JPH05119535A - Toner - Google Patents

Abstract

PURPOSE:To obtain excellent rising and stability of electrification and to prevent splashing and fogging by using a specified charge controlling resin and calixarene compd. charge controlling agent as an electrification controlling agent. CONSTITUTION:The charge controlling agent contains a charge controlling resin and calixarene compd. The charge controlling resin is obtd. by copolymn. of sulfonate-group acrylamide monomer expressed by formula I, vinyl monomers selected from styrene, etc., or mixture of these with mixing proportion of 1-20wt.% of the sulfon-group acrylamide monomers to the whole monomer amt. The charge controlling resin is incorporated by 0.1-10 pts.wt. to 100 pts.wt. of thermoplastic resin. The calixarene compd. is incorporated by 0.1-10 pts.wt. to 100 pts.wt. of the thermoplastic resin. In formula R1 is hydrogen atom or methyl group, R2 and R3 are hydrogen atoms or alkyl groups of <=10 carbon number, and (m) is an integer 1-10.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a toner for electrophotography.

[0002]

2. Description of the Related Art In recent years, the speed of electrophotographic copying machines has been further increased. For 50 or more sheets of A-4 size per minute, a photoconductor made of a photoconductive material such as a selenium-based or amorphous silicon-based material is generally used in terms of photosensitivity. In addition, a laminated organic photoreceptor is used for a high-speed printer (laser beam printer or the like) using an electrophotographic method. A high-performance negatively-charged toner is desired as a developer that visualizes an electrostatic latent image formed on these photoconductors by electrostatic attraction.

Conventionally, negatively charged toners generally have a charge control agent and a colorant having good negatively charged properties dispersed in a binder resin of the toner. When toner is used as a developer for medium and low system speeds, conventional negatively chargeable charge control agents have problems in compatibility or dispersibility with resins, but their addition is significant as such. Met.
However, the system speed is 30 cm / sec or more, especially 40 cm
In a high-speed copying machine with a speed of over 1 / sec or more, the developing device is also driven at high speed, and stirring of the developing device and rotation of the developing sleeve become faster, so the conventional developer consisting of low to medium speed toner is used as it is. It cannot be used.

For example, since the developing sleeve rotates at a high speed, toner is scattered from the carrier due to centrifugal force or the like,
This contaminates the area around the developing device, and the contaminated toner appears on the copy as fluttering of the toner or the like, or the scattered toner is fogged on the photoconductor to be developed and the image quality is deteriorated. At the time of intermittent copying, the toner charge amount gradually increases, resulting in a problem that the image density (ID) decreases. In the present specification, the system speed means the peripheral speed of the photoconductor.

[0005]

SUMMARY OF THE INVENTION The present invention solves the above problems and provides a negatively chargeable toner suitable for high-speed copying, and even when high-speed copying is performed, rising of charge and stability thereof. It is an object of the present invention to provide a toner that is excellent in heat resistance, does not cause scattering, and can form a good image without fog.

[0006]

That is, the present invention provides a negatively chargeable toner comprising at least a thermoplastic resin, a colorant and a charge control agent, which contains a charge control resin (CCR) and a calixarene compound as the charge control agent. The charge control resin (CCR) has the following general formula [I]

[Chemical 2] [Wherein R ₁ is a hydrogen atom or a methyl group, R ₂ or R ₃
Represents a hydrogen atom or an alkyl group having 10 or less carbon atoms, and m represents an integer of 1 to 10]. A sulfonic acid group-containing acrylamide monomer and a vinyl monomer selected from the group consisting of styrene, acrylic acid ester, methacrylic acid ester, and mixtures thereof, and the sulfonic acid group-containing acrylamide monomer is 1 to 20 wt% of the total amount of the monomer. % Of the thermoplastic resin, the charge control resin is contained in an amount of 0.1 to 10 parts by weight, and the calixarene compound is added to 100 parts by weight of the thermoplastic resin. To 0.1
The present invention relates to a negatively chargeable toner containing 10 parts by weight.

The negatively chargeable toner of the present invention comprises at least a thermoplastic resin, a colorant and a charge control resin, and the toner of the present invention is particularly represented by the general formula [I], a sulfonic acid group-containing acrylamide monomer and vinyl monomer. And a charge control resin (hereinafter referred to as CCR).

