JPH0777839A - Negatively chargeable toner for developing electrostatic charge image - Google Patents

Abstract

PURPOSE:To provide a stable negatively chargeable toner having satisfactory triboelectric chargeability. CONSTITUTION:This toner is based on a resin binder, a colorant and an electric charge controlling agent contg. a copolymer contg. a monomer represented by general formula I and having 1,500-10,000 number average mol. wt. A compd. represented by general formula II may further be used. In formula I, each of R<1>-R<3> is H, 1-8C lower alkyl or aryl, M<n+> is K<+>, Na<+>, Ca<2+>, Mg<2+> or Al<3+> and (n) is a positive integer. In formula II, X is -SO2- or -CO-, each of R<4>-R<7> is H, 1-10C lower alkyl or aryl, Y is I or Br, (m) is a positive integer and (n) is a positive integer.

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 negative charging.

[0002]

2. Description of the Related Art Conventionally, as disclosed in JP-A-61-147261, a method of developing an electrostatic image with toner is roughly classified, and so-called two-component development in which toner and carrier are mixed. There is a method of using a developer, and a method of using a one-component developer which is used alone without being mixed with a carrier. 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 for development (also referred to as a touchdown phenomenon. In other words, there is an induction developing method in which a magnetic conductive toner is brought into contact with the electrostatic latent image surface. As the toner applied to these various developing methods, fine powder in which a colorant such as carbon black is dispersed in a binder resin made of 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 toners. Further, a magnetic toner containing these components further containing a magnetic material such as magnetite is used.

As described above, the toner used in various developing methods has a positive or negative charge depending on the polarity of the electrostatic image to be developed. In order to allow the toner to retain an electric charge, the triboelectric charging property of the resin, which is a component of the toner, can be used, but in this method, the toner charging property is small, so the image obtained by development is easily fogged and is not clear. Will be things. Therefore, in order to impart a desired triboelectric chargeability to the toner, a dye, a pigment or a charge control agent which imparts the chargeability is added. Conventionally, as the negative charge control agent, a metal complex salt of a monoazo dye, nitrohumic acid and its salt, salicylic acid, naphthoic acid, a metal complex such as Co of dicarboxylic acid, Cr, Fe, a sulfonated copper phthalocyanine pigment, a nitro group, There are halogen-introduced styrene oligomers, chlorinated paraffins, melamine resins, and the like, but these dyes have a complicated structure, the properties are not constant, and the stability is poor.

Further, it cannot be used as a color toner because the original color tone is significantly impaired. Furthermore, during thermal kneading, decomposition or mechanical shock, friction, changes in temperature / humidity conditions, and the like are likely to cause decomposition or deterioration, and a phenomenon in which charge controllability is deteriorated is likely to occur. In many cases, the chargeability 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.

[0006] Further, since there is an advantage that the storage stability and the low temperature fixing property are compatible with each other without impairing the vinyl chloride matt fusion resistance and the original color of the color material of the color toner, recently, a polyester resin or an epoxy resin is used as a binder. It is often used as a resin. However, when a polyester resin or 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, repeated use reduces the charge amount, causing fog and toner scattering. There was a problem that it was difficult to do. This is because the polyester resin and epoxy resin have a chemical structure of -COOH, -O.
It is considered that the functional groups such as H groups remain, which hinders maintaining stable chargeability.

Conventionally, as a mechanism of a two-component dry developer, fine toner particles are formed on the surface of relatively large particles.
It is held by the electric force generated by the friction of both particles, and when the electrostatic latent image is approached, the attraction force in the latent image direction to the toner particles by the electric field formed by the electrostatic latent image is generated between the toner particles and the carrier particles. It has been proposed that the toner particles are attracted and adhered onto the electrostatic latent image to make the electrostatic latent image visible by overcoming the binding force of. Since the developer is repeatedly used while replenishing the toner consumed by the development, the carrier must always frictionally charge the toner particles to a desired polarity and a sufficient charge amount during long-term use. . However, in the conventional developer, a toner film is formed on the carrier surface due to a collision between particles, a mechanical collision such as a collision between a particle and a developing machine, or heat generated by these actions, so-called spent formation occurs, and a carrier is generated. The charging characteristics of No. 1 deteriorate with the use time, and it becomes necessary to replace the entire developer. In order to prevent such a spent state, a method of coating the surface of a carrier with various resins has been proposed, but a satisfactory method has not been obtained yet. For example, styrene-methacrylate copolymer,
Carriers coated with a resin such as styrene polymer have excellent charging characteristics, but have a relatively high surface critical surface tension,
The life as a developer was not so long because the spent was formed again during repeated copying.

