JP2009276480A - Negatively chargeable charge control agent and toner comprising the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a charge control agent which can exhibit excellent negative chargeability in wide temperature-humidity ranges from low temperature to high temperature and from low humidity to high humidity and has excellent stability, and to provide an electrophotographic toner in which triboelectric characteristics between toner particles and between the toner and a carrier can be stabilized, also, a friction charging distribution is made sharp and uniform, and the risks of fogging and toner scattering to an image are reduced by comprising the charge control agent. <P>SOLUTION: As the charge control agent, a compound which is the alkali metal salt of an organic complex anion having a specific structure with boron or aluminum as the center, and in which at least a part of the skeleton of the organic complex anion is substituted for a fluorine atom or a fluoroalkyl group is used. The toner uses the same as a negatively chargeable charge control agent. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a charge adjusting agent having high negative chargeability and a toner comprising the same and having excellent charging characteristics.

  Electrophotography is a method in which a latent image is formed on a photoreceptor composed of a photoconductive substance and the like, developed with a powder developer called toner, visualized, and then fixed on paper by heat or pressure. It is common.

  The toner includes a two-component developer made of a mixture of a binder resin in which a colorant, a charge adjusting agent, a fluidizing agent, etc. are dispersed and an iron powder or ferrite powder carrier, a binder resin, a colorant, It is divided into a one-component developer composed of a charge adjusting agent, a fluidizing agent and a magnetic material.

  The two-component developer is developed by attaching toner charged by friction with the carrier to the electrostatic latent image, and the one-component developer has a brush-like shape having the same function as the carrier of the two-component developer. Further, development is carried out by rubbing with a plate-like friction member, or the magnetic fine powder is kept in a dispersed state instead of the friction member, and development is caused by mutual friction with the magnetic fine powder.

  Since the photoreceptor can be charged positively or negatively, a positive or negative electrostatic latent image can be obtained by exposure based on the original. Depending on the polarity of the resulting electrostatic latent image, the toner is held positive or negative.

  In order to keep the toner charged, it has also been proposed to use the triboelectric charging property between the carrier and its surface material and the resin that is the main component of the toner, but the toner is small in charge and has a solid surface resistance value. Therefore, the obtained image is easily fogged and unclear. Therefore, a charge adjusting agent is added in order to impart a desired triboelectric chargeability to the toner.

  There are two types of charge control agents, positively chargeable and negatively chargeable, depending on the charge polarity. Examples of positively chargeable charge control agents include nigrosine and quaternary ammonium salt compounds. Metal-containing azo compounds, metal compounds of salicylic acid derivatives, and the like.

  Patent Document 1 discloses a compound composed of a complex of a benzylic acid derivative as a negatively chargeable charge regulator that is safe for the human body and does not contain heavy metals such as Cr and Zn and has a low environmental load. .

  When this compound is used as a negatively chargeable charge control agent, it has excellent charging characteristics, has thermal stability up to a temperature sufficient for melt kneading, has good dispersibility in the resin component, and further, this compound has Since it is white, it does not cause color tone problems and is suitable for color toners.

  Thus, a negatively chargeable charge control agent composed of a boron or aluminum complex of a benzylic acid derivative is an excellent negative chargeable charge control agent, but it has a rapid rise in charge and the charge amount of the toner during continuous printing. The stability to the environment was not fully satisfactory and needed to be improved.

JP 2000-010345 A

An object of the present invention is to provide a charge control agent that can exhibit excellent negative chargeability in a wide temperature range from low temperature to high temperature and a wide humidity range from low humidity to high humidity, and has excellent stability. is there.
In addition, by containing the charge adjusting agent, the triboelectric charge characteristics between the toner particles and between the toner and the carrier can be stabilized, the triboelectric charge distribution amount is sharp and uniform, and the charge rising is excellent. The present invention provides an electrophotographic toner that is less likely to scatter. The provision of such toner is expected to contribute to the production of a good developer that does not cause image fogging even in continuous copying and can obtain an appropriate image density.

