JPH0695435A - Negatively chargeable toner for developing electrostatic charge image - Google Patents

Abstract

PURPOSE:To provide a toner having satisfactory environmental stability, giving many multicolored copies and adaptable to a two-component developer. CONSTITUTION:A polymer contg. a monomer represented by the general formula (where R<1> is H, halogen, 1-10C alkyl or alpha-methylbenzyl) as monomeric units and having 2,000-100,000 wt. average mol.wt. is incorporated as an electric charge controlling agent into a toner.

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 charge image, and more specifically, a toner useful as a one-component or two-component developer used in electrophotography, electrostatic recording, electrostatic printing and the like. The present invention relates to a negatively chargeable toner for developing a charge image.

[0002]

2. Description of the Related Art Conventionally, as disclosed in Japanese Patent Laid-Open No. 61-147261, methods of developing an electrostatic charge image with toner are roughly classified, and so-called toner and carrier are mixed. There are a method of using a two-component developer and a method of using a one-component developer consisting of toner alone. In the above-mentioned method, the toner and the carrier are stirred and rubbed so that they are charged to different polarities, and an electrostatic image having opposite polarities is visualized by the charged toner. There are a magnetic brush method using an iron powder carrier, 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 to develop (also referred to as a touchdown developing method). , An induction developing method in which a magnetic conductive toner and an electrostatic latent image surface are brought into contact with each other. 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 a natural resin or a 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 the toner. 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 charge image to be developed. To make the toner have a charge, Although the triboelectric chargeability of the resin, which is a component of the toner, can be utilized, in this method, the toner has a low chargeability, and therefore the image obtained by development is easily fogged and becomes unclear. Therefore, in order to impart a desired triboelectric charging property to the toner, a dye that imparts the charging property,
A pigment or a charge control agent is added.

As the negative charge control agent, metal complex salts of monoazo dyes, nitrohumic acid and its salts, salicylic acid,
There are metal complexes of naphthoic acid, dicarboxylic acid such as Co, Cr and Fe, sulfonated copper phthalocyanine pigments, styrene oligomers containing nitro groups and / or halogens, chlorinated paraffins and melamine resins. The structure is complicated, the properties are not constant, and the stability is poor. In addition, during thermal kneading, decomposition or mechanical shock, friction, changes in temperature and humidity conditions, and the like are likely to cause decomposition or deterioration of the charge control property. Also, in many cases, the charging property changes depending on the environment. Furthermore, when a conventional toner containing the charge control agent is used for a long time, filming may occur on the photoreceptor due to poor charging.

On the other hand, recently, polyester resins and epoxy resins have been used as binder resins because they have both storage stability and low-temperature fixability without impairing the PVC matt fusion resistance and the original color of the color material of the color toner. It is often used. However, when a polyester resin or an epoxy resin is used as a binder resin in a toner, in any case, even if the charge amount is low, or even if it is high, the charge amount decreases with repeated use, causing fog, toner scattering, etc. There was a problem that it was difficult to do. It is considered that this is because functional groups such as —COOH and —OH groups remain in the polyester resin and the epoxy resin due to their chemical structures, which hinders maintaining stable chargeability.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to prevent frictional electrification between toner particles or between toner and carrier, between toner and a charging member such as a developing sleeve or blade in the case of one-component development. To provide a negatively-chargeable toner for electrostatic image development, which is stable, has a triboelectric charge amount distribution that is sharp and uniform, has good charge rising property and environmental stability, and can be controlled to a charge amount suitable for the developing system used. It is a thing. Another object of the present invention is to provide a vivid color toner. Still another object of the present invention is that there is no background stain and toner scattering, there is no deterioration of image quality due to edge phenomenon and charge accumulation phenomenon, and peeling of the carrier coating layer and separation of conductive fine powder even during continuous use. Therefore, the toner provides stable triboelectricity and is useful for application to a two-component developer capable of obtaining a large number of copies of images having high fidelity equivalent to the initial image.

[0007]

The present invention relates to a negatively chargeable toner for developing an electrostatic charge image containing a colorant, a binder resin and a charge control agent as main components, wherein the charge control agent is represented by the following general formula (1). The polymer is characterized by having a weight average molecular weight of 2,000 to 100,000, which is a polymer containing the monomer as a monomer unit.

