane tetrol, 1,4-sarbitan, pentaethritol, dipentaesritol, tripetaesritol, sucrose, 1,2,4-butanetriol, 1,2,2 5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,
Examples thereof include trihydric or higher polyhydric alcohol monomers such as 2,4-butanetriol, trimethylolethane, trimethylolpropane, and 1,3,5-trihydroxymethylbenzene. Further, as the carboxylic acid used to obtain the polyester resin, for example, palmitic acid, stearic acid, monocarboxylic acids such as oleic acid,
Maleic acid, fumaric acid, mesaconic acid, citraconic acid,
Itaconic acid, glutaconic acid, phthalic acid, isophthalic acid,
Terephthalic acid, cyclohexanedicarboxylic acid, succinic acid, adipic acid, sebacic acid, malonic acid, divalent organic acid monomers obtained by substituting these with a saturated or unsaturated hydrocarbon group having 3 to 22 carbon atoms, these acids Anhydrides, dimers of lower alkyl esters and linoleic acid, other divalent organic acid monomers, 1,2,4-benzenetricarboxylic acid,
1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-
Hexanetricarboxylic acid, 1,3-dicarboxyl-2
-Methyl-2-methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid embol trimer acid, trivalent or higher polycarboxylic acids such as anhydrides of these acids Monomers can be mentioned.

The epoxy resin used in the present invention is, for example, a polycondensate of bisphenol A and epichlorohydrin.
2, R364, R365, R366, R367, R36
9. {Mitsui Petrochemical Industry Co., Ltd.}, Epototo Y
D-011, YD-012, YD-014, YD-90
4, YD-017, {manufactured by Toto Kasei Co., Ltd.} and Epicoat 1002, 1004, 1007 (manufactured by Shell Chemical Co., Ltd.).

The coloring agents used in the present invention include carbon black, lamp black, iron black, ultramarine blue, nigrosine dye, aniline blue, phthalocyanine blue, phthalocyanine green, Hansa Yellow G and rhodamine 6.
G, lake, chaco oil blue, chrome yellow, quinacridone, benzidine yellow, rose bengal, triallylmethane dye, monoazo dye, disazo dye, etc. obtain.

Further, when the toner of the present invention is used as a two-component developer, it is used by mixing with a carrier powder.
As the carrier that can be used in the present invention, all known carriers can be used, for example, iron powder, ferrite powder, powder having magnetic properties such as nickel powder, glass beads, and the like, and their surfaces are treated with a resin or the like. Things.

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

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

Further, the toner of the present invention may optionally contain additives. Examples of the additives include fluororesin fibers or fine particles, a lubricant such as zinc stearate, an abrasive such as cerium oxide and silicon carbide, or a fluidity-imparting agent such as colloidal silica and aluminum oxide, a caking inhibitor, or a carbonaceous agent. Examples include a conductivity-imparting agent such as black and tin oxide, and a fixing aid such as low-molecular-weight polyolefin. Hereinafter, the present invention will be described more specifically with reference to the following examples, but the present invention is not limited thereto. All parts are parts by weight.

The carrier core particles coated with the silicone resin in the present invention may be conventionally known particles, for example, ferromagnetic metals such as iron, cobalt and nickel; alloys and compounds such as magnetite, hematite and ferrite;
Glass beads and the like can be mentioned. The average particle size of these core particles is usually 10 to 1000 μm, preferably 30 to 500 μm.
μm. The amount of silicone resin used is
Usually, it is 1 to 10% by weight based on the carrier core particles.

The silicone resin used in the present invention may be any conventionally known silicone resin. For example, KR261, KR271, KR272, and KR27 manufactured by Shin-Etsu Silicone Co., which are commercially available.
5, KR280, KR282, KR285, KR25
1, KR155, KR220, KR201, KR20
4, KR205, KR206, SA-4, ES100
1, ES1001N, ES1002T, KR3093, SR2100, SR2101, S
R2107, SR2110, SR2108, SR210
9, SR2115, SR2400, SR2410, SR
2411, SH805, SH806A, SH840 and the like are used. As a method for forming the silicone resin layer, the silicone resin may be applied to the surface of the carrier core particles by a spraying method, an immersion method, or the like, as in the related art.

