JP2000010345A - Negatively chargeable charge control agent and toner containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a white charge control agent which does not contain heavy metals, has high safety to the human body, has no risk of environmental pollution, has high negative chargeability, and has stable charge for a long period of time. Provide a toner having characteristics. SOLUTION: In a negatively chargeable charge control agent comprising a complex of a benzylic acid derivative represented by the general formula <A>, M is B
Or a negatively chargeable charge control agent, wherein Al is Li, Na or K, and a toner containing the same. (In the formula, R ₁ , R ₂ , R ₃ or R ₄ each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and R ₁ , R ₂ , R ₃ or R ₄ is
A plurality may be present, and when a plurality of R ₁ , R ₂ , R ₃ or R ₄ are present, each may be different or the same. n shows the positive integer of 1-5. )

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a negatively chargeable charge control agent and a toner containing the same. More specifically, the present invention relates to a charge control agent having high negative chargeability, and a toner containing the same, which has excellent charge characteristics.

[0002]

2. Description of the Related Art In electrophotography, a latent image is formed on a photoreceptor made of a photoconductive material or the like, and the latent image is developed with a powder developer called toner to visualize the image. Is generally fixed.

[0003] Toner is a two-component developer comprising a mixture of a binder resin in which a colorant, a charge control agent, a fluidizing agent and the like are dispersed, and a carrier of iron powder or ferrite powder;
It is classified into a one-component developer composed of a binder resin, a colorant, a charge control agent, a fluidizing agent, and a magnetic material.

A two-component developer is developed by attaching toner charged by friction with a carrier to an electrostatic latent image and developing the toner.
The component-based developer is developed by rubbing with a brush-like or plate-shaped friction member having the same function as the carrier of the two-component developer, and the magnetic fine powder is dispersed in place of the friction member. The powder is maintained and developed by mutual friction with the magnetic fine powder.

Since the photoreceptor can be positively or negatively charged,
Exposure based on the original results in a positive or negative electrostatic latent image. Depending on the polarity of the obtained electrostatic latent image, the toner is kept positive or negative.

In order to maintain the charge of the toner, it has been proposed to utilize the frictional charging property between the carrier and the material of the surface thereof and the resin which is the main component of the toner. Since the surface resistance is large, the obtained image is easily fogged and unclear. Therefore, a charge control agent is added to impart a desired triboelectric charge to the toner.

The charge control agent has a positive charge property depending on the charge polarity,
Nigrosine, quaternary ammonium salt compounds, etc. are classified into two types of negative charge,
Examples of the negatively chargeable charge control agent include a metal-containing azo compound and a metal compound of a salicylic acid derivative.

[0008]

Although most positively chargeable charge control agents do not contain metals, many of the negatively chargeable charge control agents contain heavy metals such as Cr and Zn, which are not safe for humans. And environmental pollution.

The charge controlling agent for a color toner is required to be white or light-colored. However, the metal-containing azo compound of the negatively chargeable charge controlling agent is colored, causing a change in hue and a decrease in chroma, resulting in sharpness. There is a problem that a perfect full-color image cannot be obtained. For this reason, de-metallization and whitening of the charge control agent, particularly the negative charge control agent, have been studied.

Japanese Patent Publication No. 7-104620 discloses a white or light-colored negatively-chargeable charge using an organic anionic component having boron as a central metal and a cationic component having a smaller molecular size than the organic anionic component. Modulating agents are disclosed.

Japanese Patent Publication No. 7-13765 discloses a white or light-colored charge control agent comprising an organic anionic component having a trivalent metal such as boron and aluminum as a central metal, and an inorganic cation or an organic cation. I have.

However, in the toner containing the charge control agent, a charge control agent having further improved negative chargeability has been demanded, and a toner having further improved charge characteristics has been demanded.

[0013]

The present inventors have conducted intensive studies and as a result, have found that an organic anion centered on boron or aluminum and an ionic radius smaller than the organic anion,
And found that a compound comprising a cation having an ionic radius within a limited range has excellent negative chargeability, and a toner using this as a negative chargeable charge control agent has excellent chargeability. And completed the present invention.

