JPH02167565A - Toner - Google Patents

Abstract

PURPOSE:To obtain a toner capable of forming superior picture images contg. no fog due to its superior rising characteristic of charge and high stability even in a case of high speed copy by incorporating a specified charge controlling resin (CCR) into a toner compsn. as charge controlling agent (CCA). CONSTITUTION:A CCR prepd. by a copolymn. of a sulfonic acid group-contg. acrylamide type monomer (a) expressed by the formula I with a vinyl monomer (b) selected from a group consisting of styrene, acrylic esters, etc. as CCA, wherein a proportion of (a) is 1-20wt.% basing on the total amt. of the monomers. The CCR is contained in a proportion of 0.1-10pts.wt. basing on 100pts.wt. thermoplastic resin, and other components except the CCR are contained in a proportion of 0.1-10pts.wt. basing on 100pts.wt. thermoplastic resin. In the formula, R1 is an H atom or a methyl group; each R2 and R3 is an H atom or a <=10C alkyl group; m is an integer 1-10. Thus, a toner capable of providing superior picture images in a high speed development system is obtd.

Description

[Detailed description of the invention] Industrial applications The present invention relates to an electrophotographic toner.

Prior Art and its Issues Chikagi electrophotographic copying machines are becoming faster and faster. 1
When printing 50 or more A-4 size sheets per minute, a photoreceptor made of a photoconductive material such as selenium or amorphous silicon is generally used from the viewpoint of photosensitivity. Furthermore, high-speed printers that use electrophotography (such as laser beam printers) use laminated organic photoreceptors. A high-performance negatively charged toner is desired as a developer that develops an electrostatic latent image formed on such a photoreceptor using electrostatic attraction force.

Conventionally, negatively charged toners generally include a charge control agent and a colorant having good negative chargeability dispersed in a binder resin of the toner. When using toner as a developer for medium to low system speeds, the addition of conventional negative charge control agents has some significance, although they have problems with compatibility or dispersibility with resins. Met.

However, in high-speed copying machines where the system speed is 30 cm/sec or higher, especially 40 cm/see or higher,
The developing device is also driven at high speed, and the agitation of the developing device and the rotation of the developing sleeve become high speeds, so it is not possible to use the conventional developer made of low to medium speed toner as is.

For example, because the rotation speed of the developing sleeve is fast, toner scatters from the carrier due to centrifugal force, contaminates the area around the developing device, and furthermore, the contaminated toner appears on the copy as toner droplets or scatters. The toner may form a fog on the photoreceptor and be developed, resulting in a decrease in image quality.

○ R3 [In the formula, R1 is a hydrogen atom or a methyl group, R2 or R1 is a hydrogen atom or an alkyl group having 10 or less carbon atoms,
m represents an integer from 1 to 1O. ] and a vinyl monomer selected from the group consisting of styrene, acrylic esters, methacrylic esters, and mixtures thereof. The charge control resin is copolymerized at a mixing ratio of 2 Qwt. CCA) is thermoplastic resin 100
It relates to a negatively chargeable toner characterized in that the content is 0.1 to 10 parts by weight.

The negatively chargeable toner of the present invention has a problem in that, at least during thermoplastic intermittent copying, the toner charge amount gradually increases, resulting in a decrease in image density (ID).

Note that in this specification, the system speed refers to the circumferential speed of the photoreceptor.

Problems to be Solved The present invention solves the above-mentioned problems, and provides a negatively chargeable l-ner suitable for high-speed copying, which also has excellent charge build-up and stability even during high-speed copying. 1 to 1, which can form good images without scattering, etc., and without fogging, etc.
The purpose is to provide a

Means for Solving the Problems 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 (C:CR) as the charge control agent, and the charge control resin (CCR) or a resin of the following general formula [], a colorant, and a charge control resin. It is characterized by being contained as a charge control resin (hereinafter referred to as OCR).

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

Vinyl monomers copolymerized with the sulfonic acid group-containing acrylamide monomer represented by the general formula [I] include aromatic vinyl monomers such as styrene, and unsaturated carboxylic acids and their esters such as acrylic esters and methacrylic acid. Examples include esters, maleic esters, acrylamide, etc., and mixtures thereof, but any material having an unsaturated bond may be used without particular limitation. In particular, a preferred combination is AMPS
and styrene copolymer, or AMPS and styrene,
A combination with (meth)acrylic ester is preferred.