The coating layer composition is prepared by adding a conductive fine powder and a silane coupling agent to a silicone resin solution and dispersing with a suitable mixer. The conductive fine powder dispersed in the coating layer preferably has a particle size of about 0.01 to 5.0 [mu] m, and has a particle size of 0.1 to 100 parts by weight of the silicone resin.
It is preferably added in an amount of from 01 to 30 parts by weight, more preferably from 0.1 to 20 parts by weight. As the conductive fine powder, conventionally known carbon black is preferable, and examples thereof include contact black, furnace black, and thermal black.

The silane coupling agent is a compound represented by the formula X-Si (OR) ₃ , where X is a functional group that reacts with organic substances, and R is a hydrolyzable group. In particular, an aminosilane coupling agent having an amino group is desirable, and 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, is added to 100 parts by weight of the silicone resin. Examples of the aminosilane coupling agent include γ- (2-
Aminoethyl) aminopropyltrimethoxysilane, γ
-(2-aminoethyl) aminopropylmethyldimethoxysilane, γ-anilinopropyltrimethoxysilane,
Octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride and the like. Next, a production example of a carrier having several silicone resins in the coating layer will be described. These can be performed by known means.

Production Example 1 Composition of Coating Layer Forming Solution Silicon resin solution (KR250 manufactured by Shin-Etsu Silicone Co., Ltd.) 100 parts by weight Toluene 100 parts by weight The above formulation was dispersed with a homomixer for 30 minutes to prepare a coating layer forming solution. This coating layer forming solution is made to have an average particle size of 100 μm.
A carrier A having a coating layer formed on the surface of 1,000 parts by weight of the spherical ferrite was obtained using a fluidized bed type coating apparatus.

Production Examples 2 to 12 Each component shown in Table 1 below and 100 parts of toluene were mixed and dispersed with a homomixer for 30 minutes to prepare a coating layer forming liquid.

[0055]

[Table 1]

[0056]

[Table 2]

A carrier B, C, D, E, having a coating layer formed on a surface of 1,000 parts by weight of spherical ferrite having an average particle size of 70 μm using a fluidized bed type coating apparatus.
F, G, H, I, J, K, L were obtained.

[0058]

【Example】

Example 1 Styrene-2-ethylhexyl acrylate copolymer 100 parts C.I. I. Pigment Blue 15 5 parts 4-Perfluorohexenyl oxostyrene polymer 3.5 parts The mixture having the above composition is thoroughly stirred and mixed in a Henschel mixer, and then roll-milled at a temperature of 130 to 140 ° C. to a temperature of about 3 ° C.
After heating and melting for 0 minutes and cooling to room temperature, the obtained kneaded product was pulverized and classified to obtain a blue toner having a particle size of 5 to 20 μm.
2.5 parts of this toner and 97.5 parts of a 100 to 250 mesh iron powder carrier were mixed in a ball mill to obtain a developer. Next, the above developer was set on an FT7570 manufactured by our company, and development was performed. As a result, a good image was obtained, and the image did not change even after 80,000 sheets of image were output.

When the charge amount of the toner was measured by a blow-off method, the initial charge amount was −18.3 μc / g, and the charge amount of the toner after running 80,000 sheets was −1.
At 7.1 μc / g, there was almost no difference from the initial value. 3
High humidity environment of 5 ° C 90% RH, and 10 ° C 15% RH
Even under a low humidity environment of H, an image equivalent to normal humidity was obtained. There was no toner filming on the photoreceptor.

Example 2 A toner and a toner were used in the same manner as in Example 1 except that the carrier C was used.
When a developer was prepared and a similar image display test was performed, a good image was obtained, and the image did not change even after 100,000 sheets of image were output.