On the other hand, a carrier coated with a silicone resin having a low surface tension has been proposed. However, since the silicone resin has a weak mechanical strength, for example, strong stirring such as in a high-speed copying machine, or in a developing section. The carrier particles collide with the inner wall of the developing section and the surface of the photoconductor due to long-term stirring of
Or, when particles collide with each other, the silicone resin coating layer is abraded and peeled off over time, and the frictional charge changes from the charge between the toner and the silicone resin to the charge between the toner and carrier core particles. However, there is a problem in that the image quality is deteriorated. Further, when the carrier particles are coated with a silicone resin, the silicone resin itself has a high electric resistance, so that when it is used as a developer, the image quality is deteriorated due to an edge phenomenon and a charge accumulation phenomenon.

The drawbacks of such a coated carrier can be ameliorated by dispersing a conductive substance in the coating layer. That is, when the carrier is given a certain degree of conductivity, the carrier acts as a developing electrode, and the development is carried out in a state where the developing electrode and the surface of the photoconductor to be developed are in close contact with each other. Even a large area of black area is faithfully reproduced as the original. Conventionally, carbon, tin oxide, etc. have been used as such a conductive material,
When such a conductive material is dispersed in the carrier coating layer, the following drawbacks occur.

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 becomes small, the charge generated in the toner is attenuated through the carrier, and the charge amount cannot be maintained. Further, there is a problem that the conductive material is separated from the coating layer due to use over time and the charge amount changes. In order to solve this problem, in JP-A-62-182759, carbon is treated by treatment with aminosilane, amino-modified silicone oil or the like, but the problem is that the cost increases due to an increase in treatment steps. It was

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to provide stable triboelectric charging between toner particles or between toner and carrier, a developing sleeve or a charging member such as a blade, and a sharp triboelectric charge amount distribution. (EN) To provide a toner that is uniform, has good charge rising property and environmental stability, and can be adjusted to a charge amount suitable for a developing device to be used, and yet another object is to provide a vivid color toner. Yes, an image of the same quality as the initial image is provided even during continuous use. In addition, other purposes include no scumming and toner scattering, no deterioration of image quality due to edge phenomenon and charge accumulation phenomenon, no peeling of the carrier coating layer even during continuous use, and no separation of conductive fine powder, resulting in friction. It is an object of the present invention to provide a two-component developer which is stable in charging and can provide an image with high fidelity equivalent to that of the initial image.

[0012]

As a result of intensive investigations by the present inventors, in the toner containing a binder resin, a colorant and a charge control agent as a main component, the sulfone represented by the following general formula I was used as the charge control agent. By containing a copolymer having an acid number-containing acrylamide monomer and a number average molecular weight of 1500 to 10,000, a negatively chargeable electrostatic image developing toner that improves the above-mentioned conventional defects can be obtained. discovered.

Formula I

[0014]

[Chemical 3]

Wherein R ^{1 to} R ^{3 are} hydrogen or a lower alkyl group having 1 to 8 carbon atoms,
Aryl group, Mn ⁺ ; K ⁺ , Na ⁺ , Ca ²⁺ , Mg ²⁺ , Al ³⁺ , n; positive integer, and the above charge control agent and the fluorine-containing quaternary ammonium salt represented by the following general formula II. When the compound is used in combination as an auxiliary charge control agent, a toner having a better negative chargeability, particularly a color toner, can be obtained.