  As a result of intensive studies, the present inventors have paid attention to an alkali metal salt of an organic complex anion having a specific structure centered on boron or aluminum, and at least a part of the organic complex anion skeleton is a fluorine atom or an alkyl fluoride. A compound substituted with a group has been found to have excellent properties as a charge control agent, and a toner using this as a negative charge control agent has a quick charge rise, excellent environmental stability, low temperature and low humidity. The inventors have found that a stable charge amount of toner during continuous printing can be maintained in a wide range of environments such as an environment and a high temperature and high humidity environment, and have completed the present invention.

  That is, this invention is shown to the following (1)-(8).

  (1) The following general formula (A),

（Ａ式中、Ｍは、ホウ素又はアルミニウムを表す。Ｒ_１〜Ｒ_４はそれぞれ同じであっても異なっていても良く、その少なくとも１つが、フッ素原子又はフッ化アルキル基である。Ｘは、アルカリ金属を表す。）
で表される化合物からなることを特徴とする負帯電性電荷調整剤。

(In formula A, M represents boron or aluminum. R _{1 to} R ₄ may be the same or different, and at least one of them is a fluorine atom or a fluorinated alkyl group. X is Represents an alkali metal.)
A negatively chargeable charge control agent comprising a compound represented by the formula:

  (2) The following general formula (B),

（Ｂ式中、Ｍは、ホウ素又はアルミニウムを表す。Ｒ_５〜Ｒ_８はそれぞれ同じであっても異なっていても良く、その少なくとも１つが、フッ素原子又はフッ化アルキル基である。ｎは１〜５の整数を表す。Ｘは、アルカリ金属を表す。）
で表される化合物からなることを特徴とする負帯電性電荷調整剤。

(In formula B, M represents boron or aluminum. R _{5 to} R ₈ may be the same or different, and at least one of them is a fluorine atom or a fluorinated alkyl group. Represents an integer of ˜5, X represents an alkali metal.)
A negatively chargeable charge control agent comprising a compound represented by the formula:

  (3) The following general formula (C),

（Ｃ式中、Ｍは、ホウ素又はアルミニウムを表す。Ｒ_９〜Ｒ_１２はそれぞれ同じであっても異なっていても良く、その少なくとも１つが、フッ素原子又はフッ化アルキル基である。ｎは１〜５の整数を表す。Ｘは、アルカリ金属を表す。）
で表される化合物からなることを特徴とする負帯電性電荷調整剤。

(In formula C, M represents boron or aluminum. R _{9 to} R ₁₂ may be the same or different, and at least one of them is a fluorine atom or a fluorinated alkyl group. Represents an integer of ˜5, X represents an alkali metal.)
A negatively chargeable charge control agent comprising a compound represented by the formula:

  (4) The following general formula (D),

（Ｄ式中、Ｍは、ホウ素又はアルミニウムを表す。Ｒ_１３〜Ｒ_１６はそれぞれ同じであっても異なっていても良く、その少なくとも１つが、フッ素原子又はフッ化アルキル基である。ｎは１〜４の整数を表す。Ｘは、アルカリ金属を表す。）
で表される化合物からなることを特徴とする負帯電性電荷調整剤。

(In formula D, M represents boron or aluminum. R _{13 to} R ₁₆ may be the same or different, and at least one of them is a fluorine atom or a fluorinated alkyl group. Represents an integer of ˜4, X represents an alkali metal.)
A negatively chargeable charge control agent comprising a compound represented by the formula:

  (5) The following general formula (E),

（Ｅ式中、Ｍは、ホウ素又はアルミニウムを表す。Ｒ_１７、Ｒ_１８はそれぞれ同じであっても異なっていても良く、その少なくとも１つが、フッ素原子又はフッ化アルキル基である。ｎは１〜４の整数を表す。Ｘは、アルカリ金属を表す。）
で表される化合物からなることを特徴とする負帯電性電荷調整剤。

(In the formula E, M represents boron or aluminum. R ₁₇ and R ₁₈ may be the same or different, and at least one of them is a fluorine atom or a fluorinated alkyl group. Represents an integer of ˜4, X represents an alkali metal.)
A negatively chargeable charge control agent comprising a compound represented by the formula:

  (6) The following general formula (F),

（Ｆ式中、Ｍは、ホウ素又はアルミニウムを表す。Ｒ_１９〜Ｒ_２２はそれぞれ同じであっても異なっていても良く、その少なくとも１つが、フッ素原子又はフッ化アルキル基である。Ｘは、アルカリ金属を表す。）
で表される化合物からなることを特徴とする負帯電性電荷調整剤。