That is, the present invention provides a negatively chargeable charge control agent comprising a complex of a benzylic acid derivative represented by the following general formula <A>, wherein M is B or Al, X is Li, N
a or K is a negatively chargeable charge control agent.

[0015]

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[0016] In the _{formula, R 1, R 2, R} 3 or R ₄ are each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group or a halogen atom having 1 to 4 carbon atoms, R _1, R ₂ , R ₃
Alternatively, a plurality of R ₄ may be present, and when a plurality of R ₁ , R ₂ , R ₃ and R ₄ are present, each may be different or the same. n shows the positive integer of 1-5.

The present invention also provides a toner containing the negatively chargeable charge control agent of the present invention.

Hereinafter, the present invention will be described in detail.

In the present invention, R ₁ , R ₂ , R ₃ or R ₄
Is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms,
And 4 represents an alkoxy group or a halogen atom.

Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group,
Examples include a so-butyl group, a sec-butyl group, and a tert-butyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a n-propyloxy group, an iso-propyloxy group, and a
-Butyloxy group, sec-butyloxy group and tert-butyloxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.

A plurality of R ₁ , R ₂ , R ₃ or R ₄ may be present. When a plurality of R ₁ , R ₂ , R ₃ or R ₄ are present,
Each may be different or the same. n is
Represents a positive integer of 1 to 5.

M is B or Al, and Al is preferable from the viewpoint of negative chargeability.

X is, as shown in FIG. 1, a value of L due to the correlation between the ion radius of the cation and the amount of blow-off charge.
i, Na or K, considering the moisture resistance of the toner,
Preferably it is Na or K.

The negatively chargeable charge control agent of the present invention includes, for example,
A compound of the following general formula <B> (wherein R ₁ , R ₂ , R ₃ or R ₄ is the same as general formula <A>) is added to an aqueous solution of boric acid and NaOH, KOH or LiOH, and the temperature is increased. About 2 at 80 ℃
It is easily obtained by reacting while stirring for a time.

[0025]

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The following describes the negatively chargeable charge control agent of the present invention. The compound numbers are commonly used in the examples.

[0027]

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[0028]

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The negatively chargeable charge control agent of the present invention has excellent negative chargeability, and is free from heavy metals, so that it has high safety to the human body and low possibility of environmental pollution. Further, it has thermal stability up to a temperature at which melt kneading can be sufficiently performed, and has good dispersibility in a resin component. Furthermore, it is white,
It is suitable as a charge control agent for color toner.

The toner of the present invention comprises, in addition to the binder resin, the colorant and the negatively chargeable charge controlling agent of the present invention, an internal additive or an external additive added as required.

As the binder resin used in the toner of the present invention, a well-known resin for toner is used, for example, selected from polyester resin, styrene resin, styrene-acrylic resin, styrene-butadiene resin, epoxy resin, paraffin wax and the like. One or two or more
In consideration of the charging characteristics of the obtained toner, a polyester resin, a styrene-acryl resin or an epoxy resin is preferable, and a polyester resin is more preferable.

As the colorant used in the toner of the present invention, well-known pigments and dyes are used, and are not particularly limited as long as they are commonly used. For example, black colorants such as carbon black and acetylene black; yellow colorants such as graphite and cadmium yellow; orange colorants such as permanent orange and molybdenum orange; brown colorants such as iron oxide and amber; Red colorant, purple colorant such as cobalt violet and first violet, blue colorant such as methylene blue and aniline blue, and green colorant such as chrome green and pigment green B.

As the internal additives, synthetic waxes such as polypropylene as a fixing agent for improving the strength when the molten toner is fused and fixed to a base material, and polyethylene and polypropylene as a releasing agent to prevent the adhesion of the molten toner to the roller. And natural wax.

Examples of the external additive include hydrophobic silica as a fluidizing agent for improving the fluidity of the toner powder, alumina, titanium oxide, and resin-based ultrafine particles as a cleaning agent for improving the cleaning characteristics on the photosensitive member. Is raised.

The toner of the present invention is usually used as a two-component developer by being mixed with a carrier, but may be used as a one-component developer by containing a magnetic material.