When the charge amount of the toner was measured by the blow-off method, the initial charge amount was −19.2 μc / g, and the charge amount of the toner after running 100,000 sheets was −
At 17.5 μc / g, there was almost no difference from the initial value. However, ground fogging occurred from around 120,000 sheets. Up to 100,000 sheets in a high humidity environment of 35 ° C and 90% RH, and at 10 ° C
An image equivalent to normal humidity was obtained even under a low humidity environment of 15% RH. There was no toner filming on the photoreceptor.

Example 3 Polyester resin (Lunaper 1438-6 manufactured by Arakawa Chemical Co., Ltd.) 100 parts Polypropylene 5 parts Carbon black 10 parts 4-perfluorohexenyl oxostyrene polymer 3.5 parts Exemplified compound II-2 0.5 part The raw material mixture having the composition was melt-kneaded in the same manner as in Example 1,
After cooling, pulverization and classification, a black toner having a particle size of 5 to 25 μm was obtained. To 2.5 parts of this toner, 97.5 parts of a carrier A coated with a silicone resin were mixed by a ball mill to obtain a developer. Next, this developer was set in our copier FT7570 as in Example 1, and an image test was performed. As in Example 1, a good image with high sharpness was obtained. It did not change even after displaying 10,000 images.

When the charge amount of the toner was measured by a blow-off method, the initial charge amount was -20.8 μc / g, and the charge amount of the toner after running 100,000 sheets was-
18.4 μc / g, which was almost the same as the initial value. In a high humidity environment of 35 ° C and 90% RH, and at 10 ° C and 15%
Even in a low humidity environment of RH, an image equivalent to normal humidity was obtained. Also, there was no toner filming on the photosensitive member.

Example 4 A toner and a toner were used in the same manner as in Example 3 except that the carrier F was used.
When a developer was prepared and a similar image display test was performed, a good image was obtained, and the image did not change even after 120,000 images were output.

When the charge amount of the toner was measured by a blow-off method, the initial charge amount was -21.4 μc / g, and the charge amount of the toner after running 120,000 sheets was-
20.6 μc / g was almost no difference from the initial value. However, ground fogging occurred from around 150,000 sheets. Up to 120,000 sheets in a high humidity environment of 35 ° C and 90% RH, and at 10 ° C
An image equivalent to normal humidity was obtained even under a low humidity environment of 15% RH. There was no toner filming on the photoreceptor.

Comparative Example 1 A developer was obtained in the same manner as in Example 1 except that zinc salicylate (Bontron E-84 manufactured by Orient Chemical Industries) was used instead of the 4-perfluorohexenyloxostyrene polymer of Example 1. , Image tests. As the initial image, a clear image without fog was obtained, but from about 50,000 sheets, an unclear image with fog was formed, and toner filming was observed on the surface of the photoreceptor. When an image test was performed under a high humidity environment of 35 ° C. and 90% RH, the image density was found to be 0.
The image was as low as 85, and an unclear image with fog was obtained. When the charge amount was measured in the same manner as in Example 1, the initial charge amount was −15.5 μc / g, but after 50,000 sheets, it decreased to −9.8 μc / g.

Example 5 Epoxy resin (R365 manufactured by Mitsui Petrochemical Co., Ltd.) 80 parts Epoxy resin (YD-017 manufactured by Toto Kasei Co., Ltd.) 20 parts C.I. I. Pigment Blue 15 5 parts C.I. I. Pigment Yellow 17 5 parts 4-Perfluorohexenyl oxostyrene polymer 5 parts Exemplified compound II-2 1 part The mixture having the above composition is sufficiently stirred and mixed in a Henschel mixer in the same manner as in Example 1, and then 130-1 by a roll mill.
After heating and melting at a temperature of 40 ° C. for about 30 minutes and cooling to room temperature, the obtained kneaded product was pulverized and classified to obtain a green toner having a particle size of 5 to 20 μm. To 100 parts of this toner, 3 parts of silicon carbide (particle size: 2 μm) and 0.1 part of hydrophobic colloidal silica were sufficiently stirred and mixed by a speed kneader to obtain a toner.