(In formula F, M represents boron or aluminum. R _{19 to} R ₂₂ may be the same or different, and at least one of them is a fluorine atom or a fluorinated alkyl group. X is Represents an alkali metal.)
A negatively chargeable charge control agent comprising a compound represented by the formula:

  (7) The following general formula (G),

（Ｇ式中、Ｍは、ホウ素又はアルミニウムを表す。Ｒ_２３、Ｒ_２４はそれぞれ同じであっても異なっていても良く、その少なくとも１つが、フッ素原子又はフッ化アルキル基である。ｎは１〜４の整数を表す。Ｘは、アルカリ金属を表す。）
で表される化合物からなることを特徴とする負帯電性電荷調整剤。

(In formula G, M represents boron or aluminum. R ₂₃ and R ₂₄ may be the same or different, and at least one of them is a fluorine atom or a fluorinated alkyl group. Represents an integer of ˜4, X represents an alkali metal.)
A negatively chargeable charge control agent comprising a compound represented by the formula:

(8) A toner comprising the negatively chargeable charge adjusting agent according to any one of (1) to (7) and a binder resin.
Further, the toner is characterized in that the binder resin is a polyester resin.

  The negatively chargeable charge control agent of the present invention is an organic anion complex centered on boron or aluminum having a fluorine atom or a fluoroalkyl group, and the counter cation of the organic anion complex is a compound comprising an alkali metal. Therefore, it has thermal stability up to a temperature at which melt kneading can be sufficiently performed, and dispersibility in the resin component is good. Further, since it is white, it does not cause color tone trouble and is suitable as a charge adjusting agent for color toner.

  The toner containing the negatively chargeable charge adjusting agent of the present invention has a stable triboelectric charge characteristic between toner particles or between a toner and a carrier, and a sharp and uniform distribution of triboelectric charge, thus causing fog and toner on an image. Therefore, the charge amount can be controlled to be suitable for the developing system to be used. In addition, compared to conventional negatively chargeable charge control agents, the rise of charge is faster, the environment is stable, and the change in charge amount is small in a wide range of environments, including low temperature and low humidity environments and high temperature and high humidity environments. Furthermore, a stable charge amount of toner during continuous printing can be maintained under these circumstances, and an electrophotographic image having no change in print density or image density can be obtained.

Hereinafter, the present invention will be described in detail.
The present invention is a negatively chargeable charge control agent comprising a compound shown in any of the following (A) to (G).
The negatively chargeable charge control agent of the present invention is characterized in that the organic complex anion skeleton in the compound is substituted with at least one fluorine atom group or fluorinated alkyl group.

Here, in Formula A, R _{1 to} R ₄ represent a hydrogen atom, a fluorine atom, an alkyl group, or a fluorinated alkyl group, at least one of which is a fluorine atom or a fluorinated alkyl group.

  Examples of the fluorinated alkyl group include linear or branched fluorinated alkyl groups having 1 to 4 carbon atoms, and specifically include trifluoromethyl group, trifluoroethyl group, trifluoropropyl group. Group, trifluorobutyl group, perfluoroethyl group, perfluoropropyl group, iso-perfluoropropyl group, perfluorobutyl group, iso-perfluorobutyl group, sec-perfluorobutyl group, tert-perfluorobutyl group Can be mentioned.

  Examples of the alkyl group include linear or branched alkyl groups having 1 to 4 carbon atoms, and specifically include methyl group, ethyl group, n-propyl group, iso-propyl group, n -Butyl group, iso-butyl group, sec-butyl group, tert-butyl group are mentioned.

  In Formula A, M represents boron or aluminum, and boron is more preferable in terms of charging characteristics. X represents an alkali metal, and is preferably at least one selected from the group consisting of Li, Na, and K based on the correlation between the ionic radius of the cation and the amount of blow-off charge. More preferably Na or K.

Here, in formula B, R ₅ and R ₆ represent a hydrogen atom, a fluorine atom, an alkyl group, or a fluorinated alkyl group, at least one of which is a fluorine atom or a fluorinated alkyl group.