As a carrier in a two-component developer,
A well-known material in which a magnetic material such as iron, ferrite, steel, magnetite, and nickel is coated with a silicone resin or an acrylic resin is used.

Examples of the magnetic material in the one-component developer include well-known iron oxides such as magnetite and ferrite, iron, and the like.
Metals such as cobalt and nickel, alloys such as aluminum, cobalt, copper, lead, zinc, bismuth, and calcium, or mixtures thereof are used.

The toner of the present invention is prepared by first adding a colorant, a negatively chargeable charge controlling agent of the present invention, and, if necessary, an additive and a magnetic material to a binder resin. Kneader, melted and kneaded using a heat kneader such as an extruder, dispersed or dissolved, then cooled and solidified, coarsely pulverized with a hammer mill, a cutter mill, etc., and 5 to 20 μm with a jet mill It is obtained by crushing and classifying.

As another method, a colorant and the negatively chargeable charge control agent of the present invention are dispersed in a binder resin and then spray-dried, or a colorant is added to a monomer to be a binder resin. It is obtained by mixing the agent and the negatively chargeable charge control agent of the present invention to form an emulsified suspension, followed by polymerization.

In the toner of the present invention, the amount of the negatively chargeable charge controlling agent of the present invention is added based on 100 parts by weight of the binder resin.
It is 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight. When the amount is less than 0.1 part by weight, the charge becomes non-uniform and toner scattering easily occurs. When the amount is more than 10 parts by weight, the charge adjusting agent aggregates in the toner and the charge becomes non-uniform.

The toner of the present invention is used in such a manner that the triboelectric charging characteristics between toner particles and between the toner and the carrier are stable, the triboelectric charge amount distribution is sharp and uniform, and there is no fog on the image and no scattering of the toner. The charge amount can be controlled to be suitable for the developing system.

In addition, even if the toner is used continuously for a long period of time, the toner does not aggregate, the charging characteristics do not change, and a stable image which is not affected by environmental changes can be obtained.

[0043]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below based on examples and comparative examples. Note that the present invention is not limited at all by these Examples and the like. Further, “parts” in Examples and Comparative Examples represents “parts by weight”.

Example 1 In "Compound 1," the cation moiety was replaced with an ionic radius.
H in ascending order⁺, Li ⁺, Na⁺, K⁺, Rb⁺, Cs⁺Made
A negatively chargeable charge control agent was synthesized by the above synthesis method.

The amount of blow-off charge of the synthesized negative charge control agent alone was measured by the following method.

Using a jet mill (manufactured by Seishin Enterprise Co., Ltd.), the synthesized negatively chargeable charge control agent was dispersed in an average particle diameter of 10 μm.
Crushed. Then, the pulverized negatively chargeable charge control agent 0.8
And silicon-coated ferrite carrier (Kanto Denka Kogyo
39.2 parts) was placed in a glass sample bottle, stirred and mixed for 5 minutes, and then measured with a blow-off powder charge measuring device (manufactured by Toshiba Chemical Corporation) in nitrogen gas at room temperature and room temperature. Blowing was performed for 30 seconds under humidity (25 ° C. × 60 RH) and a pressure of 1 kg / cm ² , and the blow-off charge amount of a single substance was measured. Figure 1 shows the results
Shown in

As shown in FIG. 1, when the ion radius is H ⁺ , the amount of negative charge becomes maximum, and then the smaller the ion radius becomes, the smaller the blow-off electrification amount becomes. At the time of the largest Cs ⁺ , the minimum was reached.

The amount of blow-off charge when the synthesized negative charge control agent was mixed with the polyester resin was measured by the following method.

To 100 parts of the polyester resin, 2 parts of the synthesized negatively chargeable charge control agent was added, and after melt-kneading, the mixture was pulverized to an average particle diameter of 10 μm using a jet mill. Crushed mixture
0.8 parts and 39.2 parts of a silicon-coated ferrite carrier were placed in a glass sample bottle, and stirred and mixed for 5 minutes.
Using a blow-off powder charge amount measuring device, in nitrogen gas,
Under normal temperature and normal humidity (25 ℃ × 60RH), 1kg / cm ² under pressure
The mixture was blown for 0 seconds, and the charge of the blow-off of the mixture was measured. The results are shown in FIG.