The copolymer used as a charge control agent in the present invention is produced by radical copolymerization of the sulfonic acid group-containing acrylamide monomer represented by the above general formula [I] and a vinyl 7th polymer in the presence of a polymerization initiation catalyst. It is obtained by

There are no particular restrictions on the polymerization method, and any known radical polymerization method may be used. For example, when copolymerizing with AMPS, solution polymerization is suitable because it is water-soluble.

As the polymerization initiation catalyst, azo catalysts are preferred, such as azobisisobutyronitrile, azobisdimethylvaleronitrile,
Examples include azobisdimethylmeth1-quinvaleronitrile.

The mixing ratio of both monomers is 1 wt% to 2 wt% of the sulfonic acid group-containing acrylamide monomer represented by the general formula [I].
0 wt%, preferably 2-19 wt%, more preferably 5-19 wt%, at least one diol component selected from the group consisting of ols, rosin-type diols, and glycols, and phthalic acid, isophthalic acid, terephthalic acid, Examples include at least one dicarboxylic acid selected from the group consisting of aromatic dicarboxylic acids such as, and aliphatic dicarboxylic acids such as phthalic acid, maleic acid, and ardipic acid, and polyester resins that are threatened by trimellitic acid. The fixing temperature may be selected appropriately taking into consideration the softening point of the selected thermoplastic, but in order to achieve high-speed fixing performance,
In particular, the number average molecular weight (Mn) is 2000-10000.
More preferably, it is 2,500 to 7,000.

Various charge control agents other than the charge control resin can be used, but for example, metal-containing complex salt oil-soluble dyes are preferred, which function to impart negative chargeability to the toner, and hydroxy-substituted naphthoic acids and their alkyl dyes are preferred. Derivatives, hydroxy-substituted tetrahydronaf] - Metal complex compounds such as alkyl derivatives of engineering acids and salicylic acid: Or general formula - Unisushi. If the amount is more than 20wt%, the electrical resistance of the toner will be low, and the change in the amount of charge over time will become large.
When the amount is less than t%, toner scatters a lot and there is a lot of fogging after printing, making it unusable.

The amount of CCH used in the present invention is 0.1-10 parts by weight per 100 parts by weight of the thermoplastic resin. If the amount is less than 0.1 part by weight, toner charging will be slow, causing a lot of toner scattering, and toner dropping. When the amount is more than 10 parts by weight, the toner becomes highly hygroscopic, and the charge amount changes over time and the attenuation rate becomes large.

The thermoplastic resin used in the present invention is not particularly limited, but any thermoplastic resin may be used as long as it has a softening point sufficient for general fixing and a glass transition point sufficient for storage stability.

The softening point of the thermoplastic resin suitable for the present invention is determined depending on the development speed and the mechanism of the system, as long as the effects of the present invention are not impaired.
Thermoplastic resins with a low softening point are preferred, such as polystyrene, copolymer resins of styrene and acrylic esters or methacrylic esters, hisphenol type di(wherein, X is a hydrogen atom, a lower alkyl group, a lower alkoxy group,
represents a nitro group or a halogen atom, n is 1 or 2
, m represent an integer of 1 to 3, X may be the same or different, M represents a chromium or cobalt atom, and A represents hydrogen, sodium, potassium or ammonium ion. ) A metal complex compound represented by the formula: %Formula%) A metal complex compound represented by the general formula: (wherein,
Xl and X2 represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a nitro group or a halogen atom. Xl
and X2 may be the same or different; ...and m' represents an integer of 1 to 3; R1 and R3 represent a halogen atom. As black pigments, carbon black such as channel black and furnace black, acetylene black,
Lamp black, aniline black, etc.: Yellow pigments include yellow lead, zinc yellow, cadmium yellow, yellow iron oxide, mineral fast yellow nickel titanium yellow, navel yellow, naphthol yellow S1 Hansa Yellow G, Hansa yellow JOG, benzidine yellow G1 Benzidine Yellow GR, Quinoline Yellow Lake,
Permanent yellow, NCG, tartrazine lake, etc.:
Orange pigments include red yellow lead, molybdenum orange, permanentet orange GTR, pyrasolone orange, palkan orange, industhrene brilliant orange RK,
Benzidine Orange G1 Interstole Brilliant Orange GK, etc.; Red pigments include Penkara, Gadmium Red, Red Lead, Mercury Cadmium Sulfide, Permanent Red 4R, Lysol Resod, Pyrazolone Red, Wadashi, even if R1 and R8 are the same. May be different; n
and n' represent an integer from 1 to 3, R2 and R2 represent a hydrogen atom or a nitro group, M represents a chromium or cobal l-atom, and K represents a sodium, potassium or ammonium ion. ) can be used, as well as complex salts of salicylic acid or its derivatives with metals, but are not limited to the metal-containing oil-soluble dyes listed here.