  Examples of the fluorinated alkyl group include the same ones as described in the description of the formula A, and examples of the alkyl group include the same ones as described in the formula A. The same thing as A type is mentioned also about said M. N represents an integer of 1 to 5.

Here, in formula C, R _{9 to} R ₁₂ represent a hydrogen atom, a fluorine atom, an alkyl group, or a fluorinated alkyl group, at least one of which is a fluorine atom or a fluorinated alkyl group.

  Examples of the fluorinated alkyl group include the same ones as described in the description of the formula A, and examples of the alkyl group include the same ones as described in the formula A. The same thing as A type is mentioned also about said M. N represents an integer of 1 to 5.

Here, in the formula D, R _{13 to} R ₁₆ represent a hydrogen atom, a fluorine atom, an alkyl group, or a fluorinated alkyl group, and at least one of them is a fluorine atom or a fluorinated alkyl group.

  Examples of the fluorinated alkyl group include the same ones as described in the description of the formula A, and examples of the alkyl group include the same ones as described in the formula A. The same thing as A type is mentioned also about said M. N represents an integer of 1 to 4.

Here, in the formula E, R ₁₇ and R ₁₈ represent a hydrogen atom, a fluorine atom, an alkyl group or a fluorinated alkyl group, at least one of which is a fluorine atom or a fluorinated alkyl group.

  Examples of the fluorinated alkyl group include the same ones as described in the description of the formula A, and examples of the alkyl group include the same ones as described in the formula A. The same thing as A type is mentioned also about said M. N represents an integer of 1 to 4.

Here, in Formula F, R _{19 to} R ₂₂ represent a hydrogen atom, a fluorine atom, an alkyl group, or a fluorinated alkyl group, at least one of which is a fluorine atom or a fluorinated alkyl group.

  Examples of the fluorinated alkyl group include the same ones as described in the description of the formula A, and examples of the alkyl group include the same ones as described in the formula A. The same thing as A type is mentioned also about said M.

Here, in Formula G, R ₂₃ and R ₂₄ represent a hydrogen atom, a fluorine atom, an alkyl group, or a fluorinated alkyl group, at least one of which is a fluorine atom or a fluorinated alkyl group.

  Examples of the fluorinated alkyl group include the same ones as described in the description of the formula A, and examples of the alkyl group include the same ones as described in the formula A. The same thing as A type is mentioned also about said M. N represents an integer of 1 to 4.

  Next, a method for producing the negatively chargeable charge control agent of the present invention will be described.

  The negatively chargeable charge adjusting agents represented by the general formulas (A) to (G) can be obtained by the following method. That is, boric acid or aluminum chloride was added to an aqueous solution of NaOH, KOH, or LiOH in an equal amount of each of the raw material compounds represented by the following formula, and reacted, for example, at a temperature of 80 ° C. with stirring for about 2 hours. It can be easily obtained by filtering the product.

In the above formula representing the raw material compound, R ₁ , R ₂ , R ₅ , R ₇ , R ₉ , R ₁₀ , R ₁₃ , R ₁₄ , R ₁₇ , R ₁₉ , R ₂₀ and R ₂₃ are the same as those described above. The thing is shown. N represents the same as described above.

  Specific examples of suitable negatively chargeable charge adjusting agents of the present invention are shown below. The compound number is commonly used in the examples.

  The negatively chargeable charge adjusting agent of the present invention has excellent negative chargeability, that is, the toner using this as a negatively chargeable charge adjusting agent has a fast charge rise, and is also used during repeated use and rest. In this case, a stable charge amount of the toner can be maintained, so that a change in image density can be reduced.

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

  As the binder resin used in the toner of the present invention, a known toner resin is used. For example, one kind selected from polyester resin, styrene resin, styrene-acrylic resin, styrene-butadiene resin, epoxy resin, paraffin wax, and the like. Alternatively, two or more types can be mentioned, and in consideration of the charging characteristics of the obtained toner, a polyester resin, a styrene-acrylic resin or an epoxy resin is preferable, and a polyester resin is more preferable.