As shown in FIG. 1, the blow-off zone of the mixture
The charge is H, the smallest ion radius. ⁺, The negative charge is
As the ion radius increases, the negative charge increases
Larger, Rb⁺Slightly reduces the negative charge,
Cs with the largest radius⁺In the case of
Was.

When the cation is H ^+, the amount of negative charge is large in a simple substance, but the amount of negative charge is small in a polyester resin mixture, that is, in a matrix, which is unsuitable as the negative charge control agent of the present invention. Li ⁺ , Na ⁺ or K ⁺ is suitable as the negative charge adjusting agent, depending on the amount of negative charge of a simple substance and a polyester resin mixture.

Example 2 A polyester resin (Polyester HP3) was used as the binder resin.
01, 100 parts of Nippon Synthetic Chemical Industry Co., Ltd.), 5 parts of carbon black (hereinafter abbreviated as CB) as a coloring agent, and “Compound 1” (single blow-off charge -51 μc / g, 1 part of a polyester resin mixture blow-off charge amount -56 μc / g) and 5 parts of a polypropylene wax (Viscol 550P, registered trademark of Sanyo Chemical Industries, Ltd.) as an internal additive were mixed in a blender, and then mixed with a twin-screw extruder. After melt-kneading and cooling, coarsely pulverized using a hammer mill (manufactured by Fuji Paudal Co., Ltd.), and finely pulverized using a jet mill (manufactured by Seishin Enterprise Co., Ltd.) to an average particle size of 10 μm.
Classified. Hydrophobic silica as an external additive to the obtained fine particles
0.4 parts were mixed to obtain a black toner. This black toner 4
Parts and 100 parts of a silicone-coated ferrite carrier were mixed using a blender to obtain a two-component developer. Table 1 shows the binder, colorant, and charge control agent used.

The amount of blow-off charge of the developer measured according to Example 1 was -at room temperature and normal humidity (25 ° C. × 60% RH).
55μc / g, -54μ at high temperature and high humidity (45 ℃ × 90% RH)
c / g. Table 1 shows the results.

OPC under high temperature and high humidity (45 ° C. × 90% RH)
When a development test was performed on a commercial copying machine with a photosensitive drum to make 10,000 continuous copies, a clear image of high density was obtained without fog, which is a stain on a white background, and was good even after continuous copying of 10,000 sheets Image and the durability was good. Table 2 shows the results.

Example 3 In Example 2, a polyester HP3 was used as the binder resin.
13 as a coloring agent, CI Pigment Red 5
A two-component developer was obtained in the same manner as in Example 2 except that 5 parts of 7: 1 (hereinafter abbreviated as PR57: 1) was used. Table 1 shows the binder, colorant, and charge control agent used.

The blow-off charge amount of the developer measured according to Example 1 was -54 μc / g at normal temperature and normal humidity, and −53 μc / g at high temperature and high humidity. Table 1 shows the results. In a development test performed in the same manner as in Example 2, a clear image with no fog and a high density was obtained, a good image was obtained after continuous copying of 10,000 sheets, and the durability was also good. Table 2 shows the results
Shown in

Example 4 Example 2 was repeated except that 1 part of "compound 2" (single-part blow-off charge -64 .mu.c / g, polyester resin mixture blow-off charge -69 .mu.c / g) was used as the negatively chargeable charge control agent. In the same manner as in Example 2, a two-component developer was obtained.
Table 1 shows the binder, colorant, and charge control agent used.

The blow-off charge amount of the developer measured according to Example 1 was -49 μc / g under normal temperature and normal humidity, and −48 μc / g under high temperature and high humidity. Table 1 shows the results. In a development test performed in the same manner as in Example 2, a clear image with no fog and a high density was obtained, a good image was obtained after continuous copying of 10,000 sheets, and the durability was also good. Table 2 shows the results
Shown in

Example 5 In Example 2, a compound in which the cation K ⁺ of Compound 1 was set to Li ⁺ as a negatively chargeable charge control agent (single blow-off charge: −63 μc / g, polyester resin mixture blow-off charge: −40 μc) / G) A two-component developer was obtained in the same manner as in Example 2 except that 1 part was used. Table 1 shows the binder, colorant, and charge control agent used.

