JPH04195148A - Negatively chargeable toner for electrophotography - Google Patents

Abstract

PURPOSE:To obtain a negatively chargeable toner ensuring a sharp distribution of the amt. of electric charges by using polyester resin as resin for fixing and incorporating an electric charge controlling aid incompatible with the resin for fixing but dispersible in the resin and having action in reverse polarity to an electric charge controlling agent for negative charging. CONSTITUTION:Polyester resin is used as resin for fixing and an electric charge controlling aid incompatible with the resin for fixing but dispersible in the resin and having electric charge controlling action in reverse polarity to an electric charge controlling agent for negative charging is incorporated into a toner. Since such a positive charge controlling substance is combined with the electric charge controlling agent for negative charging, the distribution of the amt. of electric charges on the toner can be made sharp. A negatively chargeable toner hardly giving a highly charged toner not used for development and a slightly charged toner causing scattering can be obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a negatively chargeable electrophotographic toner,
More specifically, the present invention relates to a negative IF electrophotographic toner that is free from toner scattering and can form high-density images.

(Prior Art) In the fields of commercial electrophotographic copying and electrophotographic printing, positive
1:'r! A method of forming an electrostatic image of L is generally adopted, and therefore, negatively charged toner is widely used as the developing toner used to develop this electrostatic image.

On the other hand, in recent years, the development of laser beam printers and digital copying machines has progressed, and in such image forming apparatuses, a latent image is written on a negatively charged organic photoreceptor using a laser.
A process of reversal development using negatively charged toner is adopted,
There has also been a demand for higher quality negative charging toner.

A developing toner is made by granulating a resin composition containing a fixing resin, a colorant, and a charge control agent as essential components to a toner particle size, generally an average particle size of 5 to 15 μm. In the case of a negatively charged toner, as a matter of course, a charge control agent having a negative charge control effect during triboelectric charging is used.

In conventional toner charge control systems, the average value of the toner charge amount for the toner as a whole is controlled by selecting the type of charge control agent and adjusting the amount added. However, in this method, although it is possible to control the average value of the charge amount of the toner as a whole, it is extremely difficult to strictly control the distribution of the IF charge amount of the toner particles.

Conventionally, toner particles have i! of opposite polarity to each other. It is already known to contain a plurality of charge control agents having different performance characteristics. For example, in Japanese Patent Laid-Open No. 54-34243, in an electrostatic image developer consisting of a toner and a carrier, the toner is added to the carrier. A developer for electrostatic images is described, which is a negatively charged toner containing a dye that becomes positively charged by friction with the toner.

JP-A-57-196264 discloses an electrically insulating magnetic component developer comprising an electrically insulating fixing medium, a magnetic material powder dispersed in the fixing medium, and a charge control agent. The charge control agent is characterized in that it consists of a combination of a negative or positive charge control agent and a reverse rod charge control agent in a weight ratio of 1:0.05 to 1:1.5. Developer is listed.

(Problems to be Solved by the Invention) In conventional negatively chargeable toners, even if the type and amount of charge control agent added are adjusted so that the average value of the charge amount is a sufficiently satisfactory value, , there is an inevitable tendency that the distribution of the i charge becomes quite wide. A particular problem here is that the amount of charge is considerably higher than the average value, and highly charged toner that is not consumed for development is inevitably generated at a frequency (amount of distribution). Another problem is that the amount of charge is considerably lower than the average value, and low charge toner that causes toner scattering occurs frequently.

The former highly charged toner particles are strongly electrically adsorbed to the surface of the carrier particles and exist in a state where they are difficult to separate from, significantly impairing the triboelectric charging performance of the carrier particles. For this reason, even if the toner has relatively few problems at the beginning of development, as development time progresses, the proportion of uncharged or low-charge toner increases, causing toner scattering, fogging, and image density. Problems such as deterioration will occur.

In the method of combining a positively chargeable dye (charge control agent) with a charge control agent for negative charge as seen in the prior art, the charge amount distribution can be shifted quite freely to the high charge amount side or to the low charge amount side. Even though this method has the advantage of sharpening the toner charge amount distribution and suppressing the generation of highly charged toner and low charged toner to a negligible level, this method is still not fully satisfactory. It was not possible.