Charge control agent other than charge control resin is thermoplastic resin 100
It is used in an amount of 0.1 to 10 parts by weight. If less than 0.1 part by weight is used, a sufficient amount of charge cannot be imparted to 1.sup. If more than 10 parts by weight is used, the amount of charge will be rather low, and the charge control agent released from the toner will adhere to the photoreceptor, causing a filming phenomenon.

The negatively chargeable toner of the present invention may further contain a colorant that exhibits a desired color and, if necessary, other charge control agents.

Chingresod, Calcium Salt, Lake Red D1 Brilliant Carmine 6B, Eon Lake, Rhodamine Lake B, Alizarin Lake, Brilliant Carmine 3B, etc. Purple pigments include Manganese Purple, Fast Violet B
1 Methyl violet lake, etc.; as a blue face, dark blue,
Cobalt blue, alkali blue lake, hyftria blue lake, 7 thalocyanine blue, metal-free phthalocyanine blue talocyanine blue partially chlorinated product, fast sky blue, industhrene blue BC, etc. Green pigments include chromium green, chromium oxide, pigment green B1 Malachite Green Lake, Final Yellow Clean G, etc. White pigments include zinc white, titanium oxide, antimony white, zinc sulfide, etc. Extender pigments include pallite powder, barium carbonate, clay,
Silica, white carbon, talc, alumina white, etc. Examples of the yellow colorant include Bendecine Yellow, Hansa Yellow, Kromofukur Yellow, etc.

These colorants may be used alone or in combination of two or more, and may be organic or inorganic, as long as they are non-polluting and have high coloring power, and are not limited to these.

The toner of the present invention is prepared by using the thermoplastic resin and the various additives described above in the proportions specified in the specification, or in the known proportions if not specified. The so-called pulverization method, which involves dispersing raw materials other than the main resin in monomers and incorporating them into the toner during polymerization of the resin, and the granulation method, which uses equipment such as spray drying. However, the method is not particularly limited to these methods. Note that the average particle diameter of the toner can be arbitrarily selected from 5 to 20 μm.

The toner of the present invention may further contain other additives, such as waxes, etc., as necessary, and in order to improve fixing properties, various thermoplastic resins, 2-acrylamide-2, etc. -Methylpropanesulfonic acid (AMPS)
100g 2-2'-azobisisobutyronitrile 60g xylene
1000g/methanol
50.More than 50g of material is equipped with a stirring device. The mixture was placed in a 4-hole flask, and after nitrogen was introduced, the temperature was raised to 80'C and the reaction was allowed to proceed for 5 hours. Next, the temperature is raised to 100'C to complete the reaction, and then the mixture is placed in a reduced pressure heating furnace to remove the xylene and methanol.

The molecular weight of the obtained styrene-AMPS copolymerization determined by gel permeation chromatography (GPC) is number average molecular weight (Mn) + 1.960°, weight average molecular weight (Mw) + 7,120, and differential scanning calorimetry (D
Glass transition point (Tg) determined by SC): 92°C.

The charge control resin obtained in this production example is designated as CCR1.

Production example of charge control resin (CCR2) - Styrene 700g It may be used within a range that does not reduce the effects of the present invention.

Alternatively, the surface of the toner may be treated with ultrafine metal oxide powder.

The toner of the present invention can be used, for example, by blending with a suitable carrier.
It can be used as a preservative developer. As the carrier, resin-coated glass beads, steel balls, etc. are used when implementing the cascade development method, and ferrite, fine iron powder, or a so-called binder type carrier are used when implementing the magnetic brush development method. Further, the toner of the present invention itself may be manufactured as an insulating magnetic toner, and a magnetic brush development method may be carried out using this as a preservative thread developer.