The blow-off charge amount of the developer measured according to Example 1 was -54 μc / g at normal temperature and normal humidity, and −48 μc / g at high temperature and high humidity. Table 1 shows the results. In a development test conducted in the same manner as in Example 2, most of the images were clear images without fog and high density, but some fog were observed. Table 2 shows the results.

Example 6 The procedure of Example 2 was repeated, except that 100 parts of a styrene-acrylic resin (Hymer SB101, registered trademark of Sanyo Chemical Industry Co., Ltd.) was used as the binder resin.
A component developer was obtained. Table 1 shows the binder, colorant, and charge control agent used.

The blow-off charge of the developer measured according to Example 1 was −50 μc / g at normal temperature and normal humidity, and −49 μc / g at high temperature and high humidity. Table 1 shows the results. In a development test performed in the same manner as in Example 2, a clear image with no fog and a high density was obtained, a good image was obtained after continuous copying of 10,000 sheets, and the durability was also good. Table 2 shows the results
Shown in

Example 7 In Example 2, a polyester HP3 was used as the binder resin.
13 as a colorant, CI Pigment Blue 1
5: 3 (hereinafter abbreviated as PB15: 3) 5 parts, “Compound 3” (single blow-off charge amount −54 μc) as a negatively chargeable charge control agent
/ G, polyester resin mixture blow-off charge amount -61μc
/ G) In the same manner as in Example 2 except that 1 part was used, 2
A component developer was obtained. Table 1 shows the binder, colorant, and charge control agent used.

The blow-off charge amount of the developer measured according to Example 1 was −50 μc / g under normal temperature and normal humidity.
It was -50 μc / g under high humidity, and was under high temperature and high humidity.
Table 1 shows the results. In a development test performed in the same manner as in Example 2, a clear image with no fog and a high density was obtained, a good image was obtained after continuous copying of 10,000 sheets, and the durability was also good. Table 2 shows the results.

Example 8 In Example 2, a polyester HP3 was used as the binder resin.
13 as a colorant, 5 parts of PB15: 3 as a coloring agent, and a compound in which the cation Na ⁺ of Compound 3 is Li ⁺ as a negatively chargeable charge control agent (single blow-off charge amount: −54 μc / g, blow-off of polyester resin mixture) A two-component developer was obtained in the same manner as in Example 2 except that 1 part of the charge amount -61 μc / g) was used. Table 1 shows the binder, colorant, and charge control agent used.

The blow-off charge amount of the developer measured according to Example 1 was -49 μc / g under normal temperature and normal humidity, and −43 μc / g under high temperature and high humidity. Table 1 shows the results. In a development test conducted in the same manner as in Example 2, most of the images were clear images without fog and high density, but some fog were observed. Table 2 shows the results.

Example 9 In Example 2, 100 epoxy resin (Asahi Epoxy Resin 330R, registered trademark of Asahi Kasei Kogyo Co., Ltd.) was used as the binder resin.
A two-component developer was obtained in the same manner as in Example 2, except that 5 parts of PB15: 3 was used as a coloring agent, and 1 part of "Compound 3" was used as a negative charge control agent. Table 1 shows the binder, colorant, and charge control agent used.

The blow-off charge amount of the developer measured according to Example 1 was -45 μc / g at normal temperature and normal humidity, and −44 μc / g at high temperature and high humidity. Table 1 shows the results. In a development test performed in the same manner as in Example 2, a clear image with no fog and a high density was obtained, a good image was obtained after continuous copying of 10,000 sheets, and the durability was also good. Table 2 shows the results
Shown in

Example 10 In Example 2, Hymer SB101 was used as the binder resin.
, And 1 part of “Compound 4” (blow-off charge of simple substance −71 μc / g, blow-off charge of polyester resin mixture −40 μc / g) as a negatively chargeable charge control agent, except that
A two-component developer was obtained in the same manner as in Example 2. Table 1 shows the binder, colorant, and charge control agent used.