General formula II

[0017]

[Chemical 4]

However, X; --SO _2- , --CO--, R ⁴ , R ⁵ , R ⁶ , R ⁷ ; H, lower alkyl group having 1 to 10 carbon atoms, aryl group, Y; I, Br, m A positive integer, n; a positive integer, and as the polyester resin used as the binder resin, (i) a diol represented by the following general formula III as an alcohol component.

Formula III

[0020]

[Chemical 5]

Where R ⁸ and R ^{9 are} hydrogen or an alkylene group having 1 to 4 carbon atoms, x and y are positive integers, and x + y = 2 to 16 (b) represented by the following general formulas IV and V 1 to 50 mol% of a divalent carboxylic acid or an acid anhydride thereof or a lower alkyl ester thereof and a polyvalent carboxylic acid having a valence of 3 or higher, or an acid anhydride or a lower alkyl ester thereof in the constituents, trimellitic acid or 10-30 of the acid anhydride
Mol%.

Formula IV

[0023]

[Chemical 6]

However, R ¹⁰ , R ¹¹ and R ^{12 of} the above-mentioned general formulas IV and V; an alkyl group and an aryl group having 4 to 20 carbon atoms. By using a polyester resin having an acid value of 5 or less, which is obtained by polycondensation of the above components, a negatively-charged electrostatic charge satisfying all the charging characteristics, low-temperature fixability, vinyl chloride mat fusion resistance, and storage stability. An image developing toner can be obtained. Further, as the epoxy resin used in the present invention,
Examples thereof include polycondensates of bisphenol A and epichlorohydrin, such as Epomic R362, R364, and R3.
65, R366, R367, R369 [Mitsui Petrochemical Industry Co., Ltd.], Epotote YD-011, YD-0
12, YD-014, YD-904, YD-017 (all manufactured by Tohto Kasei Co., Ltd.), Epicoat 1002, 100
There are commercially available products such as 4,1007 (all manufactured by Shell Chemical Co., Ltd.).

In addition, homopolymers of styrene such as polystyrene, poly-p-chlorostyrene, polyvinyltoluene and the like and substitution products thereof with respect to the above polyester resin and epoxy resin; 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, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene- Styrene-based copolymers such as isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, Polyvinyl acetate Ethylene, 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 It is also possible to use a mixture of wax and the like.

In particular, the silicone resin coating layer of the carrier contains conductive fine powder and a silane coupling agent,
Since the conductive fine powder is carbon black and the silane coupling agent is an aminosilane coupling agent, it has durability and does not deteriorate in image quality due to an edge phenomenon or a charge accumulation phenomenon, and can be used over time. A two-component developer for electrophotography having a stable triboelectric charging property was obtained. Further, according to the present invention, by coating the surface of the core particles with a silicone resin containing a conductive fine powder and a silane coupling agent, the advantages of the conventional silicone resin-coated carrier can be maintained in the same manner. By imparting conductivity, the phenomenon of charge accumulation in the carrier, peeling of the coating layer, and detachment of the conductive fine powder are effectively suppressed.

The amount of the copolymer of one or two selected from styrene and α-methylstyrene used as the charge control agent in the present invention and the sulfonic acid-containing monomer represented by the general formula I is The binder resin is determined according to the kind of the binder resin, the presence or absence of additives used as necessary, and the toner production method including the dispersion method, and is not uniquely limited, but the binder resin 100 is preferable.
It is used in the range of 0.5 to 20 parts by weight with respect to parts by weight. The range of 2 to 10 parts by weight is more preferable. 0.
If the amount is less than 5 parts by weight, the negative charge of the toner is insufficient, which is not practical. If it 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 lowered and the image density is lowered, and the toner is fixed at a low temperature. And the PVC mat fusion resistance are impaired. In addition, typical examples of the compound represented by the general formula II which is used as a negative charge control agent together with the charge control agent represented by the general formula I include the followings, all of which are white or pale Shows yellow.