Therefore, an object of the present invention is to eliminate the above-mentioned drawbacks of conventional negatively charged toners, to ensure that the average value of the toner charge amount is within the optimum range in terms of toner scattering prevention and image density, and that the toner charge amount distribution is sharp. Therefore, it is an object of the present invention to provide a negatively charged toner that has almost no highly charged toner that is not used for development and lowly charged toner that causes toner scattering.

Another object of the present invention is to provide a sharp toner charge amount distribution and! It is an object of the present invention to provide a toner for negative f-electrification, which has a rapid rise in charge in terms of quantity of electricity and whose charging characteristics are less likely to deteriorate during long-term operation.

(Means for Solving the Problems) According to the present invention, in a negative band electrophotographic toner containing a fixing resin, a colorant, and a negative charge control agent, the fixing resin is a polyester resin. The toner is characterized by containing in the toner a charge control aid which is incompatible with the fixing resin but has dispersibility and has a charge control action of opposite polarity to that of the charge control agent for negative charging. A negatively charged electrophotographic toner is provided.

In the present invention, it is preferable to use a quaternary ammonium salt, particularly a quaternary ammonium salt containing an oxyacid anion as the anion, as the charge control aid.

The charge control agent (A) and the charge control aid (B) are A:
B=1: preferably present in a weight ratio of 0.05 to 1:1, particularly 1:0.1 to 1:0.7, and a total of 0.5 to 5 weight per 100 parts by weight of fixing resin. part, especially 2
It is preferable to use it in an amount of 4 to 4 parts by weight.

(Function) The electrophotographic toner for negative charging of the present invention contains a fixing resin, a colorant, and a charge control agent for negative charging as essential components. A notable feature is that it contains a charge control auxiliary agent which is incompatible with the polyester resin but has dispersibility and has a charge control action of opposite polarity to that of the charge control agent for negative charging.

That is, in place of the conventionally used positively charged dye that is compatible with the fixing resin, the present invention uses a positively charged dye that is incompatible with the polyester resin that is the fixing resin but has dispersibility. When a control substance is used as a charge control aid in combination with a charge control agent for negative charging, the distribution of toner charge amount can be made significantly sharper than that of conventional ones, and as a result, it becomes easier to develop. This is based on new knowledge that the generation of unused highly charged toner and lowly charged toner that causes toner scattering can be effectively suppressed.

Further, in the present invention, it is also important to use polyester resin as the fixing resin. This polyester resin has sufficient frictional f-electricity (negative! electric charge) in the resin itself,
Polycarboxylic acids that can also be used as esterifying agents,
Since there are many types of polyhydric alcohols, the properties of the resin can be freely controlled. Therefore, it is easy to obtain a polyester resin in which the charge control aid is incompatible and dispersible, and it can be used as a fixing resin that can effectively exhibit the above-mentioned effects of the present invention.

Figure 2 of the accompanying drawings shows toner A using only a charge control agent for negative charging (Comparative Example 1), and Figure 3 shows toner A using a charge control agent for negative charging in combination with a positively charging dye (see Comparative Example 2). The distribution of charge amount was measured for Toner B1 used in Figure 1 and Toner C used in combination with the above-mentioned negative f-charge toner and a charge control aid (see Example 1) that satisfies the requirements of the present invention. This is a graph showing the results.

In other words, with toner A in which a negative charge control agent is used alone for a negatively chargeable polyester resin, most of the toner can be charged to the negative charge side as shown in FIG. A large amount of highly charged toner exists, and d-range oppositely charged toner and zero-charged toner are still generated. - On the other hand, in Toner B of the prior art, in which a negatively chargeable polyester resin is combined with a negatively charge control agent and a positively chargeable dye, the average value of the charge amount is shifted to the low charge amount side, as shown in Figure 3. Although it can be shifted, the breadth of the distribution is almost the same as toner A, the highly charged toner in the a region is decreased but still exists, and the proportion of oppositely charged toner and OIF charged toner in the d region increases. . On the other hand, in Donor C of the present invention, which is a combination of a negative charge control agent for a negatively chargeable polyester resin and a positive charge control substance incompatible with the polyester resin as an auxiliary agent, as shown in FIG. In the proper charging range, the amount of toner in c increases, which significantly narrows the width of the charge amount distribution in f, and increases the amount of toner in the a range. It is understood that the amount of charged toner, reverse ft toner in the d region, and zero-charged toner can be reduced (here, they are eliminated).