The blow-off charge of the developer measured in accordance with Example 1 was -46 μc / g at normal temperature and normal humidity, and -40 μc / g at high temperature and high humidity. Table 1 shows the results. In a development test conducted in the same manner as in Example 2, most of the images were clear images without fog and high density, but some fog were observed. Table 2 shows the results.

Example 11 In Example 2, the compound having the cation Li ⁺ of the “compound 4” as the negatively chargeable charge controlling agent was K ⁺ (blow-off charge of a single substance -59 μc / g, blow-off charge of a polyester resin mixture -63 μc). / G) A two-component developer was obtained in the same manner as in Example 2 except that 1 part was used. Table 1 shows the binder, colorant, and charge control agent used.

The blow-off charge of the developer measured according to Example 1 was −51 μc / g under normal temperature and normal humidity, and −50 μc / g under high temperature and high humidity. Table 1 shows the results. In a development test performed in the same manner as in Example 2, a clear image with no fog and a high density was obtained, a good image was obtained after continuous copying of 10,000 sheets, and the durability was also good. Table 2 shows the results
Shown in

Example 12 In Example 2, a polyester HP3 was used as the binder resin.
13 as a coloring agent, 5 parts of CI Pigment Yellow 12 (hereinafter abbreviated as PY12), and "Compound 5" (single blow-off charge -43 .mu.c / g,
Blow off charge of polyester resin mixture -49μc / g)
A two-component developer was obtained in the same manner as in Example 2 except that one part was used. Table 1 shows the binder, colorant and charge control agent used.
Shown in

The blow-off charge amount of the developer measured according to Example 1 was -45 μc / g under normal temperature and normal humidity,
Under high humidity, it was -44 μc / g. Table 1 shows the results. In a development test performed in the same manner as in Example 2, a clear image with no fog and a high density was obtained, a good image was obtained after continuous copying of 10,000 sheets, and the durability was also good. Table 2 shows the results
Shown in

Example 13 In Example 2, Hymer SB101 was used as the binder resin.
Example 2 except that 100 parts of PY12 were used as a coloring agent, 5 parts of PY12, and 1 part of "compound 5" as a negative charge control agent.
In the same manner as in the above, a two-component developer was obtained. Table 1 shows the binder, colorant, and charge control agent used.

The blow-off charge of the developer measured according to Example 1 was −41 μc / g at normal temperature and normal humidity, and −40 μc / g at high temperature and high humidity. Table 1 shows the results. In a development test performed in the same manner as in Example 2, a clear image with no fog and a high density was obtained, a good image was obtained after continuous copying of 10,000 sheets, and the durability was also good. Table 2 shows the results
Shown in

Example 14 In Example 2, Hymer SB101 was used as the binder resin.
100 parts, 5 parts of PY12 as a coloring agent, and “compound 6” (single blow-off charge -45 μm) as a negatively chargeable charge control agent.
c / g, polyester resin mixture blow-off charge amount -51μ
c / g) Except that 1 part was used, 2
A component developer was obtained. Table 1 shows the binder, colorant, and charge control agent used.

The blow-off charge of the developer measured according to Example 1 was -41 μc / g at normal temperature and normal humidity, and -40 μc / g at high temperature and high humidity. Table 1 shows the results. In a development test performed in the same manner as in Example 2, a clear image with no fog and a high density was obtained, a good image was obtained after continuous copying of 10,000 sheets, and the durability was also good. Table 2 shows the results
Shown in

Example 15 Example 15 was the same as Example 2 except that 1 part of "compound 7" (blow-off charge of a single substance-68 .mu.c / g, blow-off charge of a polyester resin mixture -45 .mu.c / g) was used as a negative charge control agent. In the same manner as in Example 2, a two-component developer was obtained.
Table 1 shows the binder, colorant, and charge control agent used.

The blow-off charge amount of the developer measured according to Example 1 was -44 μc / g at normal temperature and normal humidity, and −38 μc / g at high temperature and high humidity. Table 1 shows the results. Further, in a development test performed in the same manner as in Example 2, most of the images were clear images without fog and high density,
Some fog was seen. Table 2 shows the results.