[0028]

[Chemical 7]

[0029]

[Chemical 8]

[0030]

[Chemical 9]

[0031]

[Chemical 10]

[0032]

[Chemical 11]

[0033]

[Chemical 12]

[0034]

[Chemical 13]

[0035]

[Chemical 14]

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, rhodamine 6
G, lake, chalco oil blue, chrome yellow, quinacridone, benzidine yellow, rose bengal, triallylmethane dyes, monoazo dyes, disazo dyes, dyes and pigments can be used alone or in combination. obtain.

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

These ferromagnetic materials have an average grain size of 0.1 to 2
It is desirable that the amount is about 20 μm to 100 parts by weight of the resin component, particularly preferably 40 to 100 parts by weight of the resin component.
It is 150 parts by weight. Further, the toner of the present invention may be mixed with an additive as required. Examples of the additives include fluororesin fibers or fine particles, lubricants such as zinc stearate, abrasives such as cerium oxide and silicon carbide, fluidity imparting agents such as colloidal silica and aluminum oxide, anti-caking agents, or carbon. There are conductivity imparting agents such as black and tin oxide, and fixing aids such as low molecular weight polyolefin.

The carrier core particles coated with a silicone resin in the present invention may be conventionally known ones, for example, ferromagnetic metals such as iron, cobalt and nickel; alloys and compounds such as magnetite, hematite and ferrite;
Examples thereof include glass beads. The average particle diameter of these core particles is usually 10 to 1000 μm, preferably 30 to 500.
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, KR26 manufactured by Shin-Etsu Silicone Co., Ltd., which is commercially available.
1, KR271, KR272, KR275, KR28
0, KR282, KR285, KR251, KR15
5, KR220, KR201, KR204, KR20
5, KR206, SA-4, ES1001, ES100
1N, ES1002T, KR3093 and SR2100, SR2101, SR2107, S made by Toray Silicone Co., Ltd.
R2110, SR2108, SR2109, SR211
5, SR2400, SR2410, SR2411, SH
805, 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 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 preferably has a particle size of about 0.01 to 5.0 μm, and the particle size of the conductive fine powder is 0.1% to 100 parts by weight of the silicone resin.
It is preferably added in an amount of 01 to 30 parts by weight, more preferably 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 an organic substance and R is a hydrolyzable group. 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. 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 can be mentioned. Hereinafter, the present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. Further, these can be performed by known means. All parts are parts by weight.

Charge Control Agent Production Example 1 of Claim 1 Composition of Raw Material Methanol 250 g Toluene 100 g Styrene 475 g 2-Acrylamido-2-methylpropanesulfonic acid potassium salt 25 g Lauroyl peroxide 10 g Stirrer, condenser, thermometer, Charge the flask with a nitrogen introduction tube and stir while introducing nitrogen to 70
After the solution was polymerized at 8 ° C for 8 hours, the contents were taken out, dried under reduced pressure and pulverized with a jet mill to give a number average molecular weight of
The charge control agent A of was obtained.

Charge Control Agent Production Example 2 of Claim 1 Composition of Raw Material Methanol 250 g Toluene 100 g Styrene 450 g 2-Acrylamido-2-methylpropanesulfonic acid calcium salt 50 g Lauroyl peroxide 10 g Using the above raw materials and the above Production Example 1 A charge control agent C having a number average molecular weight of 5000 was obtained by the same method.

Charge Control Agent Production Example 3 of Claim 1 Composition of Raw Material Methanol 250 g Toluene 100 g Styrene 400 g α-Methylstyrene 65 g 2-Acrylamido-2-methylpropanesulfonic acid aluminum salt 35 g Lauroyl peroxide 10 g Using the above raw materials A charge control agent C having a number average molecular weight of 2000 was obtained by the same method as in Production Example 1 above.

Polyester Production Example 1 Polyoxypropylene (2,2) -2,2-bis (4-
Hydroxyphenyl) propane 70 parts, fumaric acid 20
Part, n-dodecenyl succinic anhydride 5 parts, and hydroquinone 1 part were placed in a glass flask and heated to 230 ° C.
_The reaction was carried out with stirring under a stream of _two gases. The acid value at the time when the water generated by the reaction stopped flowing out was 1.5. Further, 5 parts of trimellitic anhydride was added and reacted for about 8.5 hours. When the acid value reached 4.0, the reaction was terminated to obtain polyester A. The softening point of the obtained resin was 118 ° C.