[Chemical 1] (In the formula, R ¹ is a hydrogen atom, a halogen atom, or a carbon number of 1 to 1.
An alkyl group of 0 or an α-methylbenzyl group. )

In the toner of the present invention, it is also effective to use a metal-containing azo dye and / or a fluorine-containing quaternary ammonium salt compound in combination with the above as a charge control agent.
It is also effective to use a polyester resin or an epoxy resin as the binder resin.

The inventors of the present invention have studied various aspects of negatively chargeable toner for electrostatic image development, and as a result,
It was confirmed that a polymer containing the monomer represented by the general formula (1) as a monomer unit and having a weight average molecular weight within a certain range works well as a charge control agent. The present invention has been made on the basis thereof.

The present invention will be described in more detail below. The present invention provides a negatively chargeable toner for developing an electrostatic charge image by improving the above-mentioned conventional drawbacks by incorporating a polymer having a specific weight average molecular weight of 2000 or more and 100000 or less as a charge control agent in the toner. Here, if the weight average molecular weight of the polymer is less than 2000, the resin may become tacky at room temperature, resulting in poor fluidity and storage stability of the toner, and poor development characteristics and blocking of the toner. Occurs. The weight average molecular weight of the polymer is 1,000.
If it exceeds 00, the dispersibility in the binder resin and the pulverizability at the time of production become poor, the charge of the toner becomes non-uniform, the fog on the copy image and the toner scattering at the developing portion occur, and the productivity at the time of production becomes low. Economic efficiency.

The polymer of the present invention can be used not only as a polymer containing only the monomer represented by the above-mentioned general formula (1) but also as a copolymer with other vinyl monomers. Typical examples of the vinyl-based monomer copolymerizable with the monomer of the general formula (1) include styrene, acrylic acid ester, methacrylic acid ester, acrylonitrile, vinyl acetate and vinyl pyridine. The molar ratio of the copolymer of the monomer of the general formula (1) and the vinyl monomer is 10: 90-10.
0: 0 is suitable. Specific examples of these homopolymers or copolymers of these monomers and vinyl monomers are shown in Table 1 below.
, Which are all white or light in color.

[0012]

[Table 1- (1)]

[Table 1- (2)]

[Table 1- (3)]

[Table 1- (4)]

In the present invention, if the polymer and the metal-containing azo dye are used together as a charge control agent, a toner having a better negative charging property can be obtained. Further, even if the above polymer and the fluorine-containing quaternary ammonium salt compound represented by the general formula (2) proposed in JP-A-3-213877 are used together as a charge control agent, good negative chargeability is obtained. Toner (especially color toner) is obtained.

[Chemical 2] _{(However, X;... -SO 2} - or ^{-CO- R 2, R 3, R} 4, R 5; H, lower alkyl group having 1 to 10 carbon atoms, or an aryl group Y; I or Br n; Positive integer m. Positive integer.)

As the above-mentioned metal-containing azo dye, any of those currently on the market can be used. For example, Hozenya Chemical Co., Ltd. Aizen spirone black TRH, Aizen color T-37, 77, 95, Orient Chemical Co., Ltd. Bontron S-32, 34, 40, 44, etc., but not limited to these. Absent. In addition, the above general formula (2)
Specific examples of the compound represented by are shown in Table 2, and all of them show white or pale yellow.

[0015]

[Table 2]

As the colorant used in the present invention, carbon black, lamp black, iron black, ultramarine blue, nigrosine dye, aniline blue, phthalocyanine blue, phthalocyanine green, hansa yellow G, rhodamine 6
Any conventionally known dyes and pigments such as G, lake, chalco oil blue, chrome yellow, quinacridone, benzidine yellow, rose bengal, triallylmethane type dye, monoazo type and disazo type may be used alone or in combination.

As the binder resin used in the present invention, a homopolymer of styrene such as polystyrene, poly-p-chlorostyrene and polyvinyltoluene or a substitution product thereof;
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-maleic acid copolymers, styrene copolymers such as styrene-maleic acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, polyurethane, polyamide, Epoxy resin, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin,
Examples thereof include terpene resins, aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins and paraffin wax, which may be used alone or in combination.