A preferable example of the sulfonic acid group-containing acrylamide monomer represented by the general formula [I] is 2-acrylamido-2-methylpropanesulfonic acid (hereinafter referred to as AM
PS), 2-methacrylamido-2-methylpropanesulfonic acid and the like are preferable, and AMPS is particularly preferable.

The vinyl-based monomer copolymerized with the acrylamide-based acrylamide-based monomer represented by the general formula [I] is styrene or the like as an aromatic vinyl monomer,
Further, as the unsaturated carboxylic acid and its ester, acrylic acid ester, methacrylic acid ester, maleic acid ester, acrylamide, and the like can be exemplified, but any one having an unsaturated bond may be used,
Although not particularly limited, a preferred combination is
It is a copolymer of AMPS and styrene, or a combination of AMPS and styrene, a (meth) acrylic ester.

The copolymer used as the charge control agent in the present invention is a radical copolymerization of the above-mentioned sulfonic acid group-containing acrylamide monomer represented by the general formula [I] and vinyl monomer in the presence of a polymerization initiation catalyst. It is obtained by The polymerization method is not particularly limited, and a known radical polymerization method may be applied. However, when copolymerizing with AMPS, for example, solution polymerization is suitable since it is water-soluble.

As the polymerization initiation catalyst, an azo type catalyst is preferable, and examples thereof include azobisisobutyronitrile, azobisdimethylvaleronitrile and azobisdimethylmethoxyvaleronitrile. The mixing ratio of both monomers is the general formula
The sulfonic acid group-containing acrylamide monomer represented by [I] is 1 wt% to 20 wt%, preferably 2 to 19 wt%,
It is more preferably set to 5 to 19 wt%. 20 wt
%, The electric resistance of the toner will be low, and the change of the charge amount over time will be large. If it is less than 1 wt%, the toner will scatter a lot and fog after printing will be abundant to use.

The amount of CCR used in the present invention is 0.1 to 10 parts by weight based on 100 parts by weight of the thermoplastic resin. 0.
If the amount is less than 1 part by weight, the rise of the toner charge is poor,
A lot of toner scatters, and toner flapping occurs. 1
If the amount is more than 0 parts by weight, the hygroscopicity of the toner becomes strong, and the change of the charge amount with time and the attenuation rate increase.

The thermoplastic resin used in the present invention is not particularly limited, but may be any one having a softening point which is usually sufficient for fixing and a glass transition point which is sufficient for storage stability. As long as the softening point of the thermoplastic resin suitable for the present invention does not impair the effects of the present invention, a thermoplastic resin having a low softening point is preferable in terms of development speed and system mechanism. For example, polystyrene or styrene and an acrylic ester or a methacrylic ester may be used. At least one diol component selected from the group consisting of a copolymer resin with bisphenol type diol, rosin type diol and glycol, and an aromatic dicarboxylic acid such as phthalic acid, isophthalic acid and terephthalic acid, and malonic acid and maleic acid. And a polyester resin synthesized from at least one dicarboxylic acid selected from the group consisting of aliphatic dicarboxylic acids such as adipic acid and trimellitic acid. The fixing temperature may be appropriately selected in consideration of the selected thermoplastic softening point, but in order to achieve high-speed fixing property, the number average molecular weight (Mn) is preferably 2000 to 10000, more preferably 2500 to 7000. preferable.

In the present invention, in addition to CCR, a calixarene compound represented by the following general formula [II] is used as a charge control agent:

[Chemical 3] In the general formula [II], R ₄ is a hydrogen atom, a C ₁ -C ₁₂ alkyl group or an unsaturated alkyl group, a carboxyalkyl group such as a carboxymethyl group or a salt thereof, an acyl group such as an acetyl group, or a phenyl group. Represents an aromatic hydrocarbon group. R ₅ , R ₆ and R ₇ are each independently a hydrogen atom, a halogen atom such as a fluorine atom or a chlorine atom, and C
_{1 to} C ₁₈ alkyl group, alkoxy group such as methoxy group,
Aromatic hydrocarbon group such as aryl group, hydroxyl group, carboxyl group, amino group optionally substituted with alkyl group and / or acyl group, nitro group, sulfone group,
It is selected from the group consisting of acyl groups such as a sulfoamide group, a carbamoyl group, a cyano group, a lower alkylcarboxylic acid ester, and an acetyl group. n represents an integer of 4 to 10.