This toner was charged into a developing device as shown in FIG. 1, and continuous copying was performed, and an image test was performed.
Good images were obtained. The image did not change even after 50,000 sheets of images were displayed.

The developing method will be described. As shown in the drawing, 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. And
The toner worked on the sponge roller 4 is rotated by the sponge roller in the direction of the arrow, so that the toner conveying member 2 is rotated.
Transported, rubbed, electrostatically or physically adsorbed,
The toner conveying member 2 rotates strongly in the direction of the arrow, and a uniform toner thin layer is formed by the elastic blade 3 and is charged by friction. Thereafter, the latent image is transported to the surface of the electrostatic latent image carrier 1 which is in contact with or in proximity to the toner conveying member 2, and the latent image is developed.

The electrostatic latent image is formed by applying a negative DC voltage of 800 V to the organic photoreceptor, exposing it to form a latent image, and developing the image reversibly. Further, in order to measure the specific charge of the toner on the toner conveying member: Q / M, the toner on the toner conveying member is sucked through a Faraday cage having a filter layer on the outlet side, and trapped in the Faraday cage. The Q / M was measured by a specific charge measuring apparatus using a suction method for measuring the specific charge of the toner thus obtained. As a result, it was confirmed that the toner was sufficiently charged at -11.6 μc / g.

The amount of charge in the running of 50,000 sheets is-
10.2 μc / g was almost no difference from the initial value. Further, even under high and low humidity, image quality equivalent to that of normal humidity was obtained. Also, there was no toner filming on the photoconductor.

Example 6 Polyester resin (Lunaper 1447, Arakawa Chemical Co., Ltd.) 100 parts Polypropylene 5 parts Carbon black 10 parts 4-perfluorohexenyl oxostyrene polymer 3 parts Metal-containing monoazo dye (Bontron S-34 manufactured by Orient Chemical Industries) 1 part The raw material mixture having the above composition was melt-kneaded in the same manner as in Example 1,
After cooling, pulverization and classification, a black toner having a particle size of 5 to 25 μm was obtained. 2.5 parts of this toner was mixed with 97.5 parts of a carrier B coated with a silicone resin in a ball mill to obtain a developer.

Next, this developer was set in a copier FT7570 manufactured by our company as in Example 1, and an image test was performed. As in Example 1, a good image having high fidelity was obtained. The image did not change even after the 120,000 images were displayed.

When the charge amount of the toner was measured by a blow-off method, the initial charge amount was −22.5 μc / g, and the charge amount of the toner after running 120,000 sheets was −
It was 19.1 μc / g, which was almost the same as the initial value. In a high humidity environment of 35 ° C and 90% RH, and at 10 ° C and 15%
Even in a low humidity environment of RH, an image equivalent to normal humidity was obtained. There was no toner filming on the photoreceptor.

Example 7 A toner and a toner were used in the same manner as in Example 5 except that the carrier F was used.
When a developer was prepared and a similar image display test was carried out, a good image was obtained, and the image remained unchanged after 120,000 sheets of image were output.

When the charge amount of the toner was measured by a blow-off method, the initial charge amount was −23.3 μc / g, and the charge amount of the toner after running 120,000 sheets was −
20.2 μc / g was almost no difference from the initial value. However, ground fogging occurred from around 140,000 sheets. Up to 100,000 sheets in a high humidity environment of 35 ° C and 90% RH, and at 10 ° C
An image equivalent to normal humidity was obtained even under a low humidity environment of 15% RH. Also, there was no toner filming on the photoconductor.

Comparative Example 2 A developer was prepared and an image test was conducted in the same manner as in Example 4 except that the metal-containing monoazo dye was 1.5 parts except for the 4-perfluorohexenyloxostyrene polymer of Example 6. Was. In the initial image, fogging occurred a little and a poor image was obtained. From around 30,000 sheets, fog increased and the image became unclear. Further, when an image test was performed in a high humidity environment of 35 ° C. and 90% RH, the image density was as low as 0.92, and fog occurred. Also, when the charge amount was measured in the same manner as in Example 2, the initial charge amount was as low as -13.5 μC / g, and further decreased to −3.5 μC / g after 30,000 copies.

Example 8 100 parts of polyester resin (Lunapelle 1447 manufactured by Arakawa Chemical Co., Ltd.) 5 parts of candelilla wax 102 (manufactured by Noda Wax Co.) I. Pigment Red 57 5 parts C.I. I. Pigment Red 48 3 parts 4-Perfluorohexenyl oxostyrene polymer 5 parts Exemplified Compound II-2 0.5 parts The mixture having the above composition is sufficiently stirred and mixed in a Henschel mixer in the same manner as in Example 1, and then 110 in a roll mill. ~ 1
After heating and melting at a temperature of 20 ° C. for about 40 minutes and cooling to room temperature, the obtained kneaded material was pulverized and classified to obtain a 5 to 20 μm granular red toner. To 100 parts of the toner, 3 parts of silicon carbide (particle size: 2 μm) and 0.1 part of hydrophobic colloidal silica were sufficiently stirred and mixed by a speed kneader to obtain a toner.

This toner was developed in the same developing apparatus as in Example 3 and an image test was performed. As a result, a clear and good image was obtained, and the image did not change even after 50,000 sheets of image were output. .

As in Example 3, the Q / M was measured by a specific charge measuring apparatus using a suction method.
The charge was sufficient at μc / g, and the charge amount after running 50,000 sheets was −8.9 μc / g, which was almost the same as the initial value. Further, even under high and low humidity, image quality equivalent to that of normal humidity was obtained. Also, there was no toner filming on the photoconductor.

Examples 9 to 22 Toners and developers were obtained in the same manner as in Example 1 using the developer compositions shown in Table 2 below. Table 2 also summarizes the image properties and charging properties of these developers.

[0082]

[Table 3]

[0083]

[Table 4]

[0084]

[Table 5]

[0085]

As described above, by using the specific compound of the present invention as a charge control agent, an image having the same quality as the initial image can be obtained even after continuous copying, and stable negative friction can be obtained. A toner exhibiting chargeability is obtained. Further, a toner having good dispersibility in a binder resin and excellent environmental stability can be obtained, and a clear color image can be obtained.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram of an example of a developing device using a toner of the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 electrostatic latent image carrier 2 toner transport member 3 elastic blade 4 sponge roller 5 stirring blade 6 toner 7 toner tank

Continuation of front page (56) References JP-A-3-230169 (JP, A) JP-A-5-11489 (JP, A) JP-A-5-53367 (JP, A) JP-A-4-186367 (JP) JP-A-62-151410 (JP, A) JP-A-62-153236 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03G 9/097 G03G 9/087 CA (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. A developer mainly comprising a binder resin, a colorant and a charge control agent, wherein the charge control agent is perfluoroalkenyl polyvinyl phenyl ether represented by the following general formula I: Negatively chargeable developer for image development. Formula I Rf: a perfluoroalkenyl group of C _{6 to} C ₉ and F _{11 to} F ₁₇ n; a positive integer 2. The method according to claim 1, wherein the charge controlling agent comprises a perfluoroalkenyl polyvinyl phenyl ether represented by the general formula I and a fluorinated quaternary ammonium salt represented by the following general formula II. A negatively chargeable developer for developing a charge image. Formula II _{However, X; -SO 2 -, -} CO-. R ₁ , R ₂ , R ₃ , R ₄ ; H, a lower alkyl group having 1 to 10 carbon atoms and an aryl group. Y; I, Br m; positive integer P; positive integer 3. The negatively chargeable developer for electrostatic image development according to claim 1, wherein the binder resin is a polyester resin or an epoxy resin.