Furthermore, it may be used as a toner when performing an impression development method or a touchdown development method.

The present invention will be explained in more detail with reference to Examples below.

・2-acrylamido-2-methylpropanesulfonic acid (AMPS) 1009・n-butyl methacrylate 200g ・2-2'-Azohis (24-dimethylvaleronitrile)
60g xylene
1000g/methanol
A charge control resin copolymerized with AMPS was obtained from 50 g or more of the material by the same synthesis method as for CCRl. Molecular weight by GPC: Mn: 2.890, Mw: 9
240, and the Tg by DSC was 82°C.

The charge control resin obtained in this production example is designated as CCR2.

Manufacturing example of charge control resin (CCR3) ・Styrene 800g・A
MP3 200g
・2-2′-Azohis(24-dimethylvaleronitrile) 60g・Xylene 100g・Methanol
A charge control resin copolymerized with AMPS was obtained from 50 g or more of the material by the same synthesis method as CCR1. Molecular weight by GPC is Mn: 3,350
, Mw: 8,920, and Tg by DSC is 92
It's °C.

The charge control resin obtained in this production example is designated as CCR3.

Manufacturing example of charge control resin (CCR4) ・Styrene 750g・A
MPS 250g・2-
2'-azobis(24-dimethylvaleronitrile)
60g xylene
1000g/methanol
A charge control resin copolymerized with AMPS was obtained using a material of 50i+ or higher by the same synthesis method as CCR1. Molecular weight by GPC: Mn: 3,130, M
w: 9 190, Tg by DSC is 94°
A toner having a particle diameter of .mu.m was obtained. The surface of this toner was treated with 0.2% hydrophobic silica (R-974, manufactured by Nippon Aerosil Co., Ltd.). The toner thus obtained is referred to as Toner 1.

Production of toner 2 Thermoplastic polyester resin 100 parts by weight Mn:
5,200 Mw: 202,500 acid value・
17.8, Softening point 122°CTg: 67°C ・Carbon black 8 parts by weight MA#8
(manufactured by Mitsubishi Chemical Industries, Ltd.) - Offset prevention additive 4 parts by weight Viscol TS 200 (manufactured by Sanyo Kabo Industries, Ltd., oxidized low molecular weight polypropylene) - Pontron 5-34 3 parts by weight, manufactured by Orient Kagaku Kogyo Co., Ltd. (contains Cr) (oil-soluble dye)/Charge control resin (CCR) 22 parts by weight or more of CCR material was processed in the same manner as in the production of toner 1 to obtain an average diameter of 10.
．． A toner having a particle size of 8 μm was obtained. The toner thus obtained is referred to as Toner 2.

The thermoplastic polyester resin used in the production of Moki I-Nar was produced as follows.

・Bisphenol A/propylene oxide adduct 10
0g The charge control resin obtained in this production example is referred to as 0CR4.

Manufacture of toner l Thermoplastic styrene acrylic resin 100 parts by weight Mn: 4.500 Mw: 197,800T
g: 60.5℃ Softening point/121'0 Acid value 24,
3 ・Carbon black 7 parts by weight MA#1
00 (manufactured by Mitsubishi Chemical Industries, Ltd.) - Offset prevention additive 4 parts by weight Viscoel 660 P (manufactured by Sanyo Kabo Industries, Ltd., low molecular weight polypropylene) - Subiron Black TRH 2 parts by weight, manufactured by Hodogaya Chemical Industries, Ltd. Cr-containing metal oil-soluble Dye/Charge Control Resin CCRl 2 parts by weight or more of material in 10Q
The mixture was placed in a Henschel mixer, mixed for 2 minutes at 200 Orpm, and then continuously extruded and kneaded using PCM30 (+2/d: 32.5). Next, after cooling, it was coarsely pulverized with a 2mm mesh feather mill, finely pulverized with a jet pulverizer, and coarse and fine powders were cut with an air classifier.
] 09g trimellitic anhydride 45
g. xylene Put 50g or more of material into 4 3A flasks and heat in a nitrogen stream for 24 hours.
The reaction was carried out at 0°C for 5 hours, and then the temperature was raised to 270'0, and the reaction was carried out for 8 hours. The by-product acid water was distilled off.