In Table 341, the above toners A, B and C were used, and 1000 Image density when making continuous copies (
ID), image fog (FD), and toner scattering around the developing device were evaluated.

From FIGS. 1 to 3 and Table 1, it is confirmed that the toner of the present invention can be repurchased with preferable charging characteristics that can suppress a decrease in image density, image fogging, and toner scattering.

In this specification, the IF charge distribution of toner is determined by the following method.

i! To explain this charge amount measuring device below, as shown in FIG. , a measurement unit 3 that measures the charge amount distribution of the separated toner, and a suction device 10 such as an air pump.

The separation section 2 and the measurement section 3 are separated by a partition plate 7, and a communication hole 1a for introducing air into the housing 1 is provided in the side wall of the housing 1 slightly below the partition plate 7.
is provided. An air rectifying filter 8 is disposed slightly below the communication hole 1a.

The separating unit 2 uses an air needle 5 to blow compressed air onto the developer held on the magnet 4, leaving behind the carrier magnetically attracted to the magnet 4, and blowing only the lightweight toner upward and scattering it. let

A funnel 6 supported by a partition plate 7 is provided between the separating section 2 and the measuring section 3. A receiving opening 6d at the upper end of the funnel 6 protrudes above the partition plate 7, and a recessed portion 6a at the lower end passes through the filter 8 and faces the measuring section 3 side.

The measurement unit 3 applies a DC power supply R to a pair of electrode rods 9a and 9b embedded in the side wall of the housing 1, thereby forming a horizontal parallel electric field between the electrode rods 9a and 9b.

10 is a filter.

The suction device 11 connects the communication hole 1 from the outside of the housing 1.
A and the rectifying filter 8 to form a main air flow that flows to the measuring section 3, and at the same time, an air flow that sucks the toner into the funnel 6 is formed above the funnel 6.

According to this charge amount measuring device, the toner particles separated by the separating section 2, collected by the funnel 6, and introduced into the measuring section 3 fall vertically on the air current generated by the suction device 11, and fall vertically to the electrode rod 9a.

9b and lands on the filter 10.

At this time, the toner particles fall while being subjected to a horizontal Coulomb force H depending on the amount of charge and a vertical gravity V in the horizontal parallel electric field between the electrode rods 9a and 9b. They are dispersed on the filter 10 at positions corresponding to their mass and charge amount. Then, from the distribution of the falling positions of the toner particles, the toner charge amount distribution is calculated by image processing.

The f-coulometric distribution curves in Figures 1.2 and 3 were measured by this method.

From these results, the toner of the present invention does not cause fluctuations in image density, fog, or toner scattering, not only during the initial stage of development but also when development is performed for a long period of time, and has remarkable improvement in wit characteristics and prevention of deterioration thereof. It shows that it is effective.

In the toner of the present invention, the fact that the charge amount distribution becomes sharper by using an incompatible positive charging charge control agent in the polyester resin that is the fixing resin has been confirmed as a result of numerous experiments. The reason for this is not clear, but the positive charge dye that is compatible with the fixing polyester resin has no effect on sharpening the distribution, and the negative charge control agent is compatible or dispersed. It is presumed that the dispersed structure in which the charge control aid for positive charging is dispersed in a macroscopic particle size in the matrix acts to reduce the number of high IF charge toners and negatively charged toners. . In general, one of the major drawbacks that arises when a negative charge control agent is combined with a positive charge control agent as an auxiliary agent is that even if the charge of the toner particles is ultimately controlled to be negative, the toner and carrier When a developer consisting of husks is stirred in a developing device, the charge rises slowly. On the other hand, with the toner having the composition and dispersion structure of the present invention, the charge rise when the developer starts to be stirred and charging starts is similar to that of the negatively chargeable toner containing only the negatively chargeable charge control agent. It also has the advantage of being fast.

(Preferred embodiment of the invention)! Nikon Tanmi 1 The charge control aid used in the present invention is incompatible with the polyester resin that is the fixing resin, but has dispersibility and has a charge of opposite polarity to that of the charge control agent for negative charging. It has a controlling effect, and specifically, quaternary amminirum salt is used.

Suitable quaternary ammonium salts include the formula % Formula % wherein at least one of R is a long-chain alkyl group or a long-chain alkenyl group, and at least two of them are a lower alkyl group or a benzyl group. Under the condition that it is a base,
It is a lower alkyl group, a benzyl group, a long-chain alkyl group, or a long-chain alkenyl group, and A- represents an anion.