Specific examples of the calixarene compound used in the present invention include, but are not limited to, the following compounds.

[Chemical 4]

[0016]

[Chemical 5]

[0017]

[Chemical 6]

[0018]

[Chemical 7]

[0019]

[Chemical 8]

[0020]

[Chemical 9]

[0021]

[Chemical 10]

[0022]

[Chemical 11]

[0023]

[Chemical 12]

[0024]

[Chemical 13]

The calixarene compound of the present invention is, for example, C.I. D. Gutsche (Accounts of chemical Researc
h, 1983 (16) p161-170)

[Chemical 14] [In the general formula [IV], R _{5 to} R ₆ have the same meanings as those in the general formula [II]] Easily synthesized by reacting directly or using a suitable solvent with an inorganic strong alkaline catalyst You can The OH group having an OR ₄ group can be obtained by subjecting the compound represented by [IV] to a substitution reaction with an alkylating agent, a phenylating agent, a halogenated alkylcarboxylic acid or the like. Calix allene is used by internally or externally adding it to the toner.

When used by being internally added to the toner, it is used in an amount of 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the thermoplastic resin. If the amount is less than 0.1 part by weight, the toner cannot be given a sufficient amount of charge. If it is used in an amount of more than 10 parts by weight, the amount of electrification becomes rather low, and the charge control agent released from the toner adheres to the photoconductor to cause filming development. When externally added to the toner, 0.01 to 1 part by weight, preferably 0.1 to 0.5 part by weight, is sufficient for 100 parts by weight of the thermoplastic resin. Outside the above-mentioned range of use, the same problem as that which occurs when the amount of internal addition is not appropriate occurs.
In addition, external addition makes it possible to reduce the amount of addition and to control the charge effectively.

To the negatively chargeable toner of the present invention, a colorant exhibiting a desired color, and if necessary, other charge control agent may be added. Specific examples of the colorant that can be used in the present invention include black pigments such as channel black and carbon black such as furnace black, acetylene black, lamp black, aniline black and the like;
Yellow pigments include yellow lead, zinc yellow, cadmium yellow, yellow iron oxide, mineral fast yellow, nickel titanium yellow, navels yellow, naphthol yellow S, Hansa yellow G, Hansa yellow 10G, benzidine yellow G, benzidine yellow GR. , Quinoline yellow lake, permanent yellow, NCG, tartrazine lake, chromophthal yellow, etc .; as orange pigments, reddish yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, vulcan orange, indanthrene brilliant orange RK, benzidine orange G , Indanthrene Brilliant Orange GK, etc .; Red pigments include red iron oxide, cadmium red, red lead, cadmium mercuric sulfide, permanent red 4
R, resole red, pyrazolone red, watching red, calcium salt, lake red D, brilliant carmine 6B, eosin lake, rhodamine lake B, alizarin lake, brilliant carmine 3B, etc .;
As the purple pigment, manganese purple, fast violet B, methyl violet lake, etc .; as the blue pigment,
Navy Blue, Cobalt Blue, Alkali Blue Lake, Victoria Blue Lake, Phthalocyanine Blue, Metal-Free Phthalocyanine Blue, Phthalocyanine Blue Partial Chloride, Fast Sky Blue, Induslen Blue BC
Etc .; as green pigments, chrome green, chromium oxide, pigment green B, malachite green lake, fanal yellow green G, etc .; as white pigments, zinc white,
Titanium oxide, antimony white, zinc sulfide and the like; extender pigments include barite powder, barium carbonate, clay, silica, white carbon, talc, alumina white and the like. These colorants may be used alone or in combination of two or more, and are not limited to organic or inorganic ones as long as they are pollution-free and have a high coloring power.

In the toner of the present invention, the thermoplastic resin and the above-mentioned various additives are used in reference to the proportions in the case where they are described in the present specification, and the known proportions when they are not mentioned in the present invention. Generally used so-called pulverization method, so-called suspension polymerization method in which raw materials other than the main resin are dispersed in a monomer, and these are incorporated into a toner when the resin is polymerized, or manufacturing using a device such as spray drying. It can be produced by a grain method or the like, but is not particularly limited to these methods. The average particle size of the toner is 3 to 30.
It can be arbitrarily selected from μm.