Manufacture of Toner 3 Thermoplastic styrene/acrylic resin 100 parts by weight Mn: 3,600 Mw+ 186,400T
g: 61.2°C Softening point 124°C Copper-phthalocyanine pigment 5 parts by weight #4920 (manufactured by Ota Kasei Co., Ltd.) - Offset prevention additive 4 parts by weight Hiscole 550P (manufactured by Sanyo Kakai Kogyo Co., Ltd.) - Pontron E -84
3 parts by weight (manufactured by Orient Kagaku Kogyo Co., Ltd., Cr-containing metal dye) Charge control resin CCR 12 parts by weight or more of material was processed in the same manner as in the production of toner 1 to obtain an average diameter of 11.
．． A toner having a particle size of 6 μm was obtained. The surface of this toner was treated with hydrophobic silica (H-2000) (manufactured by Nippon Hoechst Co., Ltd.). The toner thus obtained is referred to as Toner 3.

Manufacture of toners 4 to 6 (4 salts) Among toners 1.2.3, charge control resin CCRI or C
Each toner was obtained using the raw materials except CR2. The surface treatment of the toner of each comparative example was the same as that of the example. The particle size is as follows.

Comparative example 1 10.9 μm...Toner 4 Comparative example 2
11.1 μm... Toner-5 Comparative Example 3 11.4
μm... Manufacture of toner 6 and toner 7 and 8 In the manufacture of toner 1, CCR1 is changed to CCR3, CCR4
Toner 7.8 was obtained using the same composition and manufacturing method as those for Toner 1.

Toner 7: l 1.2 μm, Toner 8: 1
Production of 1.3 μm Toners 9 to 17 Toner 9 was produced in the same manner as in the production of Toner 1, except that the following amounts of Spilon Black TRH and charge control resin CCR1 were used.
~17 were produced.

Toner 19 was obtained using the same composition and manufacturing method as for Toner 1, except that Toner 1 was used.

The average diameter of the obtained toner 19 was 10.9 μm.

Production of Toner 20/100 parts by weight of thermoplastic resin used in production of Toner 1/7 parts by weight of carbon black MA#
Toner 11 was obtained in the same manner as in Toner 1 using 10 parts by weight or more of charge control resin CCRI (manufactured by Orient Chemical Industries, Ltd.).

The average diameter of the obtained l·ner was 11.2 μm.

Manufacture of Carrier I - Styrene-acrylic resin 100 parts by weight (Prioride ACL: manufactured by Goodyear) Mapico Black BI, -500200 Parts by weight Toner 9 0.1 2 10
．． 8 toner 10 10 2 1
1.2 Toner 11 0.05 2 10
．． 91-ner 12 15 2 11.
0 toner 13 2 0.1 11.1 toner 14 2 to 1.1.4
Toner 15 2 0.05 11.
3 toner 16 2 15 11
．． 1 toner 17 4 1
1.3 Manufacture of Toner 18 (Comparative Example) Toner I8 was obtained using the same composition and manufacturing method as in Toner I, except for excluding the charge control agent Subiron Blank TRH.

The average diameter of the obtained toner 18 was 11.3 μm.

Production of Toner 19 The thermoplastic styrene-acrylic resin had the following physical properties;
Mn: 12,100, MW: 178,400-Tg+6
2.3°C1 Softening point = 126, acid value: 26°2, (triiron tetroxide; manufactured by Titan Kogyo Co., Ltd.) ・Carbon black MA#8 Part by weight (manufactured by Mitsubishi Chemical Industries, Ltd.) Three rolls of the above materials The mixture was melted, kneaded, assimilated, crushed and classified to obtain a magnetic carrier (2) with an average particle size of 35 μm.

(Resin used in the production of Toner 2) (Average particle size 0.7 μm) ・Carbon black MA#8 4 parts by weight or more was mixed in a 1012 Henschel mixer and then extruded using a PCH
30 (Ma 32.5), cooled and solidified, and then pulverized and classified to obtain a magnetic carrier (2) with an average diameter of 55 μm.

Toner evaluation Toner 1-20. A developer was prepared by combining and Carrier I or (2), and the evaluation described below was performed. The results are shown in Table 11.