Example 16 The same procedure as in Example 2 was repeated except that the binder resin was Polyester HP3.
13 as a colorant, CI Pigment Red 1
22 (hereinafter abbreviated as PR122), 5 parts, "compound 8" (single blow-off charge amount -74 µc /
g, polyester resin mixture blow-off charge -53 μc /
g) A two-component developer was obtained in the same manner as in Example 2 except that 1 part was used. Table 1 shows the binder, colorant, and charge control agent used.

The blow-off charge amount of the developer measured according to Example 1 was -41 μc / g at normal temperature and normal humidity, and −36 μc / g at high temperature and high humidity. Table 1 shows the results. In a development test conducted in the same manner as in Example 2, most of the images were clear images without fog and high density, but some fog were observed. Table 2 shows the results.

Comparative Example 1 In Example 2, an organic boron compound containing tetraphenylboron as an anionic component and H ⁺ as a cationic component (single blow-off charge amount -98
μc / g, blow-off charge of polyester resin mixture -11
μc / g), except that 1 part was used.
A two-component developer was obtained. Table 1 shows the binder, colorant, and charge control agent used.

The blow-off charge amount of the developer measured according to Example 1 was -6 μc / g at normal temperature and normal humidity, and -4 μc / g at high temperature and high humidity. Table 1 shows the results. In a development test performed in the same manner as in Example 2, toner scattering and fogging to an image became severe in the middle, and
Canceled with a piece. Table 2 shows the results.

Comparative Example 2 In Example 2, an organic boron compound containing tetraphenylboron as an anionic component and Li ⁺ as a cationic component (single blow-off charge amount -55
μc / g, blow-off charge of polyester resin mixture -14
μc / g), except that 1 part was used.
A two-component developer was obtained. Table 1 shows the binder, colorant, and charge control agent used.

The blow-off charge amount of the developer measured according to Example 1 was -5 μc / g at normal temperature and normal humidity, and 5 μc / g at high temperature and high humidity. Table 1 shows the results. Also,
In the development test conducted in the same manner as in Example 2, the toner was stopped after 1,000 sheets because toner scattering and fogging to the image became severe in the middle. Table 2 shows the results.

Comparative Example 3 In Example 2, an organic boron compound containing boron dimandelate as an anionic component and Li ⁺ as a cationic component (single blow-off charge amount -61 μm) was used as a negatively chargeable charge control agent.
c / g, polyester resin mixture blow-off charge amount -39μ
c / g) Except that 1 part was used, 2
A component developer was obtained. Table 1 shows the binder, colorant, and charge control agent used.

The blow-off charge amount of the developer measured according to Example 1 was -20 μc / g at normal temperature and normal humidity, and -15 μc / g at high temperature and high humidity. Table 1 shows the results. In a development test performed in the same manner as in Example 2, toner scattering began to be noticeable in the middle of the test.
Table 2 shows the test results.

Comparative Example 4 In Example 2, di (p) was used as a negatively chargeable charge control agent.
-Nitromandelic acid) aluminum as the anionic component,
Two components were prepared in the same manner as in Example 2 except that 1 part of an organoaluminum compound having Li ⁺ as a cationic component (blow-off charge of a single substance −40 μc / g, blow-off charge of a polyester resin mixture −32 μc / g) was used. A developer was obtained. Table 1 shows the binder, colorant, and charge control agent used.

The blow-off charge amount of the developer measured according to Example 1 was −22 μc / g under normal temperature and normal humidity, and −20 μc / g under high temperature and high humidity. Table 1 shows the results. In a development test performed in the same manner as in Example 2, toner scattering started to be noticeable in the middle, and the test was stopped at 3,000 sheets.
Table 2 shows the results.

Comparative Example 5 In Example 2, as the negatively chargeable charge control agent, a compound in which the cation K ⁺ of “Compound 1” was H ⁺ (blow-off charge of a single substance—137 μc / g, blow-off charge of a polyester resin mixture— Example 2 except that 1 part was used.
In the same manner as described above, a two-component developer was obtained. Table 1 shows the binder, colorant, and charge control agent used.