Particularly, as the binder resin suitable for pressure fixing, the following can be used alone or in combination. Polyolefin (low molecular weight polyethylene, low molecular weight polypropylene, oxidized polyethylene polytetrafluoroethylene, etc.), epoxy resin, polyester resin, styrene-butadiene copolymer (monomer ratio 5 to 30:95 to 7)
0), olefin copolymer (ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-vinyl chloride copolymer, Examples thereof include ethylene-vinyl acetate copolymer, Iomer resin), and polyvinylpyrrolidone resin.

Particularly, the polyester resin useful in the present invention is obtained by polycondensation of alcohol and carboxylic acid. Here, as the alcohol, for example, polyethylene glycol, diethyllen glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-propylene glycol,
Diols such as neopentyl glycol and 1,4-butenediol, ethers such as 1,4-bis (hydroxymethyl) cyclohexane, bisphenol A, hydrogenated bisphenol A, polyoxyethylenated bisphenol A, polyoxypropyleneated bisphenol A Bisphenols, divalent alcohol units obtained by substituting them with a saturated or unsaturated hydrocarbon group having 3 to 22 carbon atoms, other divalent alcohol units, sorbitol,
1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaethritol, sucrose, 1,2,4-butanetriol, 1,2, 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.

The carboxylic acid used to obtain the polyester resin includes, for example, palmitic acid, stearic acid, oleic acid and other monocarboxylic acids, maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid. 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, anhydrides of these acids, dialkyls of lower alkyl esters and linoleic acid. Monomer, other divalent organic acid monomer,
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
-Trivalent or higher polyvalent carboxylic acid monomers such as methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid embol trimer acid, and anhydrides of these acids. Can be mentioned.

The useful epoxy resin of the present invention is a polycondensation product of bisphenol A and epichlorohydrin, for example, Epomic R362, R36.
4, R365, R366, R367, R369 (above,
(Mitsui Petrochemical Industry Co., Ltd.), Epotote YD-011, Y
D-012, YD-014, YD-904, YD-01
7, (Made by Tohto Kasei Co., Ltd.), Epicoat 1002, 1
Commercially available products such as 004, 10007 (all manufactured by Shell Chemical Co., Ltd.) can be used.

The amount of the polymer of the monomer represented by the general formula (1) used as the charge control agent in the present invention or the copolymer of the monomer and the vinyl monomer is
It is determined by the kind of the binder resin, the presence or absence of additives used as necessary, and the toner manufacturing method including the dispersion method, and is not uniquely limited, but is based on 100 parts by weight of the binder resin. 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight. 0.
If it is less than 1 part by weight, the negative charging of the toner is insufficient, which is not practical. On the contrary, if it exceeds 20 parts by weight, the electrostatic property of the toner is too large and the electrostatic attraction with the carrier increases, so that the developer is not used. Fluidity and image density.

The toner of the present invention may further contain a magnetic material and be used as a magnetic toner. The magnetic materials contained in the magnetic toner include magnetite, hematite,
Metals such as iron oxides such as ferrite, iron, cobalt, nickel, or aluminum, cobalt, etc. of these metals
Conventionally known materials such as alloys of metals such as copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium and mixtures thereof can be used. These ferromagnetic materials have an average particle size of 0.1 to 2 μ.
The amount of m is preferably about 20 to 200 parts by weight, preferably 40 to 150 parts by weight, based on 100 parts by weight of the resin component.

Additives may be added to the toner of the present invention as required. Examples of the additives include fluororesin fibers, lubricants such as zinc steanate, abrasives such as cerium oxide and silicon carbide, fluidity imparting agents such as colloidal silica and aluminum oxide, anti-caking agents, or carbon black. , Tin oxide, and other conductivity-imparting agents, and low-molecular-weight polyolefins and other fixing aids.

When the toner of the present invention is used as a two-component developer, it is used as a mixture with carrier powder. As the carrier used in the present invention, all known carriers can be used, for example, iron powder, ferrite powder, magnetic powder such as nickel powder, glass beads, etc., and their surfaces treated with a resin or the like. The thing etc. are mentioned.

The carrier obtained by coating the surface of the core particles with the silicone resin containing the conductive fine powder and the silane coupling agent maintains the advantages of the conventional silicone resin-coated carrier. By imparting conductivity to the carrier, the phenomenon of charge accumulation in the carrier, the peeling of the coating layer, and the detachment of the conductive fine powder are effectively suppressed. Particularly, an aminosilane coupling agent having a primary and / or secondary amino group is suitable for controlling the negative charge of the toner.

The carrier core particles coated with a silicone resin may be conventionally known ones, and examples thereof include ferromagnetic metals such as iron, cobalt and nickel; alloys and compounds such as magnetite, hematite and ferrite; glass beads and the like. To be The average particle size of these core particles is usually 10 to
The thickness is 1000 μm, preferably 30 to 500 μm. The amount of the silicone resin used is usually 1 to 10% by weight based on the carrier core particles.

The silicone resin may be any conventionally known silicone resin, for example, commercially available KR261 and K manufactured by Shin-Etsu Silicone Co., Ltd.
R271, KR272, KR275, KR280, KR
282, KR285, KR251, KR155, KR2
20, KR201, KR204, KR205, KR20
6, SA-4, ES1001, ES1001N, ES1
002T, KR3093 or Toray Silicone SR2
100, SR2101, SR2107, SR2110,
SR2108, SR2109, SR2115, SR24
00, SR2410, SR2411, SH805, SH
806A, SH840 and the like. 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 method such as a spraying method or a dipping method as in the conventional method.

The coating layer composition is prepared by adding conductive fine powder and a silane coupling agent to a silicone resin solution and dispersing them with an appropriate mixer.

The conductive fine powder dispersed in the coating layer is
Particles having a particle size of about 0.01 to 5.0 μm are preferable, and 0.01 to 30 parts by weight is preferably added to 100 parts by weight of the silicone resin, and more preferably 0.1 to 20 parts by weight. As the conductive fine powder, conventionally known carbon black may be used, and examples thereof include contact black, furnace black and thermal black.

The silane coupling agent is a compound represented by the general formula (3) X-Si (OR ⁶ ) ₃ (3), wherein X is a functional group which reacts with an organic substance, and R ⁶ is hydrolyzable. It is a base. Particularly, 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. Specific examples of the aminosilane coupling agent include those shown in Table 3 below.

[0032]

[Table 3- (1)]

[Table 3- (2)]

[Table 3- (3)]

Next, production examples of carriers having some silicone resins in the coating layer will be shown. These can be performed by known means.

Carrier Particle Production Example 1 Composition of Coating Layer Forming Liquid Silicone resin solution (KR250 manufactured by Shin-Etsu Silicone Co., Ltd.) 100 parts by weight A mixture of 100 parts by weight of toluene was dispersed for 30 minutes with a homomixer to prepare a coating layer forming liquid. . This coating layer forming liquid has an average particle size of about 1
A carrier A having a coating layer formed on the surface of 1000 parts by weight of spherical ferrite having a diameter of 00 μm by using a fluidized bed type coating apparatus was obtained.

Carrier Particle Production Examples 2 to 12 Each component shown in Table 4 below and 100 parts by weight of toluene were mixed and dispersed for 30 minutes with a homomixer to prepare a coating layer forming liquid. In Table 3, the parts of the prescription amount are parts by weight.

[0036]

[Table 4] Carriers B, C, D, E, F, G, H, which are coated with the coating layer forming liquid on the surface of 1000 parts by weight of spherical ferrite having an average particle diameter of about 70 μm using a fluidized bed type coating apparatus,
I, J, K, L were obtained.

[0037]

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

Example 1 Styrene-2-ethylhexyl acrylate copolymer 100 parts C.I. I. Pigment Blue 15 5 parts Exemplified Compound No. 1-1 (weight average molecular weight 5000) 5.0 parts by sufficiently stirring and mixing the mixture in a Henschel mixer, followed by heating and melting with a roll mill at a temperature of 130 to 140 ° C. for about 30 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 100-250 mesh iron powder carrier were mixed by a ball mill to obtain a two-component developer. Next, the above developer was set in a commercially available electrophotographic copying machine (FT5570, manufactured by Ricoh Co., Ltd.),
Upon development, a good image was obtained, and the image remained unchanged after 100,000 images were printed. Further, when the toner charge amount was measured by the blow ota method, the initial charge amount was -16.8 μC / g, and the toner charge amount after running 100,000 sheets was almost the same as -14.5 μC / g. It was Further, even under a high humidity environment of 35 ° C. 90% RH and a low humidity environment of 10 ° C. 15% RH, images equivalent to those at room temperature were obtained. Further, there was no toner filming on the photoconductor.

Example 2 A toner was prepared in the same manner as in Example 1 except that the carrier C was used.
When a developer was prepared and a similar image forming test was carried out, a good image was obtained, and the image did not change even after 100,000 images were formed. Further, when the charge amount of the toner was measured by the blow-off method, the initial charge amount was -16.2 μC.
The charge amount of the toner after running 100,000 sheets was -15.1 μC / g, which was almost the same as the initial value. Also, up to 100,000 sheets, images equivalent to those at room temperature were obtained even in a high humidity environment of 35 ° C. 90% RH and a low humidity environment of 10 ° C. 15% RH. Further, there was no toner filming on the photoconductor.

Example 3 Polyester resin (Luna Pale 1438-6 manufactured by Arakawa Chemical Co., Ltd.) 100 parts Polypropylene 5 parts Carbon black 10 parts Exemplified Compound No. A raw material mixture having a composition of 1-1 (weight average molecular weight 22000) 5 parts was melt-kneaded, cooled, pulverized and classified in the same manner as in Example 1 to obtain a black toner having a particle diameter of 5 to 25 μm. 2.5 parts of this toner and 97.5 parts of carrier A coated with a silicone resin were mixed by a ball mill to obtain a developer. Next, this developer was set in the copying machine FT7570 of Example 1 and an image test was carried out. As a result, a good image with high sharpness was obtained as in the case of the example. Did not change. Also,
When the toner charge amount was measured by the blow-off method, the initial charge amount was -17.1 μC / g, and the toner charge amount after running 120,000 sheets was -16.3 μC / g, which was almost the same as the initial value. There wasn't. Also, 35 ° C 90% R
Even under a high temperature environment of H and a low temperature environment of 10 ° C. and 15% RH, an image equivalent to normal temperature was obtained. There was also no toner filming on the photoconductor.

Example 4 A toner and a developer were prepared in the same manner except that the carrier F was used and the polyester resin of Example 3 was changed to the styrene-2-ethylhexyl acrylate copolymer of Example 1 to obtain the same image. When the output test was carried out, a good image was obtained, and the image image did not change even after the output of 120,000 images. When the charge amount of the toner was measured by the blow-off method, the initial charge amount was -17.3 μC / g, and the toner charge amount after running 120,000 sheets was-.
There was almost no difference from the initial value of 16.1 μC / g. However, the ground fogging occurred from around 130,000 sheets. Also, 12
Up to 10,000 sheets under high humidity environment of 35 ° C 90% RH and 10
Even under a low humidity environment of 15 ° C. and 15% RH, an image equivalent to normal temperature was obtained. Further, there was no toner filming on the photoconductor.

Comparative Example 1 Exemplified compound No. 1 of Example 1 Instead of 1-1, zinc salicylate (manufactured by Orient Chemical Industry, Bontron E-8
A developer was prepared and an image test was conducted in the same manner as in Example 1 except that 4) was used. A clear image without fog was obtained as the initial image, but an unclear image with fog was obtained from about 50,000 sheets, and toner filming was observed on the surface of the photoconductor. Further, when an image test was performed in a high humidity environment of 35 ° C. and 90% RH, the image density was low at 0.85, 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 μ.
Although it was C / g, it decreased to −9.8 μC / g after 50,000 sheets.

Example 5 Epoxy resin (R365, manufactured by Mitsui Petrochemical Co., Ltd.) 80 parts Epoxy resin (YD-017, manufactured by Tobu Kasei Co., Ltd.) 20 parts C.I. I. Pigment Blue 15 5 parts C.I. I. Pigment Yellow 17 5 parts Exemplified Compound No. 1-1 (weight average molecular weight 2100) 6 parts of a mixture having a composition of sufficient stirring and mixing in a Henschel mixer, followed by heating and melting with a roll mill at a temperature of 130 to 140 ° C. for about 30 minutes, and cooling to room temperature to obtain the product. The kneaded product was pulverized and classified to obtain a green finely pulverized product having a particle size of 5 to 20 μm. To 100 parts of this green finely pulverized product, 3 parts of silicon carbide (particle size: about 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 loaded into a developing device as shown in FIG. 1, continuous copying was carried out, and an image test was conducted, a good image was obtained. The image did not change after 50,000 images were printed.

To explain this image method, as shown in the drawing, the toner 6 contained in the toner tank 7 is forcibly drawn to the sponge roller 4 by the stirring blade 5, and the toner is supplied to the sponge roller 4. As the sponge roller rotates in the direction of the arrow, the toner taken into the sponge roller 4 is conveyed to the toner conveying member 2 and is rubbed, electrostatically or physically adsorbed, and strongly adhered to the toner conveying member 2 in the arrow direction. The elastic blade 3 is rotated to form 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 subjected to negative DC charging of 800 V, for example, on the organic photoconductor, and then exposed to form a latent image, which is reversely developed. In order to measure the specific charge amount Q / M of the toner on the toner conveying member, the toner on the toner conveying member is sucked through a Faraday cage equipped with a filter layer on the outlet side and trapped in the Faraday cage. When the Q / M was measured by a suction method specific charge amount measuring device for measuring the specific charge of the toner, it was confirmed that the toner was sufficiently charged with −9.5 μC / g. The charge amount after running 50,000 sheets was −8.7 μC / g, which was almost the same as the initial value. Further, even under high humidity and low humidity, image quality equivalent to room temperature was obtained. Furthermore, there was no toner filming on the photoconductor.

Example 6 Polyester resin (Luna Pale 1438-6, manufactured by Arakawa Chemical Co., Ltd.) 100 parts Polypropylene 5 parts Carbon black 10 parts Exemplified Compound No. 1-2 (weight average molecular weight 8600) 3.0 parts Metal-containing monoazo dye 1.0 part (Orient Chemical Co., Ltd., Bontron S-34) A raw material mixture having a composition of melt-kneading in the same manner as in Example 1, After cooling, crushing and classification, a black toner having a particle size of 5 to 25 μm was obtained. 2.5 parts of this toner and 97.5 parts of carrier B coated with a silicone resin were mixed by a ball mill to obtain a developer. Next, this developer was set in the copying machine FT7570 of Example 1 and an image test was performed. As with Example 1, a good image with high fidelity was obtained, and the image was 150,000 sheets. It didn't change after it was served.
When the charge amount of the toner was measured by the blow-off method, the initial charge amount was -18.9 μC / g, and the toner charge amount after running 150,000 sheets was -18.2 μC.
There was almost no difference between C / g and the initial value. Furthermore, 3
5 ℃ 90% RH high temperature environment and 10 ℃ 15% RH
Even under such a low temperature environment, an image equivalent to normal temperature was obtained.
There was no toner filming on the photoreceptor.

Example 7 A toner and a developer were prepared in the same manner as in Example 6 except that the carrier F was used, and a similar image output test was conducted. As a result, a good image was obtained, and the image was 120,000. It did not change after the images were printed. Further, when the charge amount of the toner was measured by the blow-off method, the initial charge amount was -17.3.
μC / g, and the toner charge amount after running 120,000 sheets was −16.1 μC / g, which was almost the same as the initial value. A ground cover occurred from around 130,000 sheets, but 12
Up to about 10,000 sheets, images equivalent to those at room temperature were obtained even in a high humidity environment of 35 ° C. 90% RH and a low humidity environment of 10 ° C. 15% RH. Also, there was no toner filming on the photoconductor.

Comparative Example 2 Exemplified compound No. 6 of Example 6 was used. A toner was prepared and an image test was conducted in the same manner as in Example 4 except that 1-2 was used and the amount of the metal-containing monoazo dye was changed to 1.5 parts. As a result, the initial image was slightly fogged and a poor image was obtained. From around the 30,000th sheet, the fog increased and the image became unclear. Also,
When an image test was performed in a high humidity environment of 35 ° C. and 90% RH, the image density was low at 0.92 and fogging occurred. When the toner 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 was lowered to -3.5 μC / g after 30,000 sheets.

Example 8 Polyester resin (manufactured by Arakawa Chemical Co., Luna Pale 1447) 100 parts Candelilla wax 102 (manufactured by Noda Wax Company) 5 parts C.I. I. Pigment Red 57 5 parts C.I. I. Pigment Red 48 3 parts Exemplified Compound No. A raw material mixture having a composition of 1-3 (copolymer having a molar ratio of 50:50, 7.5 parts by weight average molecular weight of 9200) was thoroughly stirred and mixed in a Henschel mixer in the same manner as in Example 1, and then was rolled. After heating and melting at a temperature of 110 to 120 ° C. for about 40 minutes and cooling to room temperature, the obtained kneaded product is pulverized and classified to 5 to 20 μm.
A red toner having a particle diameter of m was obtained. To 100 parts of this red toner, 3 parts of silicon carbide (particle size: about 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 developed with the developing device shown in FIG. 1 and an image test was conducted, a clear and good image was obtained, and the image did not change even after 50,000 sheets were printed. When the Q / M of the toner was measured by the suction method specific charge amount measuring device in the same manner as in Example 3, the initial value was -11.
Sufficient charging was shown at 5 μC / g, and the charge amount during running of 50,000 sheets was −10.7 μC / g, which was almost the same as the initial value. Also, image quality equivalent to normal humidity was obtained under high and low humidity. Furthermore, there was no toner filming on the photoconductor.

Example 9 In Example 1, the compound No. 1 exemplified as the charge control agent was used. 1-
When tested in the same manner as in Example 1 except that 11 (Mw = 6000) was used, excellent results were obtained as in Example 1. The initial charge amount was −15.3 μC, and it was −14.1 μC for the 100,000th sheet.

Example 10 In Example 3, as the charge control agent, Exemplified Compound No. 1-
When tested in the same manner as in Example 3 except that 11 (Mw = 20,000) was used, excellent results were obtained as in Example 3. The initial charge amount was -14.8 μC, and it was -13.9 μC on the 120,000th sheet.

Example 11 In Example 6, as the charge control agent, Exemplified Compound No. 1-
When tested in the same manner as in Example 6 except that 14 (Mw = 7000) was used, excellent results were obtained as in Example 6. The initial charge amount was -18.7 μC, and it was -18.0 μC on the 150,000th sheet.

Example 12 In Example 8, the compound No. exemplified as the charge control agent was used. 1-
When tested in the same manner as in Example 8 except that 15 (Mw = 7500) was used, the same excellent results as in Example 8 were obtained. The initial charge amount was −8.5 μC, and −50,000 μC was −7.4 μC.

Examples 13 to 26 Developers were obtained in the same manner as in Example 1 with the compositions shown in Tables 5 and 6 below. The imageability and chargeability of these developers are also summarized in Tables 5 and 6.

[0055]

[Table 5]

[Table 6]

[0056]

According to the first aspect of the present invention, by using a specific compound 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 is obtained. A toner having chargeability is obtained. Further, the dispersibility in the binder resin is good, a toner having excellent environmental stability is obtained, and a clear color image is obtained. Claim 2
According to the invention, a toner having a better negative charging property can be obtained. According to the invention of claim 3, the fixing property of the toner is further improved.

[Brief description of drawings]

FIG. 1 is a diagram showing an outline of an electrophotographic copying apparatus using a toner 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) Inventor Fumihiro Sasaki 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd.

Claims (3)

[Claims] 1. A toner containing a colorant, a binder resin and a charge control agent as a main component, wherein the charge control agent is a polymer containing a monomer represented by the following general formula (1) as a monomer unit. A negatively chargeable toner for developing an electrostatic charge image, which has an average molecular weight of 2,000 to 100,000. [Chemical 1] (In the formula, R ¹ is a hydrogen atom, a halogen atom, or a carbon number of 1 to 1.
An alkyl group of 0 or an α-methylbenzyl group. ) 2. The negatively chargeable toner for electrostatic image development according to claim 1, further comprising a metal-containing azo dye and / or a fluorine-containing quaternary ammonium salt compound as the charge control agent. 3. The negatively chargeable toner for electrostatic image development according to claim 1, wherein the binder resin is a polyester resin or an epoxy resin.