Polyester Production Example 2 Polyoxypropylene (2,2) -2,2-bis (4-
Hydroxyphenyl) propane 70 parts, fumaric acid 15
Parts and 5 parts of isododecenyl succinic anhydride were reacted at 220 ° C. in the same manner as in Polyester Production Example 1. Further, 10 parts of trimellitic anhydride was added and reacted at 200 ° C. to obtain polyester resin B. The resin thus obtained had a softening point of 119 ° C. and an acid value of 3.0.

Polyester Production Example 3 Polyoxypropylene (2,2) -2,2-bis (4-
Hydroxyphenyl) propane 50 parts, terephthalic acid 2
0 parts, 3 parts of n-dodecenyl succinic anhydride, 0.001 part of diisopropyl orthotitanate and 20 parts of polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane in the same manner as in Polyester Production Example 1 The mixture was reacted at 230 ° C. for about 5 hours, 7 parts of trimellitic anhydride was added at 200 ° C., reacted for about 6 hours, and further reacted under reduced pressure for 2 hours to obtain polyester resin C. The resulting resin had a softening point of 112 ° C. and an acid value of 4.0. Next, a production example of a carrier having several silicone resins in the coating layer will be shown. These can be performed by known means.

Carrier Production Example 1 Composition of Coating Layer Forming Liquid Silicone resin solution (KR250 manufactured by Shin-Etsu Silicone Co., Ltd.) 100 parts Toluene 100 parts The above formulation 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 100 μm.
Carrier A having a coating layer formed on the surface of 1000 parts by weight of the spherical ferrite by using a fluidized bed coating apparatus was obtained.

Carrier Production Examples 2 to 12 The following components were mixed with 100 parts of toluene and dispersed with a homomixer for 30 minutes to prepare a coating layer forming liquid. Carrier manufacturing example 2 Silicon resin (KR206 Shin-Etsu Silicone) 100 parts Carbon black (# 44 Mitsubishi Kasei) 3 parts Carrier manufacturing example 3 Silicon resin (SR2400 Toray Dow Corning Silicone) 100 parts Tin oxide (S-1 Mitsubishi Metals) 2 parts Carrier manufacturing example 4 Silicon resin (KR2400 Toray Dow Corning Silicone) 100 parts Carbon black (# 44 Mitsubishi Kasei) 1 part Methyltrimethoxysilane (SZ6070 Toray Dow Corning Silicone) 0.5 parts Carrier manufacturing example 5 Silicon resin (SR204 Shin-Etsu) Silicone) 100 parts Carbon black (BPL Cabot Corporation) 1 part Methyltrimethoxysilane (SZ6070 Toray Dow Corning Silicone) 0.5 part Carrier manufacturing example 6 Silicon resin (SR2400 Toray) Ukoning Silicone) 100 parts Tin oxide (S-1 Mitsubishi Metals) 1 part Methyltrimethoxysilane (SZ6070 Toray Dow Corning Silicone) 0.5 part Carrier Production Example 7 Silicon Resin (SR2400 Toray Dow Corning Silicone) 100 parts Carbon Black ( Ketjen Black Lion Akzo) 1.5 parts γ-anilinopropyltrimethoxysilane (SZ6083 Toray Dow Corning Silicone) 0.3 part Carrier Production Example 8 Silicon Resin (SR2400 Toray Dow Corning Silicone) 100 parts Carbon Black (BP2000 Cabot) 1 part γ- (2-aminoethyl) aminopropyldimethoxysilane (SZ6023 Toray Dow Corning Silicone) 0.2 part Carrier Production Example 9 Silicon Resin (KR206 Shin-Etsu) Recon) 100 parts Tin oxide (S-1 Mitsubishi Metals) 1 part γ- (2-aminoethyl) aminopropyldimethoxysilane (SZ6023 Toray Dow Corning Silicone) 0.2 parts Carrier Production Example 10 Silicon Resin (SR2400 Toray Dow Corning Silicone) ) 100 parts Carbon black (# 3600 Mitsubishi Kasei Co., Ltd.) 1 part γ- (2-aminoethyl) aminopropyldimethoxysilane (SH6020 Toray Dow Corning Silicone) 0.1 part Carrier Production Example 11 Silicon Resin (SR2400 Toray Dow Corning Silicone) 100 parts Carbon black (# 44 Mitsubishi Kasei Co., Ltd.) 1 part γ- (2-aminoethyl) aminopropyldimethoxysilane (SH6020 Toray Dow Corning Silicone) 0.1 parts Carrier Production Example 12 Silicon tree (KR206 Shin-Etsu Silicone) 100 parts Carbon Black (# 44 Mitsubishi Kasei) 1.5 parts γ- (2-Aminoethyl) aminopropyldimethoxysilane (SH6020 Toray Dow Corning Silicone) 0.4 parts This coating layer forming liquid is averaged. Carriers B, C, D, E, F, G, H having a coating layer formed on the surface of 1000 parts by weight of spherical ferrite having a particle size of 70 μm by using a fluidized bed type coating apparatus.
I, J, K, L were obtained.