The blow-off charge amount of the developer measured according to Example 1 was -13 μc / g at normal temperature and normal humidity, and -11 μc / g at high temperature and high humidity. Table 1 shows the results. In a development test performed in the same manner as in Example 2, toner scattering started to be noticeable in the middle, and the test was stopped at 3,000 sheets.
Table 2 shows the results.

Comparative Example 6 In Example 2, an organic aluminum compound containing bis (3,5-di-t-butylsalicylate) aluminum as an anionic component and H ⁺ as a cationic component as a negatively chargeable charge control agent Single blow-off charge -84 µc / g, polyester resin mixture blow-off charge -27 µc / g) 1
A two-component developer was obtained in the same manner as in Example 2, except for using parts. Table 1 shows the binder, colorant, and charge control agent used.

The blow-off charge amount of the developer measured according to Example 1 was -25 μc / g at normal temperature and normal humidity, and -24 μc / g at high temperature and high humidity. Table 1 shows the results. In a development test performed in the same manner as in Example 2, toner scattering started to be noticeable in the middle, and the test was stopped at 3,000 sheets.
Table 2 shows the results.

Comparative Example 7 In Example 2, an organoaluminum compound containing bis (3,5-di-t-butylsalicylate) aluminum as an anionic component and K ⁺ as a cationic component as a negatively chargeable charge control agent A two-component developer was obtained in the same manner as in Example 2, except that 1 part of a single-unit blow-off charge amount of -32 μc / g and a blow-off charge amount of a polyester resin mixture of -30 μc / g) were used. Table 1 shows the binder, colorant, and charge control agent used.

The blow-off charge of the developer measured according to Example 1 was −30 μc / g at normal temperature and normal humidity, and −29 μc / g at high temperature and high humidity. Table 1 shows the results. In a development test performed in the same manner as in Example 2, toner scattering started to be noticeable in the middle, and the test was stopped at 3,000 sheets.
Table 2 shows the results.

[0097]

[Table 1]

[0098]

[Table 2]

In Table 2, ○ indicates good, Δ indicates slightly defective, and X indicates defective.

[0100]

As described above, the negatively chargeable charge control agent of the present invention does not contain any heavy metals, so that it has high safety to the human body and low possibility of environmental pollution. Further, it has excellent charging characteristics, has thermal stability up to a temperature at which melt kneading can be sufficiently performed, and has good dispersibility in resin components. Further, since it is white, it does not cause color hindrance and is suitable as a charge adjusting agent for color toner.

The toner containing the negatively chargeable charge control agent of the present invention has a stable triboelectric charging characteristic between toner particles and between a toner and a carrier, and has a sharp and uniform triboelectric charge distribution. The charge amount can be controlled to a level suitable for the developing system to be used without fogging or toner scattering.

Further, the toner of the present invention can obtain a stable image which is not aggregated, does not change the charging characteristics, and is not affected by environmental changes even when used for a long period of time.

[Brief description of the drawings]

FIG. 1 shows the relationship between the ionic radius of a cation and the amount of blow-off charge of the negatively chargeable charge control agent alone of the present invention, and the ionic radius of the cation and the amount of blow-off charge when the charge control agent is mixed with a polyester resin FIG.

Claims (6)

[Claims] 1. A negatively chargeable charge control agent comprising a complex of a benzylic acid derivative represented by the following general formula <A>:
Is B or Al, and X is Li, Na or K. Embedded image (In the formula, R ₁ , R ₂ , R ₃ or R ₄ each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and R ₁ , R ₂ , R ₃ or R ₄ is
A plurality of R ₁ , R ₂ , R ₃ or R ₄ may be present, and each may be different or the same. n shows the positive integer of 1-5. ) 2. The method according to claim ₁ , wherein each of R ₁ , R ₂ , R _{3 and} R ₄ is a hydrogen atom, and n is 5.
3. The negatively chargeable charge control agent according to item 1. 3. The negatively chargeable charge control agent according to claim 1, wherein M is Al. 4. The negative charge adjusting agent according to claim 3, wherein X is Na or K. 5. A toner comprising the negative charge adjusting agent according to claim 1. Description: 6. The toner according to claim 5, wherein the binder resin is a polyester resin.