  The colorant used in the toner of the present invention is not particularly limited as long as it is a commonly used pigment or dye and is usually used. For example, black colorants such as carbon black and acetylene black, yellow colorants such as yellow lead and cadmium yellow, orange colorants such as permanent orange and molybdenum orange, brown colorants such as iron oxide and amber, bengara, rose bengara, etc. Red colorants, violet colorants such as cobalt violet and first violet, blue colorants such as methylene blue and aniline blue, and green colorants such as chrome green and pigment green B.

  As internal additives, polypropylene as a fixing agent for improving strength when fusion toner is fused and fixed to a substrate, polyethylene as a release agent for preventing adhesion of molten toner to a roller, natural wax such as polypropylene Can be given.

  Examples of the external additive include hydrophobic silica that serves as a fluidizing agent that improves the fluidity of toner powder, alumina, titanium oxide, and resin-based ultrafine particles that serve as a cleaning agent that improves the cleaning characteristics on the photoreceptor. .

  The toner of the present invention is usually mixed with a carrier and used as a two-component developer, but it can also be used as a one-component developer containing a magnetic material.

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

  In addition, as a magnetic material in a one-component developer, known iron oxides such as magnetite and ferrite, metals such as iron, cobalt, and nickel, alloys such as aluminum, cobalt, copper, lead, zinc, bismuth, and calcium, The mixture is used.

  In the toner of the present invention, first, a colorant and the negatively chargeable charge adjusting agent of the present invention, and, if necessary, an additive and a magnetic material are added to a binder resin, and after mixing with a blender, a heating roll, kneader, and extensible Melt and knead using a heat kneader such as a ruder, disperse or dissolve, then cool and solidify, then coarsely pulverize with a hammer mill, cutter mill, etc., pulverize to 1-20 μm with a jet mill, classify Can be obtained.

  As another method, the colorant and the negatively chargeable charge adjusting agent of the present invention are dispersed in the binder resin and then spray-dried, or the monomer that becomes the binder resin is mixed with the colorant and An example is a method in which the negatively chargeable charge control agent of the invention is mixed to form an emulsion suspension and then polymerized.

  In the toner of the present invention, the addition amount of the negatively chargeable charge adjusting agent of the present invention is 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the binder resin. . When the amount is less than 0.1 part by weight, the charge is nonuniform and toner scattering is likely to occur.

  The toner of the present invention has a stable triboelectric charge characteristic between toner particles or between a toner and a carrier, a sharp and uniform triboelectric charge amount distribution, and is suitable for a developing system to be used without fogging or scattering of toner. It can be controlled to a suitable charge amount.

  Further, even when used continuously for a long time, the toner does not aggregate, the charging characteristics do not change, and a stable image that is not affected by environmental changes can be obtained.

Hereinafter, the present invention will be described based on examples. In addition, this invention is not limited at all by these Examples. In the examples and comparative examples, “part” represents “part by weight”.
As an evaluation method, a negative charge control agent listed in Examples and Comparative Examples was used as a raw material to prepare a two-component developer, and first, the blow-off charge amount of the developer was measured. A development test by continuous copying was carried out on a commercial copying machine having a drum. From these tests, the characteristics of charge rise, toner scattering, image density, fog state, and durability were compared.

Example 1
100 parts of a polyester resin (Polyester HP301 (registered trademark), manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) as a binder resin, 5 parts of carbon black (hereinafter abbreviated as “CB”) as a colorant, a negative charge control agent As "Compound 1" (single blow-off charge amount -54 [mu] C / g, polyester resin mixture blow-off charge amount -56 [mu] C / g), polypropylene wax as an internal additive (Biscol 550P (registered trademark), manufactured by Sanyo Chemical Industries) After mixing 5 parts with a blender, melt-knead with a twin-screw extrusion kneader, allow to cool, and coarsely pulverize using a hammer mill (Fuji Powder Co., Ltd.). It was finely pulverized and classified to an average particle size of 10 μm. The obtained fine particles were mixed with 0.4 part of hydrophobic silica as an external additive to obtain a black toner. 4 parts of this black toner and 100 parts of silicone-coated ferrite carrier were mixed using a blender to obtain a two-component developer.

The obtained developer was blown for 30 seconds in a nitrogen gas under a pressure of 1 kg / cm ² using a blow-off powder charge amount measuring device (manufactured by Toshiba Chemical Co., Ltd.), and the blow-off charge amount of the developer was measured.
The measured blow-off charge amount of the developer was −51 μC / g at normal temperature and normal humidity (25 ° C., 50% RH), −47 μC / g at high temperature and high humidity (35 ° C., 80% RH), low temperature, Under low humidity (10 ° C., 15% RH), it was −49 μC / g. The results are shown in Table 1.

  When a development test was performed in which a continuous copying of 1,000 sheets was carried out with a commercial copying machine having an OPC photosensitive drum at room temperature and normal humidity (25 ° C., 50% RH), the rise of charge was quick and there was no scattering of toner. A clear image with high density and no fogging on white background was obtained, and the image was good even after continuous copying of 1,000 sheets, and the durability was also good. Moreover, the same test was conducted under high temperature, high humidity, low temperature, and low humidity, and the result was equally good as the result under normal temperature and normal humidity. The results are shown in Table 2, respectively.

Example 2
In Example 1, 100 parts of polyester HP313 was used as the binder resin, and C.I. I. This was carried out except that 5 parts of Pigment Red 57: 1 and 1 part of “Compound 2” (single blow-off charge amount—56 μC / g, polyester resin mixture blow-off charge amount—57 μC / g) were used as the negative charge control agent. A two-component developer was obtained in the same manner as in Example 1.

  Tables 1 and 2 show the results of the developer blow-off charge amount and the rise of charge, and the results of the development test, measured in the same manner as in Example 1.

Example 3
In Example 1, 100 parts of polyester HP313 was used as the binder resin, and C.I. I. Except for using 5 parts of Pigment Blue 15: 3 and 1 part of “Compound 3” (single blow-off charge amount—53 μC / g, polyester resin mixture blow-off charge amount—55 μC / g) as a negative charge control agent A two-component developer was obtained in the same manner as in Example 1.

  Tables 1 and 2 show the results of the developer blow-off charge amount and the rise of charge, and the results of the development test, measured in the same manner as in Example 1.

Example 4
In Example 1, 100 parts of an epoxy resin (Asahi Epoxy Resin 330R, manufactured by Asahi Kasei Kogyo Co., Ltd.) as a binder resin, 5 parts of PB15: 3 as a colorant, and “Compound 4” (single blow-off charge as a negative charge control agent) A two-component developer was obtained in the same manner as in Example 1 except that 1 part of the amount -57 μC / g, polyester resin mixture blow-off charge amount-58 μC / g) was used.

  Tables 1 and 2 show the results of the developer blow-off charge amount and the rise of charge, and the results of the development test, measured in the same manner as in Example 1.

Example 5
In Example 1, styrene-acrylic resin (Hymer SB101 (registered trademark), manufactured by Sanyo Chemical Industries) as a binder resin, and C.I. I. Except for using 5 parts of Pigment Red 57: 1 and 1 part of “Compound 5” (single blow-off charge amount—49 μC / g, polyester resin mixture blow-off charge amount—52 μC / g) as a negative charge control agent. A two-component developer was obtained in the same manner as in Example 1.

  Tables 1 and 2 show the results of the developer blow-off charge amount and the rise of charge, and the results of the development test, measured in the same manner as in Example 1.

Example 6
In Example 1, 100 parts of Heimer SB101 as a binder resin, 5 parts of PY12 as a colorant, “Compound 6” as a negative charge control agent (single blowoff charge amount—48 μC / g, polyester resin mixture blowoff charge amount) A two-component developer was obtained in the same manner as in Example 1 except that 1 part of −50 μC / g) was used.

  Tables 1 and 2 show the results of the developer blow-off charge amount and the rise of charge, and the results of the development test, measured in the same manner as in Example 1.

Example 7
In Example 1, 100 parts of polyester HP313 was used as the binder resin, and C.I. I. Example 1 except that 5 parts of Pigment Yellow 12 and 1 part of “Compound 7” (single blowoff charge amount—56 μC / g, polyester resin mixture blowoff charge amount—58 μC / g) were used as the negatively chargeable charge control agent In the same manner as above, a two-component developer was obtained.

  Tables 1 and 2 show the results of the developer blow-off charge amount and the rise of charge, and the results of the development test, measured in the same manner as in Example 1.

Comparative Example 1
In Example 1, except that 1 part of “Compound 8” (shown in the following formula. Single blow-off charge amount—51 μC / g, polyester resin mixture blow-off charge amount—56 μC / g) was used as the negative charge control agent. In the same manner as in Example 1, a two-component developer was obtained.

  Tables 1 and 2 show the results of the developer blow-off charge amount and the rise of charge, and the results of the development test, measured in the same manner as in Example 1. Although there are no practical problems from the results of the charge rise and the development test results, the results were inferior in characteristics as compared with Examples 1-7.

Comparative Example 2
In Example 2, except that 1 part of “Compound 9” (shown in the following formula. Single blow-off charge amount—47 μC / g, polyester resin mixture blow-off charge amount—53 μC / g) was used as the negative charge control agent. In the same manner as in Example 2, a two-component developer was obtained.

  Tables 1 and 2 show the results of the developer blow-off charge amount and the rise of charge, and the results of the development test, measured in the same manner as in Example 1. From the results of the charge rise and the development test results, the characteristics were inferior to those of Examples 1 to 7, and the characteristics under low temperature and low humidity and high temperature and high humidity were particularly poor.

Comparative Example 3
In Example 6, except that 1 part of “Compound 10” (shown in the following formula. Single blowoff charge amount—46 μC / g, polyester resin mixture blowoff charge amount—48 μC / g) was used as the negatively chargeable charge adjusting agent. In the same manner as in Example 6, a two-component developer was obtained.

  Tables 1 and 2 show the results of the developer blow-off charge amount and the rise of charge, and the results of the development test, measured in the same manner as in Example 1. From the results of the charge rise and the development test results, the results were inferior in properties as compared with Examples 1 to 7, and the properties were not only under low temperature and low humidity and high temperature and high humidity but also at normal temperature and humidity.

表１中、◎は良好、○は可、△は不良

In Table 1, ◎ is good, ○ is acceptable, and △ is bad.

表１中、○は良好、△は可、×は不良

In Table 1, ○ is good, △ is acceptable, and X is bad.

Claims (8)

The following general formula (A),

(In formula A, M represents boron or aluminum. R _{1 to} R ₄ may be the same or different, and at least one of them is a fluorine atom or a fluorinated alkyl group. X is Represents an alkali metal.)
A negatively chargeable charge control agent comprising a compound represented by the formula: The following general formula (B),

(In formula B, M represents boron or aluminum. R _{5 to} R ₈ may be the same or different, and at least one of them is a fluorine atom or a fluorinated alkyl group. Represents an integer of ˜5, X represents an alkali metal.)
A negatively chargeable charge control agent comprising a compound represented by the formula: The following general formula (C),

(In formula C, M represents boron or aluminum. R _{9 to} R ₁₂ may be the same or different, and at least one of them is a fluorine atom or a fluorinated alkyl group. Represents an integer of ˜5, X represents an alkali metal.)
A negatively chargeable charge control agent comprising a compound represented by the formula: The following general formula (D),

(In formula D, M represents boron or aluminum. R _{13 to} R ₁₆ may be the same or different, and at least one of them is a fluorine atom or a fluorinated alkyl group. Represents an integer of ˜4, X represents an alkali metal.)
A negatively chargeable charge control agent comprising a compound represented by the formula: The following general formula (E),

(In the formula E, M represents boron or aluminum. R ₁₇ and R ₁₈ may be the same or different, and at least one of them is a fluorine atom or a fluorinated alkyl group. Represents an integer of ˜4, X represents an alkali metal.)
A negatively chargeable charge control agent comprising a compound represented by the formula: The following general formula (F),

(In formula F, M represents boron or aluminum. R _{19 to} R ₂₂ may be the same or different, and at least one of them is a fluorine atom or a fluorinated alkyl group. X is Represents an alkali metal.)
A negatively chargeable charge control agent comprising a compound represented by the formula: The following general formula (G),

(In formula G, M represents boron or aluminum. R ₂₃ and R ₂₄ may be the same or different, and at least one of them is a fluorine atom or a fluorinated alkyl group. Represents an integer of ˜4, X represents an alkali metal.)
A negatively chargeable charge control agent comprising a compound represented by the formula:   A toner comprising the negatively chargeable charge adjusting agent according to claim 1 and a binder resin.