It is possible to list the compounds represented by .

Examples of the oxyacid anion include phosphorus oxyacids such as orthophosphoric acid and pyrophosphoric acid, and anions such as molybutenic acid, tungstic acid, antimonic acid, and bismuthic acid. These quaternary ammonium salts are particularly suitable for the purpose of sharpening the charge amount distribution without slowing down the charge rise of the toner.

Uono 'tJ'! ] [1 pull 1 wind wound As the negative charge control agent used in combination with the above charge control aid, any known negative charge control agent can be used, and suitable negative charge control agents include 1 :Type 1 or 2:
Type 1 metal complex dye, naphthenic acid metal salt, especially in the formula, A and B each represent a residue of a diazo component and a coupling component having a phenolic hydroxyl group at the ortho position, and M represents a chromium, iron or cobalt metal. Representation, [
Y]” represents an organic or inorganic cation.

It is a metal complex dye represented by

Typical of these are C,1, Arashido black
123, C, 1, Solvent Black 22, C,
1, Solvent Black 23, C, 1, Solvent Black 28, c, r, Solvent Black 42, C
，! , Solvent Black 43, etc.

In the present invention, the self-charge control agent and the charge control auxiliary agent are preferably used in a weight ratio of t:o, os to 1:1, particularly 1:(1,1 to 1:0.7), These combinations are preferably present in a total amount of 1 to 5 parts by weight, particularly 2 to 4 parts by weight, per 100 parts of polyester resin as the fixing resin.

As mentioned above, the use of polyester resin as the fixing resin is also an important feature of the present invention.

As the polyester resin, a known polyester resin that is not compatible with the charge control aid but exhibits dispersibility can be used.

Generally, where R is an ethylene or propylene group and m or n is a positive integer.

It is preferable to use a polyester resin obtained by condensation polymerization of a diol component represented by the following formula and a polyhydric carboxylic acid, its acid anhydride, or its conductor as an acid component.

As the diol component represented by the above formula, polyoxypropylene-2,2-bis(4-hydroxyphenyl)
Propane, polyoxyethylene-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene-
Examples include polyoxyethylene-2,2-bis(4-hydroxyphenyl)propane.

Carboxylic acid components include maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, succinic acid, adipic acid, sepacic acid, malonic acid, Riluic acid, 1,2.4 benzenetricarboxylic acid, 1,2.5 benzenetricarboxylic acid, 1°2.4 cyclohexanetricarboxylic acid, 2.5°7 naphthalenetricarboxylic acid, 1,2.4 naphthalenetricarboxylic acid, 1, 2.5 hexanetricarboxylic acid, 1,2.
4-butanetricarboxylic acid, 1,3-dicarboxy-2-
Methylcarboxypropene, 1,3-dicarboxy-2
-Methyl-2-methylcarboxypropanetetra(methylenecarboxy)methane, 1,2,7.8 octanetetracarboxylic acid, embol trimer and acid anhydrides thereof.

This polyester resin is produced by polycondensing the diol component and the polycarboxylic acid component. In addition to the etherified bisphenol represented by the above general formula, other diol components such as ethylenoglycol and bisphenol A can also be used in combination within a range of 10 mol % during the reaction.

Colorant As the colorant contained in the resin, the following inorganic or organic pigments, dyes, etc. are used alone or in combination of two or more.

For example, carbon black such as Fehnes black and channel black; iron black such as triiron tetroxide; rutile-type or anatase-type titanium dioxide; phthalocyanine blue; phthalocyanine green; cadmium yellow; molybdenum orange; pyrazolone red: fast violet B, etc. can be mentioned.

Toner The particle size of the toner particles is preferably in the range of 5 to 15 μm, particularly 7 to 12 μm, as measured by a volume-based median diameter using a coulter counter, and the particle shape is manufactured by a melt-kneading/pulverization method. It may be amorphous or spherical produced by dispersion or suspension polymerization.

The toner of the present invention has excellent properties when used as a two-component magnetic developer in combination with a magnetic carrier known per se! Electricity is demonstrated. As the magnetic carrier, a ferrite carrier or an iron powder carrier can be used, but it is generally preferable to use a ferrite carrier. These can be used either uncoated or resin-coated.