■Charge amount measurement A total of 20 toners 1 to 20 are added to the microcarriers ■ and ■.
The sample was brought to a concentration of 10 wt%] and 100 c
Put 60g into the plastic bottle shown in c, place it on a rack at 120 rpm per minute, and calculate the amount of charge (Q) after 3 minutes, 10 minutes, and 30 minutes.
f) was calculated.

■Measurement of scattering amount Also, the carrier ■ and toner concentration were set to 20 wt%, and the scattering amount after mixing for 3 minutes was determined using the following device.

Magnet and its surroundings (Magnet 1 with this sleeve)
- Place 10g of the above developer with a toner concentration of 20WL% on the roller, and run the magnet at 1000 rpm per minute.
The scattered toner was measured for 1 minute using a digital dust meter manufactured by Shibata Chemical Co., Ltd. when the toner was rotated at a speed of 45 c++/5 ec for high-speed development. In addition, the amount of scattering at a normal system speed of 20 cm/sec is shown in the column of scattering amount (■) in Table 1 for comparison.

Splashing that can be practically used if it is 500 cpm or less 5
No fogging at all.

4 Slight fogging is observed.

3. Some fogging is observed, but there is no problem in practical use.

2. Too much fog.

1. There is a lot of fog.

(Hereinafter, blank space) Even if the amount is in a practical machine, there are almost no problems due to scattering, but if the amount exceeds 500 cpm, especially 1,000 cpm,
If it exceeds cpm, there will be a lot of scattering, which will stain the area around the developing device and cause troubles such as fogging.

■Moisture resistance Charge amount attenuation after aging The charge amount was measured (Charge amount when mixed and stirred for 30 minutes:
Qf (30 minutes), the amount of charge (Qf (3
5°C-85%-36ays)), and the attenuation amount was determined using the following formula.

(2) Image Evaluation Carrier (2) and Toners 1 to 20 were each placed in a 1Q plastic bottle so that the toner concentration was 7 wt%, placed on a Pormill stand, and a developer was prepared at IOHr, 12 Orpm.

Put this developer into EP870 made by Minolta Camera Co., Ltd.
K sheets were subjected to printing durability test 1, and the presence or absence of fog was evaluated and ranked as follows.

As seen from Table 1, the amount of AMPS added is 2Qwt%.
If the toner exceeds this value, the electrical resistance of the toner itself becomes low, causing a leakage of the charged charge, and rather the amount of charge does not increase even if the stirring time is increased, but decreases. Also, the change in the amount of charge over time is 46
%, which is not practical. Furthermore, as can be seen from the amount of scattering, there is almost no difference at normal system speeds, but in high-speed development systems, the amount of scattering increases and fog occurs, making it unusable. This is considered to be because the addition of CCR using AMPS improved the charge build-up and narrowed the distribution.

Effects of the Invention The toner of the present invention has excellent charge build-up and stability, and can provide good images with excellent fog and density. Especially in high-speed development systems, the toner does not cause toner scattering and has good image quality without offset. images.

Patent applicant: Minolta Camera Co., Ltd. Representative patent attorney: Haka Aoyama (1 person) procedural correction sound (method) 1.Display of the incident 1986 2. Name of the invention toner 3. Person who makes corrections Patent application No. 11.54.36 Name (607) 4. Agent Minolta Camera Co., Ltd. November 28, 1999 6. Subject of correction Specification (page 2) 7. Contents of correction As per attached sheet Purification (no change in content) <Date of shipment) ・Sleeping

Claims (1)

[Claims] 1. A negatively chargeable toner comprising at least a thermoplastic resin, a colorant, and a charge control agent, which contains a charge control resin (CCR) as the charge control agent;
CCR) is the following general formula [I]▲Mathematical formulas, chemical formulas, tables, etc.▼[I] [In the formula, R_1 is a hydrogen atom or a methyl group, R_2 or R_3 is a hydrogen atom or an alkyl group having 10 or less carbon atoms, m represents an integer from 1 to 10. ] and a vinyl monomer selected from the group consisting of styrene, acrylic esters, methacrylic esters, and mixtures thereof. 20wt. %, and the charge control resin is a thermoplastic resin with a mixing ratio of 100%.
It is contained in an amount of 0.1 to 10 parts by weight per part by weight, and a charge control agent (CCA) other than the charge control resin is contained in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the thermoplastic resin. Negatively chargeable toner featuring: