JP3258094B2 - Negatively chargeable 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 frictional charging property to the toner, a dye, a pigment, or a charge control agent that imparts the 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 the use time, and it is necessary to replace the entire developer.

[0009]

SUMMARY OF THE INVENTION According to the present invention, the friction between toner particles or the friction between toner and carrier particles, the frictional charge between the toner in the case of one-component development and the charging member such as a developing sleeve or a blade, is reduced. Be stable.
Furthermore, the triboelectric charge amount is sharp and uniform, and the charge rising property and environmental stability are good. An object of the present invention is to provide a toner that can be adjusted to a charge amount suitable for a developing system to be used.

Another object of the present invention is to provide a vivid color toner, and to provide a toner capable of forming an image having the same characteristics as an initial image even in continuous use.

[0011]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a terpene diphenol compound represented by the following general formula I is used in a toner containing a binder resin, a colorant and a charge control agent as main components. By incorporating it as a charge control agent, a negatively chargeable toner for developing an electrostatic image, which improves the above-mentioned conventional disadvantages, can be obtained.

Formula I

[0013]

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The compound has good charging properties even when the binder resin is a polyester resin or an epoxy resin, and is most suitable as a toner charge controlling agent for low-temperature fixability. When the compound is used in combination with a fluorinated quaternary ammonium salt compound represented by the general formula II as a charge control agent, a toner having a more favorable negative charge property, in particular, a color toner can be obtained.

[0015]

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(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; a positive integer n; a positive integer 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 and the amount used if necessary. It is determined by the toner manufacturing method including the presence or absence of the additive to be used and the dispersion method, and is not limited to a specific one.
It is used in the range of 1 to 20 parts by weight with respect to 00 parts by weight. Preferably, the range is 2 to 10 parts by weight. If the amount is less than 1 part by weight, negative charging of the toner is not sufficient. If the amount exceeds 20 parts by weight, the fluidity, the image density, and the low-temperature fixability decrease.

Typical examples of the compound represented by the general formula II which is used as a negative charge control agent together with the compound represented by the general formula I include the following compounds. Shows pale yellow.

[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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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, phenolic resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin,
Examples thereof include paraffin wax, which can be used alone or in combination.

Further, 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 3)
0: 95-70), 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, and the like. 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-carboxyl-2-
Trivalent or higher polycarboxylic acids such as methyl-2-methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid embol trimer acid, and anhydrides of these acids. Mers.

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, chalco oil blue, chrome yellow, quinacridone, benzidine yellow, rose bengal, triallylmethane dye, monoazo dye, disazo dye, pigment, 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 which can be used in the present invention, all known carriers can be used. For example, magnetic powders such as iron powder, ferrite powder and nickel powder, glass beads, etc. And the like.

For example, by coating the surface of the toner particles with a silicone resin containing a conductive fine powder and a silane coupling agent, the advantage of the conventional silicone resin-coated carrier can be maintained in the same manner, and at the same time, the carrier can be electrically conductive. By imparting the property, the charge accumulation phenomenon in the carrier, the peeling of the coating layer, and the detachment of the conductive fine powder can be effectively suppressed. In particular, an aminosilane coupling agent having a primary or secondary amino group is suitable for imparting a negative charge to the toner.

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 based on 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 to these examples. All parts are parts by weight.

As the carrier core particles coated with the silicone resin in the present invention, conventionally known carrier core particles may be used, 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.

As the silicone resin used in the present invention, any conventionally known silicone resin may be used. 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 the mixture with an appropriate mixer.

The conductive fine powder dispersed in the coating layer is
The particles preferably have a particle size of about 0.01 to 5.0 μm, and are preferably added in an amount of 0.01 to 30 parts by weight, more preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the silicone resin. 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) aminopropyl methyl dimethoxy silane, .gamma. anilinium Roh trimethoxysilane,
Octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride;
Aminosilane coupling agents containing at least one secondary and / or secondary amino group are preferred.

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 liquid 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 for 30 minutes using a homomixer to prepare a coating layer forming liquid. 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.

[0048]

[Table 1]

[0049]

[Table 2]

A carrier B, C, D, E, and a carrier were prepared by forming a coating layer 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.

[0051]

The present invention will be specifically described below with reference to examples. The amounts ( parts ) of the components described in the examples are parts by weight.

Example 1 100 parts of styrene-2-ethylhexyl acrylate copolymer I. Pigment Blue 15 5 parts Terpene diphenol YP-90 [Yashara Chemical Co., Ltd. melting point 85 ° C, purity 90%] 5 parts The mixture of the above composition is sufficiently stirred and mixed in a Henschel mixer, and then a temperature of 130 to 140 ° C by a roll mill. About 3
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.

For 2.5 parts of the toner, 100 to 25
97.5 parts of a 0 mesh ferrite carrier were mixed by a ball mill to obtain a developer. Next, the above developer was set on an FT7570 made by our company, and development was performed. As a result, a good image was obtained, and the image did not change even after 100,000 sheets of images were output.

When the charge amount of the toner was measured by a blow-off method, the initial charge amount was −16.5 μC / g, and the charge amount of the toner after running 100,000 sheets was −
At 14.7 μC / g, there was almost no difference from 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 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 −15.4 μc / g, and the charge amount of the toner after running 100,000 sheets was −
13.9 μc / g was almost the same as 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.

[0057] Example 3 Polyester resin (manufactured by Arakawa Chemical Industries, Ltd. Runaperu 1438-6) 100 parts of polypropylene 5 parts of carbon black 10 parts terpene diphenol YP-9 0 {Yasuhara Chemical Co. Melting point 85 ° C., 90% pure} 8 parts 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.

To 2.5 parts of the 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 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 sharpness 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 −19.3 μC / g, and the charge amount of the toner after running 120,000 sheets was −
At 17.5 μC / g, there was almost no difference from 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 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 −18.5 μc / g, and the charge amount of the toner after running 120,000 sheets was −
16.2 μc / g was almost the same as the initial value. However, ground fogging occurred from around 130,000 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 Instead of the terpene diphenol compound of Example 1, zinc salicylate (Bontron E-manufactured by Orient Chemical Industries, Ltd.)
A developer was obtained and an image test was conducted in the same manner as in Example 1 except that 2 parts of Compound (84) were used. 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 in a high humidity environment of 35 ° C. and 90% RH, the image density was as low as 0.85.
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 .mu.C / g, but after 50,000 sheets, it decreased to -9.8 .mu.C / g. Was.

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 of terpene diphenol YP-9 0 {Yasuhara Chemical Co. Melting point 85 ° C., 90% pure} Like 3 parts mixture of the above composition as in Example 1, were thoroughly stirred and mixed in a Henschel mixer, 130-1 with 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.

The toner was charged into a developing device as shown in FIG. 1, and continuous copying 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 charge 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 the Faraday cage When the Q / M was measured by a specific charge measuring apparatus for a suction method for measuring the specific charge of the toner trapped in the inside, it was confirmed that the toner was sufficiently charged at -8.4 μC / g.

The amount of charge in running 50,000 sheets is-
At 7.5 μC / g, there 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 6 100 parts of polyester resin (Lunapelle 1447 manufactured by Arakawa Chemical Co., Ltd.) 5 parts Polypropylene (Viscol 660P manufactured by Sanyo Chemical Co., Ltd.) 5 parts Carbon black 10 parts Terpene diphenol YP-90 [Yasuhara Chemical Co., Ltd. melting point 85 ° C., purity 90 %] 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.

To 2.5 parts of the toner, 97.5 parts of a carrier B coated with a silicone resin were mixed by a ball mill to obtain a developer. Next, this developer was set in a copier FT7570 made by our company as in Example 1, and an image test was performed. As in Example 1, a good image with high fidelity 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 −19.6 μC / g, and the toner charge amount after running 150,000 sheets was −
18.3 μC / g was almost no difference from 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 −16.4 μc / g, and the charge amount of the toner after running 120,000 sheets was −
At 14.8 μc / g, there was almost no difference from the initial value. However, ground fogging occurred from around 130,000 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. Also, there was no toner filming on the photoconductor.

Comparative Example 2 A developer was prepared in the same manner as in Example 4 except that the metal-containing monoazo dye was changed to 1.5 parts except for the terpene diphenol of Example 6, and an image test was performed. 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. Also, 35% 90% R
When an image test was performed in a high-humidity environment of H, the image density was as low as 0.92, and fog occurred.

When the charge amount was measured in the same manner as in Example 2, the initial charge amount was as low as -13.5 .mu.C / g, and further decreased to -3.5 .mu.C / g after 30,000 copies. .

Example 8 100 parts of a 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 Terpene diphenol YP-90 [Yasuhara Chemical Co., Ltd. melting point 85 ° C, purity 90%] 7.5 parts After sufficiently stirring and mixing the mixture having the above composition in a Henschel mixer as in Example 1, 110-1 on a roll mill
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 carried out. 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.
It showed a sufficient charge of μc / g, and the charge amount after running 50,000 sheets was -9.3 μC / g, which was almost the same as the initial value.

Further, an image quality equivalent to that of normal humidity was obtained under high and low humidity. 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 with the developer compositions shown in Tables 3 to 5 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 conveying member 3 elastic blade 4 sponge roller 5 stirring blade 6 toner 7 toner tank

Continuation of the front page (56) References JP-A-61-3149 (JP, A) JP-A-61-260253 (JP, A) JP-A-63-266462 (JP, A) JP-A-3-7955 (JP) JP-A-3-146964 (JP, A) JP-A-2-230163 (JP, A) JP-A-4-3076 (JP, A) JP-A-3-213877 (JP, A) JP 55-50251 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03G 9/08 CA (STN)

Claims (3)

(57) [Claims] A negative charge for developing an electrostatic image, wherein the charge control agent is a compound represented by the following general formula I in a developer containing a binder resin, a colorant and a charge control agent as main components. Developer. Formula I 2. The negatively chargeable developer for developing an electrostatic image according to claim 1, further comprising a compound represented by the following general formula II together with the compound represented by the general formula I as a charge control agent. 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, an aryl group Y; I, Br m; positive Integer n; 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.