Traditionally, ferrite carriers have been used, for example, iron zinc oxide (
ZnFe204), iron yttrium oxide (YsFes
O+z), iron cadmium oxide (CdFe204), iron gadolinium oxide (Gd3FezO+2), iron copper oxide (CuFe20n), iron oxide complex (PbFe1201)
9)% Nickel iron oxide (NiFe204), neodymium iron oxide (NdFeO3), barium iron oxide (B
aFe+20+9), magnesium iron oxide (MgFe
204) Sintered ferrite particles with a composition consisting of one or more of iron manganese oxide (MnFe204), lanthanum iron oxide (LaFeO+), etc. are used,
Especially Cu, Zn, Mg.

Soft ferrites containing at least one metal component, preferably two or more metal components selected from the group consisting of Mn and Ni, such as copper-zinc-magnesium ferrite, are used in the present invention. are also preferably used.

Coating resins for magnetic carriers include acrylic resin, styrene resin, silicone resin, fluorine resin,
Various amino-modified resins are known, but
Preferably, the toner charge is indirectly controlled to be negative by controlling the charge of the resin-coated magnetic carrier to be positive. Of course, in the present invention, charge control can be performed effectively and reliably even without the presence of such a carrier coat resin layer. The saturation magnetization of the carrier is between 40 and 75 emu/g, especially between 45 and 70 emu/g.
It is desirable that it be in the emu/g range. The magnetic carrier is particularly preferably a spherical ferrite carrier, whose particle size is 20 to 140 μm, particularly 50 to 100 μm.
It is desirable to be in the μm range.

The mixing ratio of toner and magnetic carrier varies depending on their physical properties, but is generally 1:99 to 10:1 by weight.
90. In particular, it is desirable that the ratio be within the range of 2:98 to 5:95. In addition, the electrical resistivity of the developer as a whole is 5
It is preferably in the range of X10'' to 5x1012 Ωcm, particularly 5X10' to 5x1011 Ωcm.

When developing an electrostatic image, after toner and magnetic carrier are mixed, a magnetic brush of a predetermined length is formed on a developing sleeve that has a magnet roll inside, and this magnetic brush and a photoreceptor having an electrostatic image are brought into contact with each other. The magnetic brush and the electrostatic image-holding photoreceptor are brought close to each other by rubbing or in an electric field to which an oscillating electric field is applied.

(Effects of the Invention) According to the present invention, in the negative band electrophotographic toner containing a fixing resin, a colorant, and a charge control agent for negative charging, the fixing resin is a polyester resin, and the fixing resin is a polyester resin. By incorporating a charge control aid into the toner, which is incompatible with the conventional negatively charged toner, but has dispersibility and has a charge control effect of the opposite polarity to that of the negatively charged charge control agent. Various drawbacks have been solved, the average value of the toner charge amount is within the optimum range in terms of toner scattering prevention and image density, and the toner charge amount distribution is sharp, making it a high-IF toner that is not used for development. Toner for negative charging is provided, which has almost no low-charging toner that causes toner scattering. The toner of the present invention has a sharp charge amount distribution, and the charge rises quickly during charging.
Moreover, the advantage of less deterioration of charging characteristics during long-term operation is also achieved.

(Examples) Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples. Note that the present invention is not limited to this.

100 parts by weight of polyester resin as a fixing resin, 8 parts by weight of carbon black as a coloring agent, and 1.51 parts of low molecular weight polypropylene as an anti-offset agent! A negative amount part, 2 parts by weight of a chromium-containing monoazo complex dye as a charge control agent for charging, and 0.5 part by weight of a quaternary ammonium salt of the following formula as a charge control aid incompatible with the fixing resin. The mixture was melt-kneaded using an extruder, and the kneaded product was cooled, then pulverized and classified to obtain a toner having an average particle size of 11 μm. Then, this toner and a resin-coated ferrite carrier with an average particle size of 85 μm were mixed into a toner with a toner concentration of 4.
．． A developer was prepared by mixing and stirring at 5%, and the charge distribution was measured using the toner charge distribution measuring device shown in FIG.

The result is shown in Figure 1.