[0050]

EXAMPLES The present invention will be specifically described below with reference to examples. The amounts (parts) of each component described in the examples are parts by weight. Example 1 Styrene-2-ethylhexyl acrylate copolymer 100 parts C.I. I. Pigment Blue 15 5 parts Charge control agent A 5 parts Exemplified compound II-1 1 part After thoroughly stirring and mixing the mixture having the above composition in a Henschel mixer, it is about 3 at a temperature of 130 to 140 ° C. by a roll mill.
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 was mixed with 97.5 parts of a 100-250 mesh ferrite carrier in a ball mill to obtain a developer. Next, the above developer is applied to our FT757
When set to 0 and developed, a good image was obtained, and the image did not change even after 100,000 images were printed.

When the charge amount of the toner was measured by the blow-off method, the initial charge amount was -16.9 μC / g, and the toner charge amount after running 100,000 sheets was-.
At 14.5 μC / g, there was almost no difference from the initial value. Also, in a high humidity environment of 35 ° C 90% RH, and 10 ° C 15%
Even under a low humidity environment of RH, an image equivalent to normal humidity was obtained. There was also 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 the same image output test was performed, a good image was obtained, and the image did not change after 100,000 images were output. When the charge amount of the toner was measured by the blow-off method, the initial charge amount was -17.3 μc /
The toner charge amount after running 100,000 sheets was −15.6 μc / g, which was almost the same as the initial value. However, the fog started to occur from around 120,000 sheets. Again 1
Images up to 0,000 sheets were obtained under the high-humidity environment of 35 ° C. and 90% RH and in the low-humidity environment of 10 ° C. and 15% RH. There was also no toner filming on the photoconductor.

Example 3 Polyester resin A 100 parts Polypropylene 5 parts Carbon black 10 parts Charge control agent A 2 parts Exemplified compound II-3 0.3 parts The raw material mixture having the above composition was melt-kneaded 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 was mixed with 97.5 parts of carrier A coated with a silicone resin in a ball mill to obtain a developer. Next, this developer was set in a copying machine FT7570 manufactured by our company as in Example 1 and an image test was conducted. As with Example 1, a good image with high sharpness was obtained. It didn't change even after displaying 10,000 images. When the toner charge amount was measured by the blow-off method, the initial charge amount was -19.8 μC / g, and the toner charge amount after running 120,000 sheets was-.
There was almost no difference from the initial value of 17.7 μC / g. Also, in a high humidity environment of 35 ° C 90% RH, and 10 ° C 15%
Even under a low humidity environment of RH, an image equivalent to normal humidity was obtained. Also, there was no toner filming on the photoreceptor.

Example 4 A toner was prepared in the same manner as in Example 3 except that the carrier F was used.
When a developer was prepared and the same image output test was carried out, a good image was obtained, and the image did not change even after image output of 120,000 sheets. Further, when the charge amount of the toner was measured by the blow-off method, the initial charge amount was −20.1 μc /
The toner charge amount after running 120,000 sheets was -18.3 μc / g, which was almost the same as the initial value. However, the ground fogging occurred from around 130,000 sheets. Again 1
Up to 20,000 sheets, an image equivalent to normal humidity was obtained even in a high humidity environment of 35 ° C. 90% RH and a low humidity environment of 10 ° C. 15% RH. There was also no toner filming on the photoconductor.

Comparative Example 1 A developer was obtained in the same manner as in Example 3 except that 2 parts of zinc salicylate (Bontron E-84 manufactured by Orient Chemical Co., Ltd.) was used in place of the charge control agent A of Example 3, and an image test was conducted. I went. 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 photoconductor. 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 0.82, and an unclear image with fog was obtained. Further, when the charge amount was measured in the same manner as in Example 1, the initial charge amount was -15.1 μC / g.
However, it decreased to −8.1 μC / g after 50,000 sheets.

Comparative Example 2 Development was carried out in the same manner as in Example 3 except that 2 parts of zinc salicylate (Bontron E-84 manufactured by Orient Chemical Co., Ltd.) was used in place of the charge control agent A and the exemplified compound 2-3 in Example 3. An agent was obtained and an image test was conducted. A clear image without fog was obtained as the initial image, but an unclear image with fog was obtained from around 90,000 sheets, and toner filming was observed on the surface of the photoconductor. Moreover, when an image test was performed in a high humidity environment of 35 ° C. and 90% RH, the image density was as low as 0.61 and
An unclear image with fog was obtained. In addition, Example 3
When the charge amount was measured in the same manner as above, the initial charge amount was -1.
It was 5.2, but it decreased to −7.3 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 Tohto Kasei Co., Ltd.) 20 parts C.I. I. Pigment Blue 15 5 parts C.I. I. Pigment Yellow 17 5 parts Charge control agent A 3 parts Exemplified compound II-4 1 part The mixture having the above composition was sufficiently stirred and mixed in a Henschel mixer in the same manner as in Example 1, and then 130 to 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 resulting kneaded product was pulverized and classified to obtain a green toner having a particle diameter 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 with a speed kneader to obtain a toner.

This toner was loaded into a developing device as shown in FIG. 1, continuous copying was carried out, and an image test was carried out.
A good image was obtained. The image did not change after 50,000 images were printed. This developing method will be described. As shown in the drawing, the toner 6 contained in the toner tank 7 is forcibly drawn to the sponge roller 4 by the stirring blade 5, and the toner is supplied to the sponge roller 4. Then, the toner attached to the sponge roller 4 is carried to the toner conveying member 2 by the rotation of the sponge roller in the arrow direction, and is rubbed and electrostatically or physically adsorbed, and the toner conveying member 2 is moved in the arrow direction. It strongly rotates, and the elastic blade 3 forms a uniform thin toner layer and is triboelectrically charged. After that, the toner is conveyed to the surface of the electrostatic latent image carrier 1 which is in contact with or in the vicinity of the toner conveying member 2, and the latent image is developed.

The electrostatic latent image is formed by exposing the organic photosensitive member to a negative DC charge of 800 V, exposing it to form a latent image, and then performing reversal development. 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 -10.9 μC / g. In addition, the charge amount after running 50,000 sheets was -8.9 μC / g, which was almost the same as the initial value. Also, even in high and low humidity,
Image quality equivalent to normal humidity was obtained. Also, there was no toner filming on the photoconductor.

Example 6 Polyester resin B 100 parts Polypropylene 5 parts Carbon black 10 parts Charge control agent A 3 parts Exemplified compound II-1 0.5 parts Metal-containing monoazo dye [Bontron S-34 manufactured by Orient Chemical Industries] 1 part Above The raw material mixture having the composition was melt-kneaded 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 was mixed with 97.5 parts of carrier B coated with a silicone resin in a ball mill to obtain a developer. Next, this developer was set in a copying machine FT7570 manufactured by our company as in Example 1 and an image test was conducted. As with Example 1, a good image with high fidelity was obtained. It didn't change even after displaying 10,000 images. Further, when the toner charge amount was measured by the blow-off method, the initial charge amount was −21.3 μC / g, and the toner charge amount after running 150,000 sheets was −.
There was almost no difference from the initial value, which was 19.0 μC / g. Also, in a high humidity environment of 35 ° C 90% RH, and 10 ° C 15%
Even under a low humidity environment of RH, an image equivalent to normal humidity was obtained. There was also no toner filming on the photoconductor.

Example 7 A toner was prepared in the same manner as in Example 5 except that the carrier F was used.
When a developer was prepared and the same image output test was carried out, a good image was obtained, and the image did not change even after image output of 120,000 sheets. Further, when the charge amount of the toner was measured by the blow-off method, the initial charge amount was -18.4 μc.
The charge amount of the toner after running 120,000 sheets was -16.8 μc / g, which was almost the same as the initial value. However, the ground fogging occurred from around 130,000 sheets. Also, up to 120,000 sheets, an image equivalent to normal humidity was 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 3 A developer was prepared in the same manner as in Example 4 except that the charge control agent A of Example 6 was omitted and the amount of the metal-containing monoazo dye was changed to 1.5 parts. 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. Further, when an image test was carried out in a high humidity environment of 35 ° C. and 90% RH, 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 -12.
Low as 6 μC / g, and −5.5 μC after 30,000 sheets.
It was as low as / g.

Example 8 Polyester Resin C 100 parts Defreeized fatty acid carnauba wax NX-A-03 (manufactured by Noda Wax Co.) 5 parts C.I. I. Pigment Red 57 5 parts C.I. I. Pigment Red 48 3 parts Charge control agent A 7.5 parts Exemplified compound II-3 0.3 parts The mixture having the above composition was sufficiently stirred and mixed in a Henschel mixer in the same manner as in Example 1, and then 110 to 1 with 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 product was pulverized and classified to obtain a red 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 with a speed kneader to obtain a toner. This toner was developed in the same developing device as in Example 3 and subjected to an image test. As a result, a clear and good image was obtained, and the image did not change after 50,000 sheets of images were printed.

When Q / M was measured by the suction method specific charge amount measuring device in the same manner as in Example 3, the initial value was -10.9.
.mu.c / g, which is a sufficient charge, and the amount of charge when running 50,000 sheets was -9.1 .mu.C / g, which was almost the same as the initial value. Further, even under high humidity and low humidity, image quality equivalent to 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 with the developer compositions shown in Table 1 below. The imageability and chargeability of these developers are also summarized in the table.

[0067]

[Table 1]

[0068]

[Table 2]

[0069]

[Table 3]

[0070]

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 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.

[Brief description of drawings]

FIG. 1 is an explanatory view of an example of a developing device using the 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

Claims (2)

[Claims] 1. A toner comprising a binder resin, a colorant and a charge control agent as a main component, wherein the number average molecular weight including a sulfonate-containing acrylamide monomer represented by the following general formula I as a charge control agent is 1500-500. A negatively chargeable toner for developing an electrostatic charge image, which comprises 10000 copolymers. General formula I Provided that R ^{1 to} R ^{3 are} hydrogen or a lower alkyl group having 1 to 8 carbon atoms,
An aryl group, M ^{n +} ; any of K ⁺ , Na ⁺ , Ca ²⁺ , Mg ²⁺ , and Al ³⁺ , n; a positive integer, 2. The negatively chargeable toner for developing an electrostatic charge image according to claim 1, which contains a compound represented by the general formula I together with a compound represented by the general formula I as a charge control agent. General formula II: _{However, X; -SO 2 -, -} CO-, R 4, R 5, R 6, R 7; H, lower alkyl group having 1 to 10 carbon atoms, an aryl group, Y; I, Br, m ; positive Integer, n; positive integer,