If desired, other additives such as waxes may be added to the toner of the present invention, and various thermoplastic resins may be added to the toner of the present invention in order to improve the fixing property. You may use it in the range which does not reduce an effect. Alternatively, the surface treatment of the toner may be performed with ultrafine powder of metal oxide. The toner of the present invention can be made into a two-component developer by mixing with a suitable carrier, for example. As the carrier, resin-coated glass beads, steel balls, or the like is used when the cascade development method is performed, and ferrite, fine iron powder, or a so-called binder type carrier or the like is used when the magnetic brush development method is performed. Alternatively, the toner of the present invention itself may be manufactured as an insulating magnetic toner and used as a one-component developer to carry out the magnetic brush development method. Further, it may be used as a toner when the impression developing method or the touchdown developing method is carried out.

The present invention will be described in more detail with reference to the following examples. Example of production of charge control resin (CCR1) -Styrene 900g-2-Acrylamido-2-methylpropanesulfonic acid (AMPS) 100g-2-2'-azobisisobutyronitrile 60g-Xylene 1000g-Methanol 50g The mixture is placed in a 5-liter four-necked flask equipped with a stirrer, nitrogen is introduced, the temperature is raised to 80 ° C., and the reaction is allowed to proceed for 5 hours. Next, the temperature is raised to 100 ° C. to complete the reaction, and then the reaction mixture is placed in a vacuum heating furnace to remove xylene and methanol. The molecular weight of the obtained styrene-AMPS copolymer by gel permeation chromatography (GPC) is number average molecular weight (Mn): 1,960, weight average molecular weight (Mw): 7,120, differential scanning calorimeter ( Glass transition point (Tg) by DSC: 92 ° C. The charge control resin obtained in this production example is referred to as CCR1.

Production Example of Charge Control Resin (CCR2) -Styrene 700g-2-Acrylamido-2-methylpropanesulfonic acid (AMPS) 100g-n-Butylmethacrylate 200g-2-2'-azobis (2,4-dimethylvalero) Nitrile) 60 g-xylene 1000 g-methanol 50 g By the same synthesis method as for CCR1, AMPS-copolymerized charge control resin was obtained. The molecular weight by GPC was Mn: 2,890, Mw: 9,240, and the Tg by DSC was 82 ° C. The charge control resin obtained in this production example is referred to as CCR2.

Production Example of Charge Control Resin (CCR3) -Styrene 800g-AMPS 200g-2-2'-Azobis (2,4-dimethylvaleronitrile) 60g-Xylene 1000g-Methanol 50g The above materials were synthesized in the same manner as CCR1. By the method, a resin for charge control in which AMPS was copolymerized was obtained. The molecular weight by GPC was Mn: 3,350, Mw: 8,920, and the Tg by DSC was 92 ° C. The charge control resin obtained in this production example is referred to as CCR3.

Production Example of Charge Control Resin (CCR4) -Styrene 750g-AMPS 250g-2-2'-Azobis (2,4-dimethylvaleronitrile) 60g-Xylene 1000g-Methanol 50g The above materials were synthesized in the same manner as CCR1. By the method, a resin for charge control in which AMPS was copolymerized was obtained. The molecular weight by GPC was Mn: 3,130, Mw: 9,190, and the Tg by DSC was 94 ° C. The charge control resin obtained in this production example is referred to as CCR4.

Manufacture of Toner 1 Thermoplastic styrene acrylic resin 100 parts by weight Mn: 4,500 Mw: 197,800 Tg: 60.5 ° C. Softening point: 121 ° C. Acid value: 24.3 ・ Carbon black 7 parts by weight MA # 100 (manufactured by Mitsubishi Kasei Co., Ltd.) ・ 4 parts by weight of additive for preventing offset Viscole 660P (manufactured by Sanyo Chemical Co., Ltd., low molecular weight polypropylene) ・ 2 parts by weight of calixarene compound [13] ・ 2 parts by weight of charge control resin CCR1 The above materials were put into a 10 liter Henschel mixer, mixed at 2000 rpm for 2 minutes, and then PCM30 (l /
(d: 32.5) was continuously extruded and kneaded. Next, after cooling, coarsely pulverize with a 2 mm mesh feather mill, then finely pulverize with a jet pulverizer, cut coarse powder / fine powder with an airflow classifier, and have a particle diameter of 11.2 μm average diameter. Toner was obtained. Hydrophobic silica (R-9
74, manufactured by Nippon Aerosil Co., Ltd.) was treated with 0.2%. The toner thus obtained is referred to as Toner 1.