Next, the above developer was used in a modified machine of the Sanda Beam printer LPX-1 manufactured by Sanda Kogyo, which is equipped with a negatively charged organic photoreceptor (the developing section was modified to a reversal developing system) (/!'
i Light body surface potential knee 700V, development bias potential knee 5
00V), and 1000 images were continuously formed. As a result, there is no reduction in image density or image fogging,
There was no toner scattering at all. Details are shown in Table 1.

Five layers (WII2 In Example 1, C, 1, Pigmen as a colorant
A toner having an average particle size of 11 μm was obtained in the same manner except that tRed 31 was changed to 0.5 parts by weight. Below, Example 1
A developer was obtained in the same manner as above, and images were continuously formed on 1000 sheets. As a result, similar to Example 1, good images were obtained, and there was no toner scattering inside the machine. Further, the toner charge amount distribution was sharp as in Example 1, and there was almost no toner in the high charge range or toner with O or opposite polarity.

Comparative Example 1 A toner was prepared in the same manner as in Example 1 except that the charge 1l Jall auxiliary agent was not used. When the toner f charge distribution was measured in the same manner as in the example, the results were shown in FIG. Furthermore, when 1000 images were continuously formed in the same manner, the image density was unstable and the image density occasionally dropped. Furthermore, image fogging and toner scattering also occurred.

■Soft ±l In Example 1, C, 1.5olvent Yellow, which is compatible with the fixing resin, was used instead of the charge control aid.
A toner was prepared in the same manner except that 0.5 parts by weight of No. 56 was used. Then, the toner charge amount distribution was measured in the same manner as in the example, and the results were shown in FIG. 3.

Furthermore, when 1000 images were continuously formed in the same manner, image fogging and toner scattering were severe. Further, although the image density was satisfactory to some extent, density unevenness occasionally occurred.

■ Soft ■ In Example 1, instead of the charge control aid, C, which is compatible with the fixing resin, was used.1. Ba5ic Blue 26 to 0
．． A toner was prepared in the same manner except that 5 parts by weight was used. Then, when the toner charge amount distribution was measured in the same manner as in the example, as shown in FIG. 3, a large amount of Of charge and reverse polarity toner was generated.

Furthermore, when 1000 images were continuously formed in the same manner, image fogging and toner scattering were severe. Further, although the image density was satisfactory to some extent, density unevenness occasionally occurred.

Comparative Example 4 In Example 1, 10% of the epoxy resin was used as the fixing resin.
A toner was prepared in the same manner except that 0 part by weight was used.

Then, when the toner charge amount distribution was measured in the same manner as in the example, although the width of the distribution was narrower than in FIG.
There were still many toners near charged and highly charged toner in the a range.

Furthermore, when 1000 images were continuously formed in the same manner, image fogging, toner scattering, and fluctuations in image density occasionally occurred.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing a characteristic curve of -I' charge amount distribution of the toner of the present invention, and FIG. 2 is a diagram showing a characteristic curve of charge amount distribution of a toner using only a charge control agent for negative charging. FIG. 3 is a diagram showing a characteristic curve of the charge amount distribution of a toner using a charge control agent for negative charging and a positive f-electrode dye (compatible with the fixing resin); FIG. 4 is a schematic layout diagram of a charge amount measuring device used to measure the charge amount distribution of toner.

Claims (5)

[Claims] (1) In a negative band electrophotographic toner containing a fixing resin, a colorant, and a negative charge control agent, the fixing resin is a polyester resin and is incompatible with the fixing resin. An electrophotographic toner for negative charging, characterized in that the toner contains a charge control auxiliary agent which has dispersibility and has a charge control action of opposite polarity to that of the charge control agent for negative charging. (2) The toner according to claim 1, wherein the charge control aid is a quaternary ammonium salt. (3) The toner according to claim 1, wherein the charge control aid is a quaternary ammonium salt containing an oxyacid anion as an anion. (4) The charge control agent has the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the formula, at least one of R is a long-chain alkyl group or a long-chain alkenyl group, and at least two of them are lower Under the condition that it is an alkyl group or a benzyl group,
It is a lower alkyl group, a benzyl group, a long-chain alkyl group, or a long-chain alkenyl group, and A^- represents an anion. The toner according to claim 1, which is a compound represented by: (5) The charge control agent and the charge control aid are present in a weight ratio of 1:0.05 to 1:1, and in a total amount of 0.5 to 5 parts by weight per 100 parts by weight of the fixing resin. 1. The toner described in 1.