Manufacture of Toner 2 Thermoplastic polyester resin 100 parts by weight Mn: 5,200 Mw: 202,500 Acid value 17.8 Softening point: 122 ° C. Tg: 67 ° C. Carbon black 8 parts by weight MA # 8 (Mitsubishi・ Chemical Industry Co., Ltd. ・ 4 parts by weight of anti-offset additive Viscole TS200 (manufactured by Sanyo Chemical Co., Ltd. ・ Oxidizing low molecular weight polypropylene) ・ 3 parts by weight of calixarene compound [20] ・ Charge control resin CCR2 2 parts by weight or more The average diameter is 1 in the same manner as in the production of Toner 1.
A toner having a particle size of 0.8 μm was obtained. The toner thus obtained is referred to as Toner 2. The thermoplastic polyester resin used in the production of this toner was produced as follows. -Bisphenol A-Propylene oxide adduct 1100 g-Trimellitic anhydride 450 g-Xylene 50 g The above materials were placed in a 3-liter four-necked flask and reacted in a nitrogen stream at 240 ° C for 5 hours, then heated to 270 ° C. And reacted for 8 hours. By-produced water was distilled off.

Production of Toner 3 Thermoplastic styrene / acrylic resin 100 parts by weight Mn: 3,600 Mw: 186,400 Tg: 61.2 ° C. Softening point: 124 ° C. Copper-phthalocyanine pigment 5 parts by weight # 4920 ( (Ota Seika Co., Ltd.) ・ Offset prevention additive 4 parts by weight Viscole 550P (manufactured by Sanyo Kasei Co., Ltd.) ・ Calix allene compound [28] 3 parts by weight ・ Charge control resin CCR1 2 parts by weight Average diameter 1 in the same way as
A toner having a particle size of 1.6 μm was obtained. The surface of this toner was surface-treated with hydrophobic silica (H-2000) (manufactured by Hoechst Japan). The toner thus obtained is referred to as Toner 3.

Manufacture of Toner 4 • 100 parts by weight of the thermoplastic resin used in the manufacture of Toner 1 • 7 parts by weight of carbon black MA # 100 (manufactured by Mitsubishi Kasei Co., Ltd.) • 4 parts by weight of additive for preventing offset Viscole 660P (Sanyo) Kasei Kogyo Co., Ltd.-Low molecular weight polypropylene) -Calixarene compound [29] 2 parts by weight-Charge control resin CCR1 10 parts by weight In the same manner as Toner 1, the toner 4 was obtained. The average diameter of the obtained toner was 11.2 μm.

Production of Carrier 1 Styrene-acrylic resin 100 parts by weight (Pryolite ACL; manufactured by Goodyear) -Mapico Black BL-500 200 parts by weight (ferric tetroxide: manufactured by Titanium Industry Co., Ltd.)-Carbon Black MA # 85 5 parts by weight (manufactured by Mitsubishi Kasei Kogyo Co., Ltd.) The above materials were melted by a triple roll, kneaded, solidified, pulverized and classified to obtain a magnetic carrier I having an average particle diameter of 35 μm.

Production of Carrier II 100 parts by weight of polyester resin (resin used in the production of Toner 2) 500 parts by weight of Zn ferrite (σm: 68Oe: Hc: 135emu / g) (average particle diameter 0.7 μm) Carbon black MA # 8 4 parts by weight The above components were mixed in a 10 liter Henschel mixer, melted and kneaded in an extruder PCH30 (l / d 32.5), cooled and solidified, and then pulverized and classified to obtain a magnetic carrier II having an average of 55 μm. ..

Manufacture of Toner 5 Thermoplastic styrene-acrylic resin having the following physical properties; Mn: 1
2,100, Mw: 178,400, Tg: 62.3 ° C., softening point: 126, acid value: 26.2 Obtained. The average particle size of the obtained toner 5 was 11.0 μm.

[0041] except for excluding the calixarene compound in the manufacture toner 1 in the toner 6 to obtain toner 6 in the manufacture and all toner 1 same composition and production method. The average particle size of the obtained toner 6 was 11.2 μm.

Manufacture of Toner 7 The same procedure as in the manufacture of Toner 1 except that the charge control agent of Spirone Black TRH (Hodogaya Chemical Industry Co., Ltd.), which is a Cr alloy oil-soluble dye, is changed to 4 parts by weight. Toner 7 was obtained with the composition and production method described in 1. The average particle size of the obtained toner was 11.3 μm.

Production of Toner 8 Toner 1 was obtained in the same manner as in the production of Toner 1 except that only the carric allene compound was used as the charge control agent in Toner 1, and the same composition and production method as that of Toner 1 were obtained. The average particle size of the obtained toner 8 was 11.0 μm.

Evaluation of Toners Toners 1 to 8 and Carrier I or II were combined to prepare a developer, and the following evaluations were performed. The results are shown in Table 1.

Charge amount measurement 16 total of toners 1 to 8 on the microcarriers I and II
The toner concentration of the sample is 10 wt%, 60 g is put in a 100 cc plastic bottle, and it is placed on a stand of 120 rpm for 3 minutes.
Minutes, 10 minutes, and 30 minutes later, each charge amount (Qf) was determined.

Measurement of Scattering Amount of carrier II and toner concentration were set to 20 wt% and scattering after 3 minutes mixing was determined using the following device. 10 g of the developer having a toner concentration of 20 wt% is set on a magnet and a magnet roller having a sleeve around the magnet, and when the magnet is rotated at 1000 rpm (system speed of high-speed development 45 cm / sec), it scatters. A value obtained by measuring the toner for 1 minute using a digital dust meter manufactured by Shibata Chemical Co., Ltd. is shown in the column of the amount of scattering in Table 1. Also, the amount of scattering at a normal system speed of 20 cm / sec is shown as a comparison in the column of amount of scattering in Table 1. When it is 500 cpm or less, there is almost no trouble due to scattering even in a practical machine with a practically usable scattering amount, but 500 cpm or more, especially 10
If it exceeds 00 cpm, the scattering is severe, which may stain the periphery of the developing device or cause fog problems.

Amount of charge attenuation after aging of moisture resistance The amount of charge was measured (charge amount when mixing and stirring for 30 minutes; Q
f (30 minutes), the amount of charge (Qf (35 ° C-8 ° C) after opening the lid of the bottle in the environment of the developer at 35 ° C and 85% and leaving it for 3 days.
5% -3 days)) was measured and the amount of attenuation was calculated by the following formula.

[Equation 1]

The image evaluation carrier II and the toners 1 to 8 are placed in a 1-liter plastic bottle so that the toner concentration becomes 7 wt%, placed on a ball mill stand, and a developer is prepared at 120 rpm for 10 hours. Put this developer into EP870 made by Minolta Camera Co., Ltd. for 10K
A printing durability test was performed on the sheets, and the presence or absence of fog was evaluated and ranked as follows. 5 No fog at all. 4 Fog is slightly observed. 3 Fog is slightly recognized, but there is no problem in practical use. There is a lot of fog. 1 Fog very much.

ID Evaluation ID evaluation is performed by a Sakura reflection densitometer (model PO-A-60).
Was measured.

[Table 1]

[0050]

EFFECT OF THE INVENTION The toner of the present invention is excellent in the rise of charge and its stability, and can provide a good image with excellent density without scattering and fog. In particular, in a high-speed developing system, toner scattering does not occur. It is possible to provide a high-quality image without fog or offset.

Claims (1)

[Claims] 1. A negatively chargeable toner comprising at least a thermoplastic resin, a colorant and a charge control agent, comprising a charge control resin (CCR) and a calixarene compound as the charge control agent, the charge control resin (CCR) Is represented by the following general formula [I] [Wherein R ₁ is a hydrogen atom or a methyl group, R ₂ or R ₃
Represents a hydrogen atom or an alkyl group having 10 or less carbon atoms, and m represents an integer of 1 to 10]. A sulfonic acid group-containing acrylamide monomer and a vinyl monomer selected from the group consisting of styrene, acrylic acid ester, methacrylic acid ester, and mixtures thereof, and the sulfonic acid group-containing acrylamide monomer is 1 to 20 wt% of the total amount of the monomer. % Of the thermoplastic resin, the charge control resin is contained in an amount of 0.1 to 10 parts by weight, and the calixarene compound is added to 100 parts by weight of the thermoplastic resin. To 0.1
A negatively-chargeable toner containing 10